Archacomefry 17,2 (1975). 177-190.

Printed in Great Britain

THE SCIENTIFIC A N A L Y S I S O F A G R O U P O F
R O M A N - A G E E N A M E L L E D BROOCHES
J. D. BATESON
Ulster Museum,Belfast, N. Ireland

and R. E. M . H E D G E S
Research Laboratory for Archaeology
and the History of Art, Oxford University, England

1. I N T R O D U C T I O N
We describe here the results of a scientific investigation of a representative selection of
Romano-British and Continental enamelled brooches. Previously published analytical
data on enamelled objects are limited to a few isolated examples (e.g. the Wall brooch-
see Werner and Organ 1964, pp. 46-47), with the exception of one group (i.e. the British
Museum collection of head stud brooches-see Painter and Sax 1970, pp. 153-174) and
are generally incomplete. We believe that the results from a more comprehensive study
contribute to knowledge of the techniques employed in enamelling, as well as providing data
for studies concerning the economics (e.g. geographical and historical variations, trade
patterns) of technically specialized materials.
Three separate aspects of enamelling may be studied; the chemical nature of the vitreous
material used; the composition of the metal substrate; and the mechanical relation between
these two phases. Thus as complete an analysis as possible using non- (or minimally-)
destructive techniques was made of the ‘glass’ with the aim of establishing its relationship
to contemporary ordinary glass and to pottery glazes, and of compiling the materials used
as colourants and opacifiers. That the metal substrate is an important influence on enamel-
ling capability is indicated in modem enamel-working textbooks (e.g. Wenger 1967, pp.
5-7, Bates 1951, pp. 169-171), although this aspect has been largely neglected in previous
studies of ancient enamels. Several deductions from the analysis of the metal and glass can
be made which relate to the mechanical bond at the interface. The general question of the
methods used in applying enamel to metal (e.g. the use of a frit or solid insert, mechanical
treatment of the metal to ‘key’ onto the enamel, cell sizes and enamel thickness, etc.) will
more appropriately be dealt with on another occasion, depending as it does primarily on
visual examination; but the particular case of millefiori enamels (where a frit would be
impossible) is considered in this paper.

2. SELECTION OF OBJECTS

The objects examined are listed in tables 1 and 2. They are all from the collections of the
Ashmolean Museum, Oxford, and may be identified by their registration numbers. Through-
out this text they are referred to by the code numbers also listed. The brooches of table 1
177
 178 J. D . Bateson and R. E. M . Hedges
are displayed in plates 1 and 2, and publications relating to their provenance are given in
the Appendix.
Those objects listed in table 1 constitute a representative selection of colours in con-
junction with dates; broadly early (first to second centuries A.D. (nos. 1-12)) and late
(third to fourth centuries A.D. (nos. 13-16)) as well as areas of manufacture; either British
Table 1 The objects

Ash. Mus. Probable Enamel

No reg. no. Description Provenance origin Date analysed

1 R75 disc brooch Woodeaton British ? I1 red

2 1927.386 peacock brooch ? Bath ? Cont. I1 red
3 1927.872 dragonesque brooch Brough British I1 yellow
4 1927.296 disc brooch Ixworth ? British ? I1 yellow
5 1836 Cat. S(ii) brooch Brough British I1 blue
p. 123, 62
6 1927.383 cock brooch England British I1 blue
7 1936.383 sandal brooch Ditchley British ?II blue
8 1927.302 disc brooch Brough ? British ? I1 green
9 1927.356 S(ii) brooch Cologne ? British I1 green
10 R76 lozenge brooch Woodeaton ? British ? I1 white
11 1927.250 disc brooch Derbyshire ? British ? I1 black
12 1927.350 sandal brooch Gt. Wallingfield British ? I1 orange
13 1927.274 oval plate brooch Brettenham British IV blue and
white
14 1927.273 oval plate brooch Appleton British IV blue and
white
15 1927.272 oval plate brooch Bury-St.-Edmunds British IV blue and
white
16 1950.85 oval plate brooch Campsfield British IV blue and
white
17 1889.693 disc brooch Tyre W.Cont. ? I1 red
18 1927.365 cock brooch S. France ? British I1 yellow
19 1927.594 belt plate Trier W. Cont. ? blue
20 1927.287 disc brooch Amiens W.Cont. ? blue and
green
21 1889.647 plate brooch Byblos W. Cont. ? white
22 1927.409 lozenge brooch Etaples Gaul ? I1 black
23 1927.313 lozenge brooch Etaples Gaul ? orange
24 1927.615 terret Suffolk British I red and
blue
25 1927.265 disc brooch Icklingham British ? white

(nos. 1-16) or Continental (nos. 17-23). The continental examples were included for the
sake of comparison and especially to identify criteria which might distinguish different
origins. The brooches represent the wide range of those produced in the Roman period,
and only nos. (13)-(16) form a group of the same type (Hunter and Kirk 1952, p. 60). A
major consideration in the choice of an object was the condition of the enamel to be ex-
amined; decayed or weathered enamels were not included, and the subject of deterioration
facing page 178
 The scientific analysis of a group of Roman-age enamelled brooches I79
Table 2 The objects with millefiori decoration

Ash. Mus. Probable

No reg. no. Description Provenance origin Date

a 1954.46 circular stud Asthall ? British ? 11+

b 1927.315 lozenge brooch Bardwell W. Cont. ?
C 1970.156 circular stud Shakenoak ? British ? 11+
d 1936.394 circular stud Ditchley ? British ?
e 1927.295 disc brooch Lancing Down
f 1927.596 belt plate Kent
g 1927.264 stud Brough
h 1927.271 stud France Gaul
i 1927.270 disc brooch France Gaul
i 1927.397 circular stud France Gaul

did not enter the scope of the project. (In any more extensive study this would have to be
considered, as some chemical compositions are likely to weather much more strongly, and
so may not be represented in the analysis.)

3. M E T H O D OF E X A M I N A T I O N

The analysis of enamelled brooches present some unique problems; rarely can even a minute
sample be removed without disfigurementwhile the area of any enamelled cell is seldom more
than a few square millimetres. For a non-destructive analysis specialized X-ray fluorescence
equipment is required.
Analysis was therefore made with the Isoprobe (Hall et al. 1973), a non-dispersive X-ray
fluorescence spectrometer,for elements heavier than Si. The sample has an effective area of
4 mm2 with X-ray tube excitation, and 8-10 mm2 with excitation by the Amz4’ source
required for measurements on such elements as Ag, Sn, Sb. Several enamel cells were smaller
than this, and so were masked by a lead sheet with a suitable aperture. The depth sampled
depends on the element analysed, and particularly on the lead content of the enamel, but
is generally less than 100 pm. We believe that such surface analyses are reasonably repre-
sentative of the bulk composition for apparently well-preserved vitreous materials; the
main change by weathering is a leaching of alkalis. The measurements for Ca and Fe
were repeated on samples extracted from the enamel (see below), and their agreement
demonstrates no great change in composition with depth. The Isoprobe was also used for
the analysis of the metal substrate; the metal was ground to a fresh surface and duplicate
measurements made.
In a number of cases it was possible to remove a small (about 2 mg) sample from the
enamel in order to analyse it by emission spectroscopy for the important lighter elements
NayMg, and Al. X-ray diffraction (X.R.D.) of powdered samples was also made for some
of the yellow enamels to identify the colourants/opacifiers.
Absolute concentrations were calculated from the fluorescent intensities by means of
calibration graphs prepared from standard glasses and alloys. Since the enamels have a
rather unusual composition (especially for the Pb and Sn content) it is necessary to apply
considerable corrections of the matrix absorption to the standard calibrations with a con-
D
 Table 3 Results of analyses
c1
00
Glass mmposirion Alloy composirion 0
C&
no Cobw SiO, Nu20 MgO A1201 K20 COO PbO SnO, Sb,Ol Mn,O3 Fe203 Cu,O COO ZnO Sn Pb Zn Cu
1 RCd 1 4 7 0.4 0.7 0.4 2.2 1.4 n n 5.5 4 n 90
2 Red 1 5 20 2 n 0.3 3 1.4 n n 5.5 3 4 87
3 Yellow 0.5 4 24 n 9 0.6 1.7 0.2 n n 6.5 1 n 92
4 Yellow 40.5 7 10 1.5 0.4 0.7 0.7 2.5 n 0.2 8 2.5 8 81
5 Blue 40.5 8 5 t 12 1 2 0.8 0.2 n n n 12 88
6 Blue e0.5 6 2 1.5 5.5 0.7 1.3 0.7 0.2 n 5.5 3 3 88
7 Blue 1 7 3 1.3 4.6 0.8 1.2 0.8 0.2 n 6.5 2 t 91
8 GlXell 40.5 8 4 5.5 1.1 0.7 1 1.9 n n 12 3.5 n 84
9 oran e0.5 5 16 4.5 1.8 0.2 1.2 4.6 n n 2.5 1 4 93
10 White 0.5 6 1 0.4 3 0.2 1 0.1 n n 5 3.5 9 82
11 Black 40.5 6 0.4 0.5 0.3 0.4 10 0.2 n n 6 1 4 89 .r,
12 Orange 40.5 4 22 5.5 2.5 c 0.2 1.7 5.5 n n 6 4 7 83
13 Blue e0.5 7 3 - - 1 2.3 0.6 0.2 n 11 4.5 n 85
b
White e0.5 7 1.5 - - n 0.9 0.3 n n
14 Blue 1 6 2 1.8 1.8 1 1.5 0.4 0.2 n 8 5 n 87 B
white 1 6 0.5 1.3 1.8 n 0.8 0.1 n n
15 Blue e0.5 7 1.5 - - 1 1.7 0.2 0.2 n 6 5 n 89 3
White 40.5 9 2.5 - - n 0.9 0.15 n
16 Blue 40.5 6 3 - - 0.7 1.1 0.7 0.2 n 4 6 n 90 s
White 40.5 6.5 0.6 2 3 n 0.5 0.1 n n
17 RCd 1 8 13 4 n 0.2 3 3.6 n 0.2 7.5 4 4 84
18 Yellow 1.5 10 12 n 3.1 n 1.5 1 n n t 1 20 79 8
19 Blue 1 8 3.5 2.5 3.5 1.1 2.1 0.6 0.1 0.2 9.5 3.5 n 87 P
20 BIUC 40.5 8 2 - - 0.8 1.4 0.5 0.1 n 6 2 9 83
20 Green 40.5 8 35 t n n 1.2 6 n 0.8 6 2 9 83
h
22 Black 1 6 0.5 0.7 t 0.2 12 0.1 n n 3.5 2.5 9 85 g
23 orange 60.5 4 7 2 0.8 0.2 2.2 9 n n 7 3 3 87
24 RCd 0.5 2 17 0.8 1.5 n 1 6.4 n n 8 5.5 4 82 k
24 Blue 1 6 n 0.8 n 1.6 1.6 0.2 t n 8 5.5 4 82
25 white - - 0.6 0.5 6 - - - - - - - - - c2
a Blue - - 4.5 - - - - - - - 8 5.5 4 82
b Red - - 5 - - - - - - - 3 1 10 86
C - - 6 - - - - - - - 11 4 n 85
d RCd - - 12 - - - - - - - 9 11 n 80
e - - 3 -
-
-
- -
- -
-
- -
-
- 5.5 3.5 9 a2
f Blue - - 4 - - 8.5 6 6 80
S Blue 2.5 - - - - - - - 8 6 6 80
GRXU - - 12 - - - - - - -
h White - - 0.2 - - - - - - - I5 7 n 78
i - - - - - - - - - - 13 5.5 n 81
j White - - 0.1 - - - - - - -
Blue - - 3.5 - - - - - - - 10 5.5 n 84

Results are given as (wt %) for the oxides listed. Note that Cu is expressed as CuzO even where it may actually be present as CuO. ‘t’ refers to a
trace quantity present, ‘n’ to below the limit of detection, and ‘-’ denotes that the element was not sought.
Cu in the alloy analyses is determined by difference from 100% where it is established that no elements other than Zn, Pb, Sn are present in significant
amounts.
 The scientific analysis of a group of Roman-age enamelled brooches I81

sequent uncertainty in the accuracy (the error would be systematic). Recently, more useful
glass standards have become available (through the British Glass Industry Research Associ-
ation) and it has been possible to check the results retrospectively. However, the combina-
tion of systematic and other errors (e.g. from the use of masks) leads to an uncertainty of
up to f25% for some of the Sn and Sb analyses in the worst cases. The accuracy of the
other elements is estimated to be about f10%and, for those elements measured by emission
spectroscopy, .Itl5%. The accuracy of the alloy determinations is believed to be f5%.
The precision of the data, and hence the comparison of similar compositions, is largely
determined by the physical and chemical homogeneity of the surface, and is estimated
from the results to be f 5 % (for one standard deviation). In one case (no. 12), chemical
variations were found to be much greater. Any special difficulties, limits of detection etc.,
are considered in the section on results.

4. RESULTS
The results of the elemental analyses are presented in table 3. Note that this table also
includes analyses of the metal backing for comparison. In addition, samples from nos.
3, 10, 12, 18, and 23 were analysed by X-ray diffraction, and the identification of the
major crystalline components is given in table 4. The chemical significance of the results is
discussed below.

Table 4 Results of X-ray diflraction analysis

Sample Colour Identification Comments

3 yellow Pb2Sb207
10 white Ca2Sbz07
12 orange CuzO PbSnOt a d .
18 yellow PbzSbz07
23 orange CuzO PbSnOs a d .

The glass-forming elements: Na, K, Mg, CayA1

The levels of these elements, on the eight analyses made, show a notable consistency which
is in contrast to the rest of the data. Furthermore their proportions to that of silica (esti-
mated by difference from 100%) are typical of analyses of Roman soda-lime glasses (see
e.g. Caley 1962, pp. 93-104). The characteristic correlation between K and Mg for glass
produced in the western Roman Empire, as noted by Sayre (Sayre and Smith 1967, pp.
279-311) is maintained (with the exception of no. 15).

Lead
Lead is also a glass-forming element and may be deliberately added to influence the physical
properties of glass such as the melting point, expansion coefficient, colour (e.g. of Cu(I1)
ions), or the high-temperature solubility of Cu,O or SnO,. It may also be present as a
colourant or opacifier.
The concentrations found in these enamels are extremely variable, reflwting the com-
I 82 J. D . Bateson and R. E. M . Hedges
plexity of the various functions of the element. Only one example (the transparent pale blue
glass spots of the Iron Age terret, no. 24) contains no lead at all; all other examples there-
fore have a composition quite distinct from that of ordinary Roman glass, ranging from
levels having very little influence on the enamel properties (nos. 11, 14, 16, 25-all
black or white) to levels characteristic of contemporary lead glazes (no. 20, with 35%
PbO). The presence of lead (and of copper) in Iron Age glass has been the subject of a recent
study (Hughes 1972), and the red enamels of our study clearly are chemically similar,
but show greater variation and quantitatively are much closer to enamel compositions for
other colours. The universal deliberate addition of lead is a most interesting finding, and is
discussed in the next section.
Transition metals giving coloured ions: Mn, Fe, Co, Cu
The deliberate addition of these elements (or rather, natural materials specifically containing
them) for their colour is to be expected. There seems to be no example here where an enamel
colour is primarily due to Mn. (Although this apparently occurs in the Wall brooch.)
Mn is a common impurity in both sands and ashes and this fact may explain its abundance
here. However, there is reason to believe that levels over 0.5% (Sayre & Smith 1967, p. 294)
may be the result of deliberate addition in order to remove the colour from iron containing
glass, and so Mn might be incorporated into an enamel if it was made from a mass-produced
decoloured glass base. There appears to be a high correlation of Mn with Co. This has been
noted in other contexts (Sayre and Smith 1967, p. 295; Chinese cobalt underglazes, Young
1956), and is common as a geochemical association (Goldschmidt 1958, p. 627).
The deliberate addition of iron is very likely for nos. 11 and 22; a level of 10% is typical
for a very dark brown glass. The other analyses suggest iron is present at its characteristic
impurity level (from sand, the main source of silica); amounts present above 1% would
have some influence on the colour, however, and it is significant that the paler colours (nos.
4, 13, 15, 16, white) have the lowest levels.
Cobalt is only detected in the blue enamels. The detection limit and accuracy for Co are
poorer than for other metals because of unresolved interference from iron K, radiation;
the detection limit (in the presence of iron) is not much below O.l%, and a figure of 0.2%
would have a 50% error. An amount of 0.2% COO is quite sufficient to colour glass a
deep blue, however. The colour of no. 24 is much paler and is consistent with the detection
of Co at a trace level. Co is unlikely to be an unintentional additive since it does not com-
monly occur in the raw materials of glass.
Blue, green and red glass may all be produced by copper, depending on its oxidation
state and coordination. There is no sample of blue enamel analysed here for which the colour
is due to copper (it is just possible, though extremely unlikely, that no. 24 may be an
exception to this). The red cuprous oxide enamels, nos. 17 and 24 fit well enough into the
pattern established by Hughes for Iron Age red glass; the red enamels, nos. 1 and 2 are sur-
prisingly low in copper and may also contain colloidal metallic copper. Examination by
a high-powered microscope shows a similar abundance of minute Cu,O crystals, however.
High amounts of Cu are present in the orange enamels. All the green enamels are attribut-
able to copper. Copper is also present in all the enamels examined in concentrations too
high to be due to impurity in the raw material, but is significantly lower in the white enamels
where it might cause discolouration. The ubiquitous presence of copper might be explained
by a transfer of corrosion products from the bronze substrate to fissures and pores in the
 The scientific analysis of a group of Roman-age enamelled brooches 183
enamel. (No attempt was made to chemically clean the enamel; but care was taken, e.g. by
masking, to ensure that all the X-ray fluorescence detected was solely due to the enamel.)
However, one would not expect there to be less copper in the white enamels if this were
generally true.
Opacifiers and colourants: Sn and Sb
In only one example is there virtually no Sn or Sb. Lead antimonate (PbzSbzO,) and cal-
cium antimonate are common opacifiers, and could account for the presence of Sb in the
yellow and white enamels respectively. However, tin lead oxide (SnPbO,) and tin oxide
have also been used as yellow and white opacifiers, although not to our knowledge in
the Roman period. The results for the white enamels (very little lead and tin, but appreciable
antimony) suggest calcium antimonate is used consistently for their production. This is
confirmed in the X.R.D. study of no. 10 in which CazSb20, was identified.
Lead antimonate was identified in nos. 3 and 18 by X-ray diffraction, a finding consistent
with the analysis. Unfortunately a sample for X.R.D. could not be obtained from no. 4
where it is not clear if Sb or Sn (or both) is responsible for the yellow colour (in this example
the colour is unusually pale).
The two orange examples have compositions suggesting the colour is produced as a
mixture of red from Cu,O and yellow from PbSnO,. X.R.D. analysis of nos. 12 and 23
showed only Cu20 as a crystalline component. While it is disappointing not to identify
any other colourant or opacifier, we think that PbSnO, is still the most likely compound
used, but the evidence must remain circumstantial.While for most brooches the composition
is reasonably homogeneous, in no. 12, which has a large expanse of orange, there was
considerable variation in the Sn/Sb ratio (but not in other elements). Table 3 gives the
average composition, but the ratio was found to have values from 8 :1 to 3 :2. There was
much less variation found for no. 23, although that brooch also has a large area of orange.
Less clear is the part played by Sn and Sb in the other enamels. Calcium antimonate could
be used to opacify all the enamels (it is noteworthy that the one transparent enamel, the
blue of no. 24, is free of Sb, and that the opaque reds (opacified by crystalline Cu,O)
contain low levels of Sb) but the amounts of lead also present will complicate the chem-
istry. The relatively high amounts of Sb for the blue enamels is interesting, and there seems
no obvious explanation for this. The part played by tin is not at all clear.
Zinc
Zinc can act as a glass-forming element, and under some conditions as an opacifier, but
there is no evidence, and it is technically most unlikely, for such uses in Roman times. The
levels encountered here might be attributed to contamination from the metal substrate,
except for no. 19 which contains no zinc. It is more likely that the zinc is introduced along
with the copper in the enamel, e.g. by adding brass, or oxides prepared from it, although the
volatility of ZnO might be expected to decrease the ZnO/Cu20 ratio to lower values than
those found.
The alloy composition
The results displayed in table 3, show a fairly consistent alloy composition in use. 31 of 33
analyses have typical levels for a tin bronze, all except one (no. 5 ) contain lead, with an
average level corresponding to that for a typicaI casting bronze. The variation in zinc is
184 J. D. Bateson and R. E. M.Hedges
much greater, but the level seldom exceeds 10%. However, zinc is consistently absent where
there is more than 10% Sn. All metallic elements present in concentration greater than
about 0.25% have been measured, so that other possible metals, for example silver, are
present, if at all, in traces.

5. THE VISUAL EXAMINATION OF T H E ENAMELS: RESULTS

A N D DISCUSSION

High-power microscopy was used to examine any crystalline structure, inclusions, etc.,
within the enamel material, while the interface between the enamel and metal was examined
with a low-power binocular microscope. Greater clarity was obtained by immersing the
objects in methanol. In most cases the only interface observable was between the glass and
metal cell sides, as seen from above, but the interface at the cell base could be examined for
a few incomplete brooches.
Particular attention was paid to the millefiori enamels for these cannot be made by a
fritting process. Since the softening of glass is related to its surface area, direct adhesion of
millefiori plaques would require a higher temperature, would be more difficult to control,
and moreover would run the risk of fusion and destruction of the millefiori pattern. This
difficultycould be surmounted by embedding the plaque in a layer of more fusible red glass.
Henry (1933, pp. 67-70) has argued that both methods were practised, although con-
vincing evidence is lacking, but the more generally held view is that of Jope (see Wainwright
1953, p. 68) in which a red enamel matrix is held to be consistently used.
Enamels which disclosed interesting features on microscopic examination are described
below.

No. 24-the Suffolk Terret (Iron Age)

In this case (the only such enamel in this study) the blue spots are transparent, and red glass
underneath can be clearly seen. Nor does the blue glass have the appearance of being fused
in situ. This is consistent with other similar examples of Iron Age enamel decoration (e.g.
the Hod Hill stud, British Museum reg. no. 92.9-1.528).

No. Il--at disc brooch with black

This is an example of a type of small, simple, flat disc brooch with a single six-lobed septum
(for other examples see Thompson 1965, p. 83, fig. 20, no. 9 or Mackreth 1973, p. 26, fig.
27). Usually the outer cell contains black and the centre spot red enamel. Around the edge
of the black enamel could be seen a thin red strip (50-100 pm). This is presumably red
enamel into which the black is set. The black enamel could not have been cut to the complex
shape of its containing cell, but it could have been pressed in whilst hot. Alternatively, a
black frit could be used. Black is also used as an inlay in other enamels, usually in the form
of a cylinder so that it appears as a black spot. Such is the case for no. 21 (an enamel in too
poor a state of decay for useful chemical analysis) in which the 1 mm dia., 2 mm long
cylinder is inserted into a white enamel ground. Spots where cylindrical inserts appear to
have been lost occur in specimens nos. 10,12, and 23. Possibly there is a particular technical
difficulty in enamelling black directly to the metal. The unusually low lead content of black
glass may be significant in this context.
 The scientific analysis of a group of Roman-age enamelled brooches 185
The mille$ori enamels, a-j
We examined ten objects (listed in table 2) with millefiori decoration. These were fairly
representative of the patterns in use during the Roman period and remained in varying
degrees of quality and quantity. It should be noted that in some cases red forms part of
the intentional millefiori pattern-usually as a border-and that this must be distinguished
from a bed of red enamel into which the millefiori glass may have been laid. In
general, a number of examples were observed for which there clearly was no red enamel
matrix. (For example, clean metal could be seen through a very thin non-red enamel
layer in b, h and i.) Several cases were found in which it appeared highly probable that red
enamel was not used as a matrix (e.g. c, g, andj). Thin traces of red were found under the
enamel of a, d, e and one plaque off. Even here the evidence is not compelling proof since
it is conceivable that reaction with the bronze matrix could produce a thin interfacial layer
of red Cu,O. But we believe, at least for a and e, that the green plaques are very probably
set in a red enamel matrix. Thus it appears that at least two different techniques were
practised. It should be noted that the partial composition of the millefiori glass, and in
particular the lead content, is not different from that of the simpler, fritted, enamels (see
table 3). Unfortunately it is seldom that an unequivocal answer can be given to the question
of the use of a red glass matrix; a destructive examination is required.
It was possible to see small evenly distributed crystals, presumably of Cu20,in nos. 1,
2, 12, and 23 under high magnification. Examination of the yellow and blue enamels
revealed yellow and white particles, respectively, of a similar size but much less regular in
size and frequently clumped together. They had the appearance of having been mechanically
distributed rather than having crystallized from the melt.

6. DISCUSSION

We consider here the technological and economic implications of our findings.

Metal-glass bond
The formation of a permanent bond between coloured glass and metal brings problems in
addition to those of preparing the glass itself. In particular, the glass must fuse well below
the melting point of the metal alloy, it must 'wet' the metal, and preferably form a bond with
the substrate. On cooling, the difference in thermal expansion should not be able to cause
detachment or disintegration of the enamel. The melting point of a glass is largely deter-
mined by its silica and alumina contents, which here are low. According to Forbes (Forbes
1957, pp. 221-228) the 'melting' temperature of most Roman glass lies in the region of 700-
800"C,and we should expect the enamel glass, with their greater proportion of fluxes, to
melt in the range 650-700", which is at least 200" below the melting point of any of the
alloys used. It is unlikely that the lead is present to make the enamel more fusible (except
where red enamel is used to embed black and millefiori glass). This could be achieved with
a high soda glass, where a better expansion match would also be obtained. It is most likely
that the function of the lead is to reduce the surface tension and viscosity of the glass. Lead
is particularly effective for this, and a few per cent of lead oxide would be sufficient for the
enamel to wet the metal much more effectively. This is probably the most important single
factor in the manufacture of these types of enamels. All the enamels contain lead, except
where it may influence the colour (e.g. in Sb containing white enamels). Chemical bonding
186 J. D. Bateson and R. E. M . Hedges
between enamel and metal takes place at high temperatures and modem studies (Vargin
1967) indicate that formation of CuO, or better, Cu20, at the interface is particularly
desirable. This is probably promoted by the small but significant amount of copper added
to all the enamels, although it must be speculation to consider the addition of copper for
this purpose to be intentional. Copper (and to a lesser extent zinc, tin and lead) could be a
contaminant introduced, for example, by using bronze-casting crucibles for the enamels.
If so, one might expect the cast metal to contain impurities characteristic of the enamels in
trace amounts. A high level of zinc in the substrate is detrimental to good bond formation
because of oxide development at low temperatures, and it is interesting to note that only
one example is found with a zinc content of more than 12%. (Vargin states that Cu/Zn
alloys with more than ‘10-13% Zn’ are hard to enamel.) The difference in expansion of
metal and glass is too large to be eliminated by a suitable glass composition, and the
enamel composition we find does not appear to have been formulated to produce a high
expansion. The expansion coefficient (301) is 540x for copper and about 300x lo-’
for glass. In modern practice it is not considered necessary to achieve a better match than
this for copper, silver or gold enamelling since the metal substrate is quite soft when annealed.
It is expected to be more difficult for the harder alloys encountered. However, the difference
in expansion is such as to cause compression of the enamel, and provided the cells are fairly
small and deep, which in general they are, there is probably not much danger of loss of
the enamel.
Glass type
The composition of the base glass shows the technical proficiency characteristic of Roman
glass in general; the apparently haphazard variations in lead, tin and antimony contents are
in striking contrast. It is possible that such elements were added to a basic glass frit together
with the desired colouring materials, and refritted. The red enamels can be regarded as a
continuation of the opaque red glass of Iron Age times (Hughes 1972) although the lead
contents are generally much below the average found by Hughes. Nevertheless, the com-
position is entirely sensible for their function (i.e. to enable the high-temperature solubility
of Cu20 and to produce a well-flowing, wetting glass). The green enamel of no. 20 is the
only one to resemble a contemporary pottery glaze in composition (Jope 1956, p. 300),
and it would appear that there is little technical interaction between the basically similar
processes of enamelling and glazing. (Only one colour, that of oxidized copper, is used for
colouring glazes of this period.)
Colour
There is some consistency in the quantities of tin and antimony, especially for the white,
yellow and orange pigments. Thus yellows tend to contain Sb rather than Sn, and oranges
Sn rather than Sb. However, even in these examples many features are hard to understand;
for example the occurrence of more than 1% SnO, in two of the whites (nos. 14 and 16).
Also, the position is confused by the compositional variation found in brooch no. 12
where the Sn/Sb ratio varies from about 8 :1 to 1.5 :1. Perhaps different frits were mixed
together in situ. Most of the blues have a high level of Sb, while for the remaining colours no
particular pattern emerges, at least for the limited number of examples here analysed. There
is clearly some appreciation of the different reactions of Sn and Sb (which are chemically
rather similar in many ways) with Pb,
 The scientijk analysis of a group of Roman-age enamelled brooches 187
Nevertheless, the apparently unpredictable quantitative levels of Sn, Sb and also of Pb
show far less control or understanding in the manipulation of these materials. This is clearly
an area where further investigation, both of a much larger population and to a greater
accuracy, combined with X-ray diffraction, would be very rewarding. For example, there
may exist local traditional formulations favouring quite different mixtures of Sn, Sb and Pb.
The identification of the additives producing the characteristiccolours brings no surprises.
All the colourants found are common in much earlier glass (e.g. Egyptian glass; see Lucas
1948, p. 219) with the exception of lead-tin yellow, for which the only pre8axon example is
known from a La Tene I11 burial at Welwyn (Werner and Bimson in Stead (1967)). Orange
glasses do not seem to have been considered before, and it is interesting to find that their
colour is produced as a mixture of red and yellow (it cannot be shown whether this is
a mixture of red and yellow glass or of the colourants). It is significant that lead-tin yellow
apparently occurs only and consistently for the orange enamels, even when made in two
quite different places. We cannot think of any reason why lead antimonate is not equally
suitable. It would be most interesting to see if this distinction is universal. The green glasses
have a similar elemental composition to the reds; here the copper is in its oxidized (cupric)
state, and the lead is present not for purposes of dissolving cuprous oxide, but for providing
the coordination environment for the Cu(I1) ion to produce a green colour rather than the
blue familiar in alkaline glass. We cannot be sure that slow oxidation of a red (Cu(1))
enamel would not produce an apparently intentional green (Cu(I1)) glass, although this
seems unlikely. No borderline cases were observed, and the enamels were rich and homo-
geneous in colour. Red and green enamels require different firing conditions (Hughes has
pointed out the difficulty of producing a red glass under the necessary reducing conditions
and implies that it would not be used as a frit (where oxidation would be much faster)).
In view of the skill in applying millefiori glass it may well be that red glass was applied in
this way; visual inspection of the brooches is not helpful, though the very common usage
suggests a simple method of application. Reducing conditions could be achieved by fusing
the frit under charcoal, though there is some danger in reducing the lead oxide in the glass
to metal. It is significant that no example of red and green together was noted. No. 20
contains orange as well as blue and green, but the blue and green enamels are not separated
by a metal barrier and appear to have been inserted as plaques. They need not have been
fired at the same time as the orange, and so it would be possible to arrange for the appropriate
oxidizing/reducing conditions in each case.
The finding of enamel consistently coloured by cobalt appears to be unusual. Thus Harden
(1956) and Forbes (1957) indicate that Co does not occur in Roman glass, although Cayley
(1962, p. 102) does list two examples. The blue enamel on the Wall brooch was apparently
due to copper, while the blue of the Southacre armlet was attributed to Co (Mottram 1968).
All of the blues encountered here were quite intense (excepting no. 24) and could not have
been produced by Cu (which in any case would have produced a very green blue on account
of the lead also present).
Metal type
The brooches themselves appear to have been cast, for which their composition is entirely
suitable (Tylecote 1962, p. 55). Considerable variation in composition is to be expected as
undoubtedly a high proportion of bronze would be recycled. The relationship of the range
of composition found for enamelled brooches to that for other bronze objects is interesting
I 88 J. D. Bateson and R. E. M . Hedges
and important, but too few analyses of Roman bronzes have so far been published for this
to be fairly studied. It would be desirable to know the extent to which compositions for
enamelling were specialized, and the degree to which they were controlled. A high propor-
tion of the brooches contain no zinc, which appears to be atypical, judging from Tylecote’s
compilation. Furthermore, there is a consistent absence of zinc where the level of tin is
greater than 10% which is suggestive of control of the alloying ingredients. Where zinc is
present its range is fairly narrow, and in any case does not exceed 10% except on two occa-
sions; this may well be due to the difficulty encountered in enamelling a high zinc alloy,
referred to above. Nevertheless, an alloy composition of 0-2% Sn, 2 4 % Pb and 10-20%
Zn appears to have been a popular one for small decorative objects (Craddock, to be pub-
lished), but clearly was avoided for enamelled material. The average zinc level is somewhat
higher than given by Tylecote for cast objects, and may be deliberate in order to impart a
gold-like appearance to the decorative object. No example of pure copper occurs; this is
consistent with Tylecote’s review of compositions of non-enamelled bronzes, although such
a metal would be very easy to enamel.

The economic implicationsare less definite, and it is clear that a larger sample is necessary
for useful information. A number of questions can be suggested that a comprehensive
analytical survey could help answer; how local and how large were the production centres?
Were the brooches cast in the enamel-working workshops ? Were the frits prepared locally,
or was coloured glass traded? In what form were the rarer additives (cobalt, antimony)
transported 7 Were there different technical traditions and, if so, how long did they last?
Our work suggests tentative answers to some of these questions. The variations in chemical
composition could be brought about by the enameller adding his own ingredients to the
widely available standard soda-lime glass. This suggests fairly small-scale practice, with
consequent variation in the levels of specialized enamelling elements. The bronze used is
also rather specialized, and could well have been made by those experienced in enamel-
working. There is some evidence for contamination of the enamel by bronze working. An
analysis of the date of Hughes (on Iron Age red glass) shows that objects likely to have been
made in the same workshop have very similar compositions for Cu,O and PbO (M.
Spratling, personal communication). If batch members can be so identified, or if workshops
can be shown to work to a specific composition, a very large programme of analysis would
be most useful for settling these questions. Our work suggests that no great differences in
technique existed either between the Continent and Britain, or the first and fourth centuries
A.D.; on the other hand, there are intriguing differences in the treatment of tin, lead and
antimony, which, when better understood, may well be most informative.

7. CONCLUSIONS
As the first analytical survey of representative Roman enamels, this study raises as many
questions as it answers. Throughout the period of the Roman Empire in the West enamel-
work appears to have been made from common soda-lime glass to which characteristic
elements, in particular lead, tin and antimony, together with traditional colourants, have
been added. The addition of lead, and the general control of chemical composition when
necessary (e.g. for white enamels) shows a high degree of technical sophistication, as does
the careful choice of the range of metal alloys in use. Cobalt is consistently found in the
 The scientific analysis of a group of Roman-age enamelled brooches 189
blue enamels: while the red enamels show a basic chemical similarity to those of the Iron
Age, they too could have been derived from available soda-lime glass. It is not clear whether
the red enamel was used as a frit; it was almost certainly used as a matrix for embedding
millefiori enamel, but millefiori enamel was also produced without recourse to this tech-
nique.
There were no obvious distinctions in composition for different periods, nor for different
regions, in our sample, and any such distinction will be hard to demonstrate. However, the
levels of tin and antimony are rather unpredictable, and their further study is likely to
prove most informative.

ACKNOWLEDGEMENTS
We would like to express our thanks to the Keeper of the Ashmolean Museum for permitting us to examine
the group of enamels and to Mr P. D. C.Brown for his help in arranging the selection; to Miss H. Hatcher
(Research Laboratory for Archaeology) for her help with the emission spectrographic analyses, and to
Mr L. Biek (Ancient Monuments Branch, Dept. of the Environment) for helpful discussions. Finally, thanks
are due to Professor E. M. Jope, Queen’s University, Belfast for helping to initiate this project and for much
useful discussion.

BIBLIOGRAPHY
Bates, K. F., 1951, Enamelling: Principles and Practice, New York.
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in Conservation, ed. G. Thompson, London, pp. 145-151.
Caley, E. R., 1962, Analysis of Ancient Class 1790-1957, New York.
Forbes, R. J., 1957, Glass, in Studies In Ancient Technology, vol. V., Leiden, pp. 110-231.
Goldschmidt, V. N., 1958, Geochemistry, Oxford.
Hall, E. T., Schweizer, F. and Toller, P. A. 1973, X-ray fluorescence analysis of museum objects: A new
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Harden, D. B., 1956, Glass and Glazes, in A History of Technology, ed. Singer et al., Oxford, pp. 311-346.
Henry, F., 1933, Emailleurs D’Occident, Prehistoire II, pp. 65-146.
Hughes, M. J., 1972, A technical study of opaque red glass of the Iron Age in Britain, Proc. Prehhtoric
SOC.38, pp. 98-107.
Hunter, A. G. and Kirk, J. R., 1952, Excavations at Campsfield, Kidlington, Oxfordshire, Oxoniensia XVII,
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Jope, E. M., 1956, A History of Technology, II, Oxford, p. 300.
Lucas, A., 1948, Ancient Egyptian Materials and Industries, Arnold, London.
Leeds, E. T., 1933, Celtic Ornament, Oxford.
Mackreth, D., 1973, Roman Brooches, Salisbury and South Wiltshire Museum.
Mottram, A. S., 1968, An Enamelled Bronze Armlet from Southacre, Norfolk Archaeology 34, pp. 259-262.
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Sayre, E. V. and Smith, R. W., 1967, Archaeological Chemistry, ed. Levey, U . in Pennsylvania.
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Thompson, F. H., 1965, Roman Cheshire, Chester.
Tylecote, R . F., 1962, Metallurgy in Archaeology, London.
Vargin, V. V., 1967, Technology of Enamels, ed. Shaw. Maclaren and Sons.
Wainwright, F. T., 1953, A Souterrain Identified in Angus, Antiquaries Journal 33, pp. 65-71.
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190 J. D. Bateson and R. E. M . Hedges

APPENDIX
Publications on the material analysed
Brooch Reference
no.
1 Taylor 1917, p. 115, no. 70.
2 Unpublished.
3 Feacham 1951, p. 40,no. 22 (fig. 5).
4 see Collectanea Antigua ILI, pl. 36.
5 see Catalogue of the Ashmolean Museum, Oxford, 1836, p, 123, no. 62.
6 Unpublished.
7 Radford 1936, p. 56, no. 4 (pl. IX, 4).
8 Unpublished.
9 Unpublished.
10 Taylor 1917, pp. 115-116, no. 71.
11 Unpublished.
12 Unpublished.
13 Hunter and Kirk 1952, p. 60,mention only.
14 Hunter and Kirk 1952, p. 60, mention only.
15 Hunter and Kirk 1952, p. 60, mention only.
16 Hunter and Kirk 1952, pp. 59-60 (fig. 26, 1).
17-23 All unpublished.
24 Leeds 1933, pp. 40-41, 124 (PI. 1, 3) and Clarke, 1939, p. 70.
25 Unpublished.
a Mentioned in Oxoniensia 19, 1954, p. 117.
b Hills 1871, pp. 258-259 (PI. 12, 1).
c Brodribb, Hands and Walker 1968, p. 86, no. 12 (figs. 29, 12).
d Not noted in Radford 1936.
e-j All unpublished.

BIBLIOGRAPHY
Brodribb, A. C. C., Hands, A. R. and Walker, D. R., 1968, Excavations At Shakenoak I (privately).
Clarke, R. R., 1939, The Iron Age In Norfolk and Suffolk, Archaeological Journal 96, pp. 1-1 13.
Feacham, R. W., 1951, Dragonesque Fibulae, Antiquaries Journal 31, pp. 3244.
Hills, 0. M. 1871. Description of three ancient brooches, Journal British Archaeological Association 27,
258-259.
Leeds, E. T., 1933, Celtic Ornament, Oxford.
Radford, C . A. R., 1936, The Roman Villa at Ditchley, Oxon, Oxoniensia 1, pp. 24-69.
Taylor, M. V., 1917, Woodeaton, Journal Roman Studies 7 , pp. 98-119.