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FACTORS INFLUENCING THE WASH-FASTNESS OF

WATERCOLOURS
a
Dr Vincent Daniels
a
Department of Conservation , British Museum , London, WC1B 3DG, U.K.
Published online: 17 Sep 2010.

To cite this article: Dr Vincent Daniels (1995) FACTORS INFLUENCING THE WASH-FASTNESS OF WATERCOLOURS, The
Paper Conservator, 19:1, 31-40, DOI: 10.1080/03094227.1995.9638411

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 FACTORS INFLUENCING THE WASH-FASTNESS OF WATERCOLOURS
Vincent Daniels
Introduction
Many conservation treatmentsfor printed paper involve
immersing the paper i n aqueous solutions; the stability
of the printed image hardly ever presents a problem.
However, watercolour paintings on paper are seldom
subjected t o immersion treatments, because there is a
danger that migration of pigments may occur. In
particular, when watercolours are washed (e.g. for
removal of disfiguring stains), techniques such as
float, blotter or suction-table washing are usually
employed. These limit the amount o f water available
for pigment transport. Movement of pigment can still
occur over small distances into the paper or across its
surface, however.
Interviews with several paper conservators have
revealed a general opinion that of the watercolour
paints, those containing lake pigments have a tendency
to be fugitive in water, and that old watercolour
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paintings tend t o be more wash-fast than recent
paintings. The Paper Conservation Catalog states that
vermilion and gamboge watercolours may be fugitive,
that paint on watercolours over sixty years old tends t o
be less fugitive, and that thickly applied paint may be
more fugitive than thin.'
The purpose of the present study is t o examine some
factors which make watercolour paints on paper more
or lesswash-fast in aqueouswashing. Links have been
sought primarily between the chemical nature o f the
pigment (and other paint constituents) and wash-
fastness, but physical properties of the paint layer and
paper substrate were also shown t o affect wash-
fastness.
Watercolours
When the first watercolour cakes were manufactured
theywerecomposed of gum and pigmentwith perhaps
a surfactant (often oxgall). They were hard and gritty
and on ageing became harder and brittle, sometimes
eventually crumbling. The mode of use was t o rub
them on an unglazed ceramic surface to abrade off
finely divided pigment. This was then worked up into
a paint with water.* By about 1820, moist cakes had
been developed which included a hygroscopic material
such as honey or sugar. This often enabled the artist
to take pigment directly off a block with a wet brush. In
the 1830s, the British paint manufacturers Winsor and
Newton replaced the customary honey and sugar with
glycerol. This innovation made their paints very
popular, as the working properties of the paints were
good. In 1841 the first paste watercolours became
commercially available i n tubes; these contained more
water and glycerol than the cake colours. To this day,
paste watercolours are more popular in the U.S.A than
in the U.K.
Often a thick mixture of watercolour paint and water is
taken from the cake or tube and applied to the paper.
Unless one ofthe constituents of the paint is absorbed
preferentially by the paper, the composition of the
applied paint when dry must be very similar to that of
the paint cake itself. The ageing properties of the paint
The Paper Conservator 19 (1995)
cakes should therefore be similar t o the ageing
properties of the painted surface. For example, a now
insoluble paint cake (which was originally soluble)
should have produced an image stable i n water. Note
that use of the word 'soluble' in this context is not
scientifically correct, as the wetted paint is a suspension
of particles and not molecularly dispersed; no other
word, however, so w el l describes the intended
meaning.
Lake Pigments
A large numberof pigmentsavailabletodayarederived
from organic dyes. Dyes are not used directly as
pigments because they are transparent, i.e. they have
poor hiding power (theabilitytocover upothercolours)
and behave in an uncontrollable manner, often dyeing
thesurface on whichthey areapplied in an unpredictable
way. Dyes are rendered easier to use i n paints by
combining them with a (usually) white pigment.
According t o Hurst the most usual of these in 1896
were barium sulphate, china clay, calcium sulphate,
diatomaceous earth, zinc oxide, lead sulphate, calcium
carbonate, aluminium phosphate, calcium phosphate
and, most common of all, aluminium hydrate produced
by alkaline precipitation from alum. The recipes for
lake pigments derived from natural dyes such as
madder are often extremely complex, with many stages
and apparently unnecessary ingredients. White
pigments may also be added to pigments of high
tinctorial strength to extend them and increase their
hiding power.
The solubility of gum arabic
The major factor i n the wash-fastness of a thick paint
layer is the solubility of the paint binder, e.g. gum
arabic in watercolours. Daniels and Shashoua reported
that accelerated heat ageing at 100 "C produced
progressive development of insolubility in gum arabic.
A mixture of pigment and gum developed insolubility
faster than the gum alone, suggesting that the gum-
pigment interaction played a significant r t ~ l e Moorjani
.~
and Narwani reportedthattheviscosityof gum solution
increased after heat ageing at 100-160 "C. After
ageing at 170 "C the gum swelled in water but did not
dissolve. The lack of solubility was attributed t o
irreversible loss of water and aggregation of polymer
chains. Anderson et al. found that, on ageing, some
samples of g u m arabic (Acacia senegal) formed
mucilaginous gels rather than the desired viscous
solutions; the cause of this phenomenon was not
determined.6 Anderson purified samples of fresh gum
arabic by dialysis against distilled water, then by
electrodialysis. Some of these solutions were
concentrated and freeze-dried; when stored for 3-6
months the freeze-dried samples gradually became
insoluble. If the concentration exceeded 5% in a fresh
gum solution, an insoluble mucilage formed over
several days. In subsequent work using molecular
sieve chromatography, Anderson found that after
purification, several Acacia gums appeared to become
insoluble in water on storage. This was attributed t o
molecular aggregation i n the gum.'
31
 FACTORS INFLUENCING THE WASH-FASTNESS OF WATERCOLOURS
Gum arabic can also become insoluble when mixed
with various chemical species. The best known of
these reactions, in museums at least, is the now
antiquated gum bichromate process for producing
photographic images. In this process potassium
bichromate (= dichromate, K,Cr,O,) is mixed with
pigment, water and gum arabic, and then coated onto
paper. When exposed to light, e.g. through a negative,
a latent image is formed i n parts of the gum rendered
insoluble by the light; the image is developed by
washing the photographs. The precise mechanism for
this process has not been elucidated fully, but cross-
linking of the gum by chromium ions is considered to
play a major r61e.
A variety of other chemical reagents give precipitates
or heavy jellies with g u m arabic: borax, ferric chloride,
basic lead acetate, potassium and sodium silicate, and
gelatine.g In general, trivalent metal salts cause
precipitation of gum arabic.1°
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The cross-linking of hydrocolloid polysaccharide gels,
such as gum arabic (gelation), has received some
attention in recent years as cross-linked gums are used
in petroleum drilling for hydraulic fracturing. For this
application gum arabic is relatively expensive compared
with other gums, such as guar, and therefore has
received little specific attention. However, research
has generally addressed gums as a whole. Conway
reports that many water-soluble polymers can be
cross-linked with a variety of agents, optimal cross-
linking occurring at a certain pH, concentration, and
metal-oxidation state.” Twenty-two metallic elements
are listed as proposed cross-linking agents for
polysaccharide gums. The strength of the bond
between metal ion and hydroxyl (OH) group is increased
considerably if there are t w o adjacent OH groups
oriented so that an additional bond can be made to the
same polymer molecule, i.e. a cis diol t o chelate with
the metal. Gum arabic has cis diol groups from one
of its constituent sugars, L-rhamnose. Menjivar
mentions that borax, and the salts of chromium,
antimony, aluminium, titanium and zirconium are
commercially successful cross-linking agents for guar
gum and its derivatives.’,
Although a suspension of pigment i n gum may at first
sight seem t o be lacking i n ions, one must consider the
surfaces of individual particles of pigment. For greatest
covering power the optimum size for a pigment
particle is 0.2-0.4 p, which means that particles would
be only several hundred molecular units in diameter.
Unsatisfied valencies will cover the surface of the
particle and are potentially available for reaction.
The surface area of a finely divided material is large.
A I - c m cube has a 30 m 2area when divided into cubes
of 0.2 p edge. Thus, surfaces of pigments can be
significantly chemically reactive. Furthermore, traces
of soluble compounds may remain on pigment
particles after the pigment manufacturing process.
32
The paint and its interactions with fibres
When a thick paint layer o n paper is immersed in
water, the properties of the layer will be dictated by the
properties of the paint itself. However, i n thin layers
of paint, the pigment-to-fibre interaction is of primary
importance. For the surface chemist, the position is
very complex as the presence of sizing agent, gum,
and surfactant further complicates a situation already
very difficult t o interpret theoretically. However, the
principal phenomena are generally understood.
Cellulose is a reactive fibre, w i t h a very high
concentration of surface hydroxyl groups available for
hydrogen bonding to other cellulose fibres or pigments.
Paper is often extensively fibrillated, and this enhances
the possibilities for hydrogen bonding by increasing
the surface area of the fibre. When paper is sized with
gelatine, many of the hydrogen bonding sites and
some of the physical surface irregularities are covered.
When particles i n a liquid medium (e.g. watercolour
paint) are deposited on paperfibres, they are absorbed
by the paper into remote crevices and between fibres.
As water evaporates, the fibre and particle are drawn
closer together; a collapsing force of as much as 1.38
MN/m2(200p.s.i) is exerted by a column of evaporating
water 0.02 p i n diameter. There are 3 mechanisms for
the retention of particles on cellulosic fibres in textiles:
1. Macro-occlusion, or entrapment of particles in the
intra-fibre or inter-fibre spaces.
2. Micro-occlusion, or entrapment of particles i n the
irregularities of the fibre surface.
3. Sorption of materials by van der Waals’ or
electrostatic forces at the surface or within pores and
crevices.
Most pigments have a broad range of pigment sizes
and synthetic organic pigments and carbon black
particles are sometimes as small as 0.01 p i n diameter.
The ease with which particles stick to fibres increases
as the size of particle decreases. Jones reports that
particles below about 0.2 p are ‘virtually impossible t o
remove from cotton cellulose except by drastic
mechanical action, and washing is difficult even with
particles as large as 5p’.l3
Almost all watercolour paints contain a surfactant
which helps to disperse the pigment i n the gum and
subsequently over the paper. Pigment particles
naturally tend t o aggregate and need mechanical
action to break them up. A detergent can coat each
pigment particle with molecules which change its
electrical charge. This makes the individual particles
mutually repulsive, breaking up aggregates and giving
them affinity for water. Both surfactant and gum
arabic act as agents which suspend pigment particles
and therefore aid in making a good paint, but as both
are present i n the dried paint layer they should also
enhance the removal of the pigment from the fibre
during washing.

Light-fugitive paints chiefly owe theirfading properties
to the pigments they contain. This is also the case for
alkaline-fugitive painbas, in bothcases, it isthechemical
characteristics of the pigments which dictate the
properties of the paint. However, wash-fastness is not
so simple. Many factors influence the properties of the
paint: the properties of the pigment itself, the presence
of other ingredients in the paint, and the shape and size
distribution of the pigment particles. Of course, the
pigment particles have to be washed off something,
and the pigment particles stick differently to different
substrates.
Lifting
One technique used by watercolour artists is t o use a
wet brush t o redistribute watercolour paint after it has
dried on the paper. In a pamphlet by Winsor and
Newton it isstatedthat 'certain pigmentstendt0"stain"
the paper more than others. This attribute will make it
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less or more difficult to pick up the colour once it has
dried'.14 The pamphlet ranks the comparative staining
power of pigments (after three or four minutes' drying)
as L, M and H. Colours marked 'L' are those for which
Little difficulty in lifting would be encountered; 'M'
- matrix effects are reduced. Consequently the low
signifies Moderate difficulty, and 'H' colours are Hard
to lift off.
'L' paints listed are cerulean blue, cobalt blue and
cobalt violet. 'M' paints are Antwerp blue, cadmium
orange, cadmium red deep, chrome yellow, orange
and yellow deep, Indian red and yellow, olive green,
raw sienna, Vandyke brown and Winsor green. The
range of paints tested was that marketed in the United
States and is similar to that in the UK today.
Some correlation between the colours easy t o lift and
those which are water-fugitive is t o be expected.
Materials and Procedure
Paint cakes
An important resource for the present research was a
set of over 200 Winsor and Newton watercolour cakes
dating from the period 1850-1950, kindly donated by
the manufacturers to the British Museum some fifteen
years ago. A feature of Winsor and Newton's range of
paints is the declaration of the principal pigments they
contain. However, no information is given on the
binders, surfactants or other ingredients and, more
importantly, no information on the bases for lakecolours
from this group. There are Winsor and Newton
publications on the composition of artists' pigments
for the 1920s and the current range. l5The 1850-1950
watercolour cakes were sampled about ten years ago
by Dr Rosamund Harley, who ground off one edge to
prepare washes. Each cake therefore had one edge
guaranteed not t o be covered by a protective varnish.
A ten-year-old box of cakes by Winsor and Newton
containing sixty cakes was also used.
33
Vincent Daniels
Papers
Three papers were used: Whatman No. 1 filter paper
(an unsized, pure cellulose paper) and tw o watercolour
papers - a modern Arches paper and a Whatman paper
dating from the nineteenth century. The watercolour
papers were gelatine-sized. The Arches paper contained
no detectable aluminium (alum), but the Whatman
paper did.
Analysis of the paint cakes and papers
Samples of all the paint cakes were analysed by X-ray
fluorescence spectroscopy (XRF). The apparatus had
anairpathandwhenoperatedtooptimisethedetection
of elements with a l ow atomic number (0.6 mA, 20 kV)
could detect aluminium (atomic number (Z) = 13) if
present in appreciable quantity. The limitations of the
technique are considered in greater detail in the
Discussion (see pp. 38-39, below). Some samples were
analysed using energy dispersive X-ray analysis (EDXA)
i n the vacuum chamber of a scanning electron
microscope. In this process the fluorescent X-rays are
generated by electrons instead of higher-energy X-
rays and, as the depth of penetration is much smaller,
atomic number elements sodi um ( Z = 11) and
magnesium (Z = 12) are more readily detected. The
sensitivity isfurther enhanced by operating in a vacuum,
where the absorption of low-energy X-rays by air is
eliminated. Quantitative results can be obtained with
this method. For EDXA, samples were embedded in
epoxy resin and polished so that a flat face of paint was
available for analysis.
TheXRFanalysiswas not quantitative, soall detectable
elements were listed. It was noted when an element
was present in such a high concentration that it was
obviously the major component, or when a very small
concentration was present. In Tables 1 and 4 the
elements are listed in order of diminishing height ofthe
principal peak on the XRF trace.
The gelatine contents of the papers were determined
by heating the paper in water at 60 "Cfor one hour and
then determining the gelatine content of the water
using biuret reagent.16 The densities of the samples
were measured with the aid of a balance, ruler and
micrometer.
Preparation and washing of painted papers
As a paint layer increases i n thickness, the maximum
depth of colour (saturation) is eventually reached and
addition of further paint causes no detectable change.
The aim, therefore, was t o produce a painted band of
colour on paper which, although well coloured, was
not saturated, so that loss of some pigment would
cause a change in appearance.
Each ofthepaintsfromthe modern boxofwatercolours
was used to create a band of colour on each of the
experimental papers. Although some paints were
 FACTORS INFLUENCING THE WASH-FASTNESS OF WATERCOLOURS

becoming insoluble and difficultto use by stroking with

a wet brush, enough paint was obtainable from these Table 1. Elemental compositions of modern
after leaving them t o soften while wet and repeatedly paint cakes
stroking them with a brush. The resulting painted
papers were stored for at least 24 hours before use; Pigment name Elements detectable by XRF
none was stored for more than a week. Storage of
painted paper for longer than twenty-four hours Alizarine carmine Q, Zn, Cu, Fe, P, K
produced no detectable differences. The painted bands Alizarine red Zn. Ca, Fe, K, P
were cut so that a portion could be held for reference, Antwerp blue Fe,Ca Prussian blue
and another portion washed. Washing of the painted Aureolin -
Co, K
paper was performed i n photographic developing Aurora yellow Cd, S
Azure cobalt Q, Zn, Cr, Ca, Fe
dishes using distilled water at 20 "C. The dishes were
Blue black Trace (Ca, K)
rocked gently after 30 minutes' and after 60 minutes' Bright red Ba,S, CI, K, Ca, Fe
soaking. At the end of the 60-minute washing process Burnt umber Fe, Mn, Ca, Zn
-
the paper was removed from the water and laid on a Cadmium orange a, S, Se, Ba
polythene sheet t o dry in ambient conditions. When Cadmium red Cs, S , Se, Ba
dry the washed colours were compared with the Cadmium red deep Cd, S, Se, Ba
reference strips t o see if there was a loss of pigment- Cadmium scarlet &i ,Se, Ba, Ca, K
S,
a subjective judgement. Cadmium yellow Cd, S,K, Zn
-
Cerulean blue Sn, Co, Cr. Zn,
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Charcoal grey K, Ca
It should be noted that although immersion in water
waschosen as a meansfor detecting the wash-fastness
Chinese white zn
Cobalt blue Ti, Co, Zn
of pigments it does not represent the most frequently Cobalt green & cl
u,
used method for washing watercolour works of art. Crimson lake K, Ba, P, Zn, Al, Ca, Fe, Se
Other methods of washing cause much less change. Cyanine blue Co, Al, P, Fe, K Prussian blue
Davy's grey Fe, Zn, Si, K
Solubility of the old paint cakes Hooker's green (dark) Traces (Cu, CI, Ba, Ca, S)
The solubility (and hence usability) of the paints was Hooker's green (light) Ba, K
Indigo Ba, Trace Cu
assessed by attempting to load a wet brush with paint. Indian red b,Ca, Zn, S
The procedure was t o wet a brush and stroke (forward Indian yellow Ca, S, Fe, Zn
-
and back) the face of the paint cake twenty times. The Ivory black Ca
paint brush was then stroked once (forward only) Lamp black No detectable elements
across the surface of a piece of watercolour paper. The Light red Fe, Ba
resulting paint stroke was visually assessed as Naples yellow zn
containing inadequate or sufficient paint for use by an New gamboge Ca, Ba, Zn
Olive green -
Fe, Alumina
artist-a subjective assessment. On account of the
Oxide of chrome Cr
extreme fragility o f many o f the cakes and the Payne's grey Fe, K Prussian blue, Ultramarine
impossibility of obtaining samples of similar size, it Permanent blue Fe, K Prussian blue, Ultramarine
was not thought desirable to determine solubility by Permanent magenta Ca
immersing detached samples in water. Permanent mauve -
Mn, P
Prussian blue Ee, K, Ca, Zn (Prussian blue)
-
Purple lake Ca, S, Ba, Fe, Zn
Results Raw sienna Fe , Ca
-
Raw umber Fe,Mn, Ba, Cu
Sap green Zn, Ba, K
Analysis of modern paint cakes Scarlet lake CI, K, Ca, Fe
Elemental composition wasdetermined by XRF. Some Sepia Fe, Traces (K, Zn, Ca, As)
-
additional compositional data has been obtained from Terre vert Fe, Cr, K, Si, Zn
the Winsor and Newton publications; in the tables this Ultramarine ash blue Ca, Ba, Fe, K, Si
is denoted by the use of italics. Underlining indicates Vandyke brown Traces (Fe, Zn, Cu)
that the element is unmistakably present in large Viridian Cr, K
-

amounts. The prefix 'Trace' indicates that only a very Yellow ochre k,K, Cu
Venetian red Fe, Traces (Ca, K )
small amount of that element was considered t o be
Vermilion red HJ As, S
present. The results in Table 1 can be compared with Violet carmine Ba, Ca, S
the results in Table 3, which show the water-fugitive Warm sepia -
Fe, Traces (Ca, K, Zn)
paints. Winsor blue Ba, Ca, Cu
Winsor emerald a,Ba
Winsor green Ba, Br, Cu, S, CI, Cu
Winsor red Traces (CI, Zn, Ca)
Winsor violet Ba, Cu, S, K, Fe
Winsor yellow Ba

34
 Vincent Daniels

Gelatine content and density of papers The wash-fastness of modern watercolour paints
The results for protein content (w/w) and density are Visually uniform coatings of each of the modern paints
displayed i n Table 2. examined were made on each of the three papers.
Most of the coatings did not lose paint as a result of
Table 2. Protein content and density of the three immersion. Table 3 lists the paints that did lose some
papers used pigment on at least one of the papers. The other paints
listed in full i n Table 1 were not visibly fugitive. The
Paper type % protein density glcm'
p i g m e n t c o m p o s i t i o n s g i v e n i n Table 3 are a
combination ofXRF resultsandthe Winsorand Newton
Whatman No. 1 0.0 0.425 declared composition. It can be seen that in every case
Arches 8.8 0.557 there was least paint lost from the filter paper samples
I Whatman watercolour 12.9 0.872 I and most from the old Whatman watercolour paper.

able 3. Relative wash-fastness of fugitive pigments on three different papers

igment name Pigment composition Whatman No. 1 Arches Whatman

watercolour

lizarine carmine Alizarine lake on base * **

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containing calcium and zinc.

Some Cu, Fe, P and K present.

ntwerp blue Prussian blue and alumina, some Ca. *

zure cobalt Cobalt aluminate or phosphate ** **

containing some alumina
also some Zn, Cr, Ca and Fe.

right red Organic dyes on a Ba-containing base; **

some S, CI, K, Ca and Fe detected.

admium orange Cadmium sulphide and selenide with Ba.

adrnium red Cadmium sulpho-selenides with Ba.

obalt blue Cobalt aluminate or phosphate

containing some alumina.

:obalt green Complex mixtures of cobalt and zinc *

oxides with Cu.

:yanine blue Prussian blue and cobalt blue. **

looker's green Organic dyes with Ba. **

looker's green dark Organic dyes with Ba. **

ndigo Alizarine crimson, lamp black and Winsor blue, *

some Ba.

Japles yellow Cadmium sulphide, ferric oxide and zinc oxide ** *

Yew gamboge Organic dyes with Ca, Ba and Zn. *

'errnanent magenta Organic dyes on a calcium containing base. **

'urple lake Alizarine lakes on base with Ca, Ba, Fe and Zn. **

Sap green Organic dyes with Zn and Ba. * **

Scarlet lake Organic dyes on a base with some Ca, Fe and CI. *

Winsor emerald Organic dyes, zinc oxide and some Ba present ** **

Winsor violet Lake on barium base; some Cu, S, K and Fe present ** **

Key - no visible loss * some loss of pigment ** most of pigment lost

35
 FACTORS INFLUENCING THE WASH-FASTNESS OF WATERCOLOURS

Effect of paper on wash-fastness these20paints, 18containawhiteextenderasindicated

The wash-fastness of watercolour paints on paper
evidently depends partly on the nature of the paper.
The three papers used in the experimental work
demonstrated that th e wash-fastness o f paints
decreased as both the amount of sizing on the paper
increased and the density of the paper increased. The
relatively extensive penetration of the particles into
the paper may account for the good wash-fastness of
paint on filter (unsized) paper; on the sized papers the
pigments stayed more on the surface, making them
easierto wash off. Gelatine sizing also blocks some of
the hydrogen bonding sites on the cellulose and
decreases the surface roughness of the fibres, making
adhesion of pigments more difficult. Mostwatercolour
artists are aware of the extent to which wet paint is
absorbed into paper, and h o w easy it is to lift colour
from a dried wash on a sized paper and redeposit i n a
different place. The observations recorded in Table 3
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by the presence of Ba or Zn. In these paints the Ba is
present as barium sulphate, and Zn as zinc oxide. Of
the 18 paints that did not contain either detectable or
Winsor and Newton-declared Ba or Zn, all but two
were wash-fast. It thus appears that the presence of
Ba or Zn may decrease wash-fastness of paints. Of the
60 newer paints (Table I ) , 33 contained Ba or Zn
(55.5%)and of the older paints (Table 4), 14 out of 106
(13.2%). Thisdifferencecould be afactorin explaining
why recent paintings are less wash-fast than new
ones.
Analysis of old paint cakes and their usability
Often there was more than one sample of a paint of a
particular name, representing different production
batches. All paintsweretestedfor usability (solubility),
and the numbers presented in Table 4 show how
many cakesofthat name fell intothetwocategoriesof

should reflect their experiences.
Effect of extenders on water-fugitive paints
Of the 60 modern paints tested, 20 were fugitive on at
least one of the papers. It is interesting to note that of
usability. When there were several cakes of the same
name, i n only tw o cases (violet carmine and Mars
yellow) were significant differences seen in the XRF
analysis. Hence usually only one analysis is presented
for each paint name.

Table 4. Usability of old paint cakes

Na m e of Paint Paint cake yielding Paint cake yielding Elements detectable
a satisfactory amount of colour inadequate colour by XRF
Alizarine carmine 1 Al, Ca, K, Fe
Alizarine crimson L Al, K, Ca, P
Alizarine green 1 1 K, Ba, S
Alizarine orange 1 Ba
Alizarine scarlet 1 Al, K, Ca, Fe
Alizarine scarlet K, Q, P, Cu, As
Alizarine yellow Al, P, K
Alizarine yellow Al, Ca, P, K
Antwerp blue Fe, Ca, P, S Prussian blue
Aureolin 1 Co, K
Aurora yellow 1 Cd, S
Bistre Ca, Fe
Black lead Fe, K, Ca
Blue black 2 K, Trace (Ca, Fe)
British ink 2 K, Ca, Fe
Bronze 2 zn,Fe,cr
Brown madder 1 &, K, Ca
Brown ochre 2 Eg, Zn, Ca
Brown pink 1 K, Ca, Fe, Cu
Burnt carmine 1 Ca, Mg, Fe, Cu
Burnt carmine 1 K, Ca, Fe
Burnt sienna 1 -
Fe
Burnt umber 2 Fe, M n
Cadmium middle 2 Cd, S
Cadmium orange 1 Cd, S
Cadmium orange (deep) Cd, S
Cadmium yellow 1 Cd, S
Cadmium yellow (deep) 1 Cd, S
Carmine 1 K, Ca
Cerulean blue 2 Co, Sn, K
Charcoal grey K, Ca, Al
Chinese white 2 zn
Chrome yellow Pb, Cr, S
Cobalt blue Co, Al
Cobali green 1 -
co
Cologne earth Ca, S, Fe
Constant white 2 Ba, S
Crimson lake 2 -
Ca, K

36
 Vincent Daniels

I e e p chrome 2 Pb, Cr, S

h a g o n ' s blood 2 ca.Fe
imerald green 2 clr,As
%Id's orange vermilion 2 b, S, Trace A g
'lake white 2 -
Pb, S
'rench blue 2 1 K, S, Ca Ultramarine
3allstone 1 Ca, K, Z n
3amboge 2 No elements detected
3reen oxide of c h r o m i u m 1 1 Cr
-
-looker's green No. 1 2 Fe, Trace (K, Ca) frussian blue
-looker's green No. 2 1 k, Trace (K,Ca) Prussian blue
ndian purple 1 &, Fe,Ca
ndian red 2 Fe
ndian yellow No. 2 1 1 Ba, S
ndigo 2 2 Trace (K, Ca)
ntense blue 1 Trace (Cu, Fe, K, Ca)
talian pink 2 Trace (Ca)
vory black 2 -
Ca, K
(ing's yellow 2 Cd, Zn, S
-amp black 2 K, Ca, Fe
-eitche's blue 2 Co, Fe, Ca, Prussian blue
-emon chrome
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3 Pb, Cr, Ba
-emon yellow 2 Ba, Cr
-ight red 2 Fe
bladder carmine 2 K. S, Al
bladder lake 2 K, Al, S, Fe
-
Mars orange 2 Fe, Zn
-
Mars yellow 1 Fe, Trace (Ca, S)
-
Mars yellow 1 Fe,Car S. K
Naples yellow 1 1 a, Fe, Cd, K
Neutral orange 1 Fe,Cd, S
Yeutral tint 2 -
Ca, K, Fe,
New blue 2 Trace (Fe, Ba, Ca, K, S, Si)
Ultramarine
Olive green 2 Fe, Mn, Ca, K
Orange chrome 2 pb, Cr
Orange vermilion 2 Hg, S
Payne's grey 2 Ca
Permanent mauve 3 -
As
Permanent violet 2 -
Mn, P
Prussian blue 2 Fe,K, Ca frussian blue
Prussian green 2 Fe, K, Ca frussian blue
Purple lake 2 Zn, Ca, K
Purple madder 1 Cu, Ca
Purple madder 1 Cu, Ca, Al, K, S
Raw sienna 1 Fe, As, Ca
-
Raw umber 1 1 k, Mn, Ca
Roman sepia 2 Fe, As, Ca, K
Rose doree 2 K, Ca, P, S, Al
-
Rose madder 1 K, Ca, S, Al
-
Rubens' madder 2 K. Ca
Sap green 2 K, Ca, Al
Scarlet lake 2 b, Ca. S. P
Scarlet madder 2 K, Ca, S, Al
Scarlet vermilion 1 1 Hg, S
Sepia 3 Fe, Ca
Smalt 2 K, Co, P
Spectrum red 2 &,S, K, Ca
Steel 2 Ca, Fe, K, A l
Terre vert 1 1 Fe, K, Si
Ultramarine ash 1 1 Ultramarine, Ca
Vandyke brown 2 Fe, Ca, S
Venetian red 2 Fe
Vermilion 1 1 Hg. S
Violet carmine 1 K, Ca
Violet carmine 1 K, Ca, Al
Viridian 3 Cr, K, Ca
-
Warm sepia 2 k,As, Ca
Yellow lake 1 1 Al, S, K, Ca
Yellow ochre 2 Fe, S, K, Ca, T i

37
 FACTORS INFLUENCING THE WASH-FASTNESS OF WATERCOLOURS

EDXA
Ten ofthe old paint cakes were additionally analysed
by EDXA. The results in Table 5 show the detectable
elements in calculated percentage concentrations
(i.e. not normalised to 100%).

1
I

Table 5. Concentration (YO)of elements in old lake pigments, determined by EDXA

Paint name Ca K Al S P CI Fe Si Mg
Alizarine crimson 1.0 1.8 3.4 0.4 4.0 0.1 0.1 -
Alizarine scarlet 1.6 1.9 2.6 - 3.2 0.1 -
Alizarine yellow 0.8 0.5 4.1 - 6.3 - 0.1
Burnt carmine 1.2 0.5 0.4 0.1 - - 0.1 -
Carmine 1.4 0.4 0.7 0.1 0.1 0.1 -
#Crimson lake 3.0 0.5 0.4 - - 0.1 - 0.1 -
Madder carmine 0.2 4.1 6.2 3.3 - 0.1 -
* Madder lake 0.3 3.2 4.4 2.5 - - 0.1 -
* Rose doree 0.3 3.7 4.7 1.4 2.9 -
* Rose madder 0.5 1.9 6.1 3.3 - 0.2 - 0.1 -

I
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Key * Totally insoluble paint f Very soluble paint - No detectable material

Discussion

Analytical results
X-ray fluorescence was a generally useful, non-
destructive method for determining the elements
present in the paints. It was much faster and more
convenient than EDXA i n the SEM. However, the XRF
analysis was not quantitative except in the crudest
sense. Sensitivity of detection drops with decreasing
atomic number (Z) and is also dependent on which of
the atomic series (K, L, or M ) the fluorescent X-rays are
generated from. Detection of elements with Z less than
20 ( = calcium) cannot be relied upon, even if the
element is present in quantity, because the fluorescent
radiation has low energy and can be fully absorbed by
a surrounding pigment of higher Z, e.g. Pb or Zn.
However, some relative concentration data have been
presented.
About a third of each watercolour cake is gum arabic,
and elements contained i n the gum itself may appear
each time a paint cake is analysed. Gum arabic is a
mixture of calcium, potassium and magnesium salts of
arabic acid (Z = 20, 19, and 12 respectively). XRF
analysis was performed on three types of gum arabic:
an old sample from Winsor and Newton, and newly
acquired gum from Cordofan (Sudan) and Nigeria.
Each contained a detectable quantity of calcium and
potasssium, in different ratios. Magnesium is of too
low an atomic number to be detected by XRF.
In XRF examinations of paint cakes the adjacent weak
K/Ca peaks from gum arabic were usually seen, unless
there were large quantities of heavier elements present.
The presence of Ca and K indicated i n Tables 1 and 4,
could have been produced by the pigment or the gum.
However, if these elements are present in large
concentrations, as indicated by underlining, then the
elements must be present in the pigment, e.g. crimson
lake (Table 4).
As a general rule, dyes have a highertinctorial strength
than pigments; thus they are not always present in
high concentrations. For example, the copper in copper
phthalocyanine was not detected in any of the cases
where it was stated t o be present. As it is a dye of great
strength it is present in low concentrations, typically
5% of the total pigment solids. The copper is only a
small part of the large, mainly organic, molecule (one
atom in 56, of the order of 0.5% by weight of the paint).
Copperwastherefore not detected in modern Hooker's
green, which hascopper phthalocyanine as its principal
colouring agent.
XRFcannot distinguish between thetypes of compound
in which elements may be found, thus iron i n Prussian
blue cannot bedistinguishedfrom that i n iron oxide. In
some cases, therefore, a particular class of pigment,
such as Prussian blue or ultramarine, is singled out in
the Table for interest. When these pigments appear in
the composition column the information (in italics)
comes from the manufacturer's data. Prussian blue
contains the XRF-detectable elements K and Fe, while
ultramarine contains Al. S and Si.
Solubility of old paints
Of the older cakes, 97 cakes out of 194 were soluble
(50%). Manganese phosphate-containing permanent
violet (in the newer cakes called permanent mauve)
was insoluble. Oftwelve paints containing chromium,
eightwere insolub1e;ofthefourthat remained soluble,
chromium was not the main ingredient. The hydroxy-
anthraquinone lakes (madder, carmine, etc.) were the
main ingredients in 34 cakes, of which 15 were
insoluble (44%). Some of these cakes contained
XRF-detectable aluminium. Of the 17 cakes that
contai ned XRF-detectable al umi ni um, 12 were
i nso Iu bIe (71% ) .

38

Ten lake paints were additionally analysed by EDXA.
The results support those obtained by XRF. Three of
thecakes were in the 'insoluble'category: madder lake,
rose madder and rose doree. The results also suggested
that the aluminium concentration could be important
as those three paints had the highest Al concentration
of the paints examined. However, alizarine yellow had
anAlconcentrationaImostas high andyetwassoluble;
the associated highest calcium concentration might
have mitigated the effect of the Al. Of all the soluble
paints, the crimson lake-with highest Ca and low Al
content-was the most soluble.
Vandyke brown isan organicearth which can becalcined
to form the pigment known as Cologne earth; XRF
detected onlytracesof iron, sulphurandcalcium. All of
thefivesampleswere insoluble. Sepia in old cakes was
made from the ink sac of the cuttlefish. Roman sepia
hasa littlesiennaadded,whilewarm sepia hasadditions
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of madder lake and sienna. The three sepias, tw o
Roman sepias and t w o warm sepias were all insoluble.
Prussian blue was used either alone or in mixtures, e.g.
in Hooker's green. Eleven cakes containing Prussian
blue all gave little or no colour when brushed with a wet
brush. Seven out of the ten cobalt-containing blue
paints were insoluble.
As predicted by the gelation hypothesis, there appears
to be a link between the presence of certain elements
and the development of insolubility in paint cakes.
Aluminium, chromium, cobalt, iron and manganese
are polyvalent metals known to effect cross-linking
betwen gums and the insolubility data for the paint
blockssupportthis hypothesis. However, it seems that
the presence of diluent pigments (extenders) attenuates
the crosslinking. For example, Mars yellow, an iron
oxide, was present in t w o formulations. The cake with
low calcium Concentration was insoluble, while that
with high calcium concentration retained its solubility.
Conclusion
This research has pointed to some reasons why old
watercoloursshould be more wash-fastthan new ones.
Gum arabic, normallywater-soluble, iscapableofcross-
linking with certain metals in pigments. The survey of
old paint cakes has shown that many do become
insoluble (and therefore unusable). The development
of insolubility apears to be linked to the presence in the
paintsof multivalent metalssuch as manganese,cobalt,
chromium and aluminium. Development of insolubility
in a paint implies that the paint will be wash-fast.
However, the fact that a paint is capable of being
worked into a suspension with a brush does not imply
that the paint will be fugitive in immersion washing, as
the latter generally involves less mechanical agitation.
A survey of the wash-fastness of modern paint cakes
showed an apparent link between the presence of zinc
oxide and barium sulphate in the paints and loss of
pigment on washing. Finally, the wash-fastness of a
paintedarea dependsgreatlyonthe natureofthe paper
surface.
39
Vincent Daniels
References
C.I. Maynor, "Media Problems," Paper Conservation
Catalog, 9th ed. (Washington, D.C.: American Institute for
Conservation, 1993) Part 3.
M.B. Cohn, WashandGouache(Cambridge,Mass.: Center
for Conservation andTechnical Studies, Fogg Art Museum,
1977).
G.H. Hurst, Painters' Colours, Oilsand Varnishes(London:
Griffin, 1896).
V.D. Danie1sandY.R. Shashoua,"TheEffectofGumArabic
Solubilityon the Washing of Watercolours," lCOM Triennial
Meeting, Washington,D.C. 7993, II (Paris:ICOM Committee
for Conservator Paris, 1993) 442-46.
M.N. Moorjani and C.S. Narwani, "Influence of Heat on the
Chemical Composition and Physical Properties of Gum
Arabic", Journal of the lndian Chemical Society 25, no. 11
(1948): 503-508.
M.W.Anderson and R.N. Smith, "Studieson Acid Materials
Part XIX, The Composition of the Gum from Acacia laeta
var. hashab," Carbohydrate Research 4 (1967): 55-62.
D.M.W. Anderson, I.C.M. Dea and A.C. Munro, "Molecular
Sieve Chromatography with 'Sepharose 48': the Detection
of Artefacts of High Molecular Weight i n Acidic
Polysaccharides," Carbohydrate Research 9 (1969): 363-
65.
L. Nadeau, Gum Dichromate(New Brunswick: Atelier Luis
Nadeau, 1987).
C.L. Mantell, "Technology of Gum Arabic," in NaturalPlant
Hydrocolloids, vol. 11 (Washington: American Chemical
Societv.1954).
10 R. L. Whistler, lndustrial Gums (New York: Academic
Press,1933) 231.
11 M.W. Conway, "Chemical Model for the Rheological
Behaviour of Crosslinked Fluid Systems," Journal of
Petroleum Technology (Feb. 1983): 315-20.
12 J.A. Menjivar, "Use of Gelation Theory to Characterize
Metal Cross-linked Polymer Gels," in J.E. Glass, Water
Soluble Polymers: Beauty with Performance, Advances in
chemistryseries No. 213 (Washington:American Chemical
Society,l986) 209-20.
13 T. G. Jones, "Dirt Removal," in K. Durham, Surface Activity
and Detergency (London: Macmillan,l961) Chap. 4.
14 Artists' Water Coloiirs, Technical Information Sheet No. 6
and 6a (New Jersey: Winsor and Newton,l990).
15 Composition of Pigments (London: Winsor and Newton,
[c.19201). Notes on the Composition & Permanence of
Artists' Colours (London: Winsor and Newton, [c.19861).
16 V. Daniels, and Y. Shashoua, "Evaluation of Reagents for
the Determination of Protein in Solution," in N.H. Tennent,
ed., Conservation Science in the UK(London: James and
James, 1993) 122-24.
Materials and Suppliers
Arches watercolour paper
Falkiner Fine Papers
76 Southampton Row
London WC1 B 4A
U.K.
Watercolour paints
Winsor and Newton
Wh itefria rs Avenue
Wealdstone
Harrow HA3 5RH
U.K.
 FACTORS INFLUENCING THE WASH-FASTNESS OF WATERCOLOURS

Acknowledgements
I would like to thank Yvonne Shashoua for carrying out the
EDXA. Iwould also like t o thank M r Alan Foster, chief chemist
at Winsor and Newton, for providing useful comments and
information and for revealing some confidential data which
are not reproduced here. M y thanks go to Susan Bradley and
Dr Andrew Oddy for advice on the text.

Summary
The wash-fastness of watercolour paintings on paper has
been found to depend on the constituents of the paints and on
the type of paper used. The wash-fastness of a range of
modern watercolour paints has been assessed, and there
appears to be a link between water-fugitive paints and the
presence of zinc oxide or barium sulphate used as extenders.
Over 200 old paint cakes were analysed and tested to see if the
binder(gumarabic)wasstillsoluble. Thereisanapparent link
between the presence of certain elements in the pigments and
the development of insolubility. lnsolubiiityofold paint cakes
implies that these paints will not be water-fugitive on paper.
Insolubility of the gum arabic binder is effected by cross-
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linking of the gum by metal ions, eg. chromium, aluminium

and cobalt.

Resume
La resistance8 I'eau descouleursaquarellessur papier depend
des constituants de la peinture et de la nature d u papier de
support. On a evalue la resistance a I'eau d'une serie
d'aquarelles moderneset il sembleyavoir un rapport entre les
couleursfugitives dans I'eau et la presence de charges, soit de
I'oxyde de zinc, soit du sulphate de baryum. Plus de 200
specimens de peintures en godets ont subi des tests pour voir
si le liant (la gomme arabique) etait toujours soluble. II existe
apparemment un rapport entre la presence de certains
elements dans les pigmentset le developpement d'insolubilite.
L'insolubilite desvieilles couleursen godets implique qu'elles
ne seront pas fugitives dans I'eau apres leur application sur le
papier de support. L'insolubilite du liant, la gomme arabique,
est le resultat de la formation de 'crosslinks' a cause des ions
metalliques, comme par exemple le chrome, I'aluminium ou
le cobalt.

Zusammenfassung
Die Wasserloslichkeit von Aquarellen hangt, so das Ergebnis
dieser Studie, von den Bestandteilen des Farben und des
aquarellierten Papieres ab. Die Wasserloslichkeit einer Reihe
moderner Aquarellfarben wurde ausgewertet und es zeigte
sich, da13 ein Zusammenhang zwischen Wasserloslichkeit
und dem, Vorhandensein von Zinkoxid oder Bariumsulfat
bestcht. Uber200 alte Farbnapfchen wurden analysiert urn zu
ermitteln, ob das Gummiarabikum-Bindemittel noch loslich
war. Unloslichkeit alter Farbnapfe impliziert, da13 diese Farben
auf Papier ebenso unloslich sind.

Biography
Vincent Danielsstudied chemistry at University College, Cardiff,
where he obtained his first degree and Doctorate. He joined
the British Museum i n 1974 to work on paper conservation
science; since then he has worked on a wide range of
conservation problems.

Contact Address
Dr Vincent Daniels
Department of Conservation
British Museum
London, WC1 B 3DG
U.K.

40