The Examination of Ceramics by X-Ray Powder Diffraction

Author(s): M. Bimson
Source: Studies in Conservation , May, 1969, Vol. 14, No. 2 (May, 1969), pp. 83-89
Published by: Taylor & Francis, Ltd. on behalf of the International Institute for
Conservation of Historic and Artistic Works

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Studies in Conservation, 14 (1969), 83-89 83

THE EXAMINATION OF CERAMICS BY X-RAY

POWDER DIFFRACTION

M. BIMSON

Abstract-By using X-ray powder diffraction to identify the crystalline constituent

mics, especially porcelains, a considerable amount of information can be obtained
very small sample. The characteristic mineral in hard-paste porcelains, stonewares
fired earthenwares is shown to be mullite, an aluminium silicate, 3A1203 .2SiO2, (A.s
776); where there is a high calcium content aluminium silicates may occur e.g. a
CaO. A1203 . 2SiO2, (A.S.T.M. 10-379) and gehlenite 2CaO . A1203 . SiO2, (A.S.T.M
Among the soft-paste porcelains, whitlockite, P calcium orthophosphate, Ca3(PO4)2
9-169), is typical of those containing bone-ash, and enstatite, magnesium meta
MgO. SiO2 (A.S.T.M. 7-216) is typical of those containing soapstone. The glassy-f
celains generally contain a calcium silicate, wollastonite or pseudowollastonite, C
(A.S.T.M. 10-487 and 10-486). In addition, silica - either as 0c quartz or cristobalit
occur in varying proportions in all these bodies.

INTRODUCTION

The Research Laboratory of the British Museum is frequently

material. The problem may be one of authenticity; for example, w
with an English mark is of the correct type of soft paste or if it
Samson of Paris for his reproductions of English porcelain. On
may be undoubtedly genuine, and identification of the type of pas
its correct attribution. It is not necessary to carry out a full chem
the type of paste, very often it is quite sufficient to identify the
ceramic body by means of X-ray powder diffraction. This tec
information on the crystalline structure of ceramics, which is not
method, but it also requires such a small amount of material that
as a non-destructive technique. An adequate sample may weig
hardly visible to the naked eye. This is particularly important in th
objects whose owners would otherwise not permit a sample to b
sampling are diamond pencils and diamond-faced spatulas or f
cleaning relay contacts. It is preferable to sample from a brok
this is not possible, a sample is usually obtained from the undersid
after removing any glaze with the diamond spatula. The method c
grains of powder on the tip of a gelatine filament* and placing it
it is rotated in a very fine beam of X-rays; this radiation is diffrac
sample to form a series of concentric cones which intercept a curve

* This mounting technique, which employs strips cut from large gelat
R. K. SOREM in 'X-Ray Diffraction Techniques for Small Samples', Ame
1104-1108 (cf. Fig. 1).
t The equipment at the Research Laboratory, British Museum, consists
powder cameras used in conjunction with a Hilger micro-focus X-ray gener

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 84 M. Bimson

FIG. 1 A powder sample m

with a pin-head.

camera. The pattern so

regarded as a type of
and filed by the Americ
will be quoted for refer

I. LOW-FIRED EARTHENWARES

When clays, which are hydrous aluminium silicates, are heated above a ce
their crystal structure breaks down (for the common kaolinic clays this
the range 450-6500C). Thus if a sample of a low-fired earthenware is
diffraction, there will be no diffraction pattern derived from the clay;
clays contain free silica, there will generally be a component due to c
others arising from associated minerals such as micas, calcite (calci
haematite (iron oxide). If crushed stone has been added to the clay as
possible to separate a fragment for examination. In this way a rare glass
has been identified as forming the gritty surface of a mortaria recov
wreck off Malta.t The Department of Mineralogy, British Museum
reported that 'Adularia is a feldspar having a limited number of kn
Europe and in any case a very restricted paragenesis. Nearest known loca
the supposed beginning of the voyage are Piedmont, Italy; Salzburg
localities in Switzerland.'

* Sets of file cards and index books may be obtained from The American Society for Testing Materials,
1916 Race Street, Philadelphia, Pa. 19103, U.S.A.
t Miss H. Frost, who carried out the excavation of the wreck, considers that it dates from the third
century A.D. and that the ship was probably sailing from Italy to North Africa.

Studies in Conservation, 14 (1969), 83-89

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 The examination of ceramics by X-ray powder diffraction 85

II. HIGH-FIRED EARTHENWARES, STONEWARES AND HARD-PASTE PORCELAIN

Hard-paste porcelain, such as that imported into Europe from China, was made from
mixture of kaolinite (china clay) and a decomposed granitic rock containing silica a
feldspar. True hard-paste porcelain was first manufactured in Europe by B6ttger in t
early eighteenth century and was introduced from Meissen into Austria, Italy and France;
it was developed in England by William Cookworthy who took out a patent in 1768. These
porcelains are very hard (Mohr scale 6-7), translucent and non-porous. Stonewares, wh
are the indigenous 'hard paste' of Europe, are physically very similar, being hard and almo
completely impermeable; however they are not translucent. The characteristic minera
high-temperature ceramic bodies is mullite (3 A1203 . 2SiO2, A.S.T.M. 15-776), which
formed by the re-combination of silica and alumina derived from the clay. The high-fired
earthenwares, such as Wedgwood's creamware, also contain mullite, but do not conta
sufficient vitrified material to make the body non-porous. X-ray diffraction shows t
mullite may occur alone in the glassy matrix, but silica - either as a quartz or cristobalite
is frequently present. It is probable that a quartz represents undecomposed quartz gra
and that the cristobalite occurs as a product of the devitrification of the glassy phase
earthenwares with a high lime content a calcium aluminium silicate may be formed, thoug
this is relatively uncommon in the material we have examined, e.g. anorthite (CaO . A1203
2SiO2, A.S.T.M. 10-379) and gehlenite (2CaO. A1203 . SiO2, A.S.T.M. 9-216).

III. ARTIFICIAL OR SOFT-PASTE PORCELAINS

From the time when Chinese porcelain first became known in Europe
it was the object of wonder and emulation. For many years th
European potters could achieve was earthenware covered with a
decorated with Chinese designs. In the seventeenth and eighteenth c
of 'artificial' or soft-paste porcelains were developed, some of which
even after the technique and raw materials for making hard-p
generally known, in the latter half of the eighteenth century.

A. Glassy-frit porcelains
A basic source of inspiration for experiment was the belief tha
between glass and earthenware; attempts were made to combine the
with clay, by fritting (sintering) the soluble alkali salts with other co
the paste. These experiments gave rise to the glassy-frit porcelains w
and most widespread of the soft pastes. The first successful manufa
'Medici porcelain' at Florence in the late sixteenth century; from th
century, the technique passed to France where this porcelain wa
Cloud, and later at Chantilly, Vincennes, Sevres and elsewhere. A
porcelains were characterized by a high calcium content due to the u
[1]. A peculiarly English development, probably connected with the
lead glass, was a glassy-frit porcelain with a high lead content. T
of porcelain to be made at Chelsea (during the triangle mark per
1748); it was also made at the 'Girl-in-the-swing' factory (from
c. 1749) and at Longton Hall (from c. 1749). During the raised and re
at Chelsea (1749-58), under the management of Nicholas Sprimo

Studies in Conservation, 14 (1969), 83

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 86 M. Bimson

Liege, an almost lead-

used in France and B
introduced in 1758.
The great majority of glassy porcelains have been found to contain wollastonite (calcium
silicate, CaO. SiO2, A.S.T.M. 10-487) with a variable amount of cristobalite (silica, SiO2,
A.S.T.M. 11-695); and this is true of both high- and low-lead porcelains, indicating that the
lead remains in solution in the glassy phase and no lead compound crystallizes out. The
percentage of glass in this type of porcelain is very high indeed. Calcium silicate can also
occur in a high-temperature form (pseudowollastonite, A.S.T.M. 10-486), depending on the
temperature at which crystallization takes place. It has been found that pseudowollastonite
occurs fairly frequently in Chelsea porcelains (five times in twelve samples), but less fre-
quently in early Derby and Longton Hall porcelains (only twice in forty samples). Porcelain
from the 'Girl-in-the-swing' manufactory, so far examined, forms a very consistent group
with well-developed wollastonite patterns.

B. Soapstone porcelains
In a series of letters from China on the manufacture of hard-paste porcelain, published
[2] early in the eighteenth century, a mineral is described, called hoa che, which could be
used instead of kaolin: 'Elle se nomme hoa parce qu'elle est glutineuse, et qu'elle approche
en quelque sort du savon'; it was probably this remark which suggested the use of soapstone
in European porcelain bodies. The chief English manufactories making soapstone porcelain
were Bristol (from c. 1750), Worcester (from 1752), Caughley (from 1772) and also a
number of Liverpool factories. Supplies of 'soapy rock' were obtained from Cornwall,
chiefly from the area of the Lizard. Soapstone or magnesite is said also to have been used
for porcelain-making in Italy, at Venice, Nove, Treviso and Doccia.*
When soapstone (a hydroxy magnesium silicate) is fired, the combined water is driven off
and enstatite (MgSiO3, A.S.T.M. 7-216) is formed; this mineral has been found to be
characteristic of all the standard soapstone porcelains which have been examined. It should
be noted that the term enstatite is intended to include all the forms of magnesium meta-
silicate; the presence of cristobalite makes it difficult to differentiate between enstatite and
clinoenstatite. The conversion of a quartz to cristobalite has almost invariably proceeded
to a point where cristobalite predominates; however, a quartz does occur in some samples.
Two examples of William Ball's (Liverpool) porcelain were found to give a pattern which
has been identified as calcium magnesium metasilicate (CaMg(Si03)2, A.S.T.M. 3-0860).
This suggests that he used a paste with a relatively high calcium content, and it may be that
other variants will be found among the Liverpool factories.

C. Bone-ash porcelains
It is difficult to be certain how bone-ash came to be used as an ingredient of porcelain.
Perhaps it derived from the use of bone-ash in some white opal glasses or from its use in the
cupellation of gold, since most of the 'arcanists' were jewellers rather than potters. Alterna-
tively it may have been discovered during trials of white refractory materials. In any case,
bone-ash porcelains were a purely English production; they were first made on a large scale
at Bow (from c. 1748), then at Liverpool (from c. 1754), at Lowestoft (from 1757), at
Chelsea (after 1758, i.e. the gold anchor period) and at Derby (after 1770). The porcelain
*Our current work on Italian porcelains indicates that the subject is much more complex than is sug-
gested in the literature. It seems clear that these groups differ from English soapstone porcelains and also
from each other.

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 The examination of ceramics by X-ray powder diffraction 87

body used at Bow was noted by Josiah Wedgwood [3] to consist of '4 parts bone ash;
4 parts Lynn sand; a 1 part of gypsum plaster or alabaster; a - part of blue ball clay'.
When china clay and china stone became freely available in England after the expiration of
William Cookworthy's hard-paste monopoly, they were used with bone-ash to produce the
so-called 'bone-china' which is still the standard fine porcelain body made in England.

FIG. 2 The diffraction pattern given by a sample of 'bone-ash' porcelain; the spotty lines are those
due to t quartz.

The characteristic mineral in bone-ash porcelains was found to be whitlockite (#1 calcium
orthophosphate, Ca3(PO4)2, A.S.T.M. 9-170); these porcelains usually contain whitlockite
and cristobalite with a small amount of : quartz, though occasionally the o quartz pre-
dominates. In some examples there is a considerable amount of coarsely crystalline
quartz, e.g. the sample of Bonnin and Morris* porcelain; the spotty lines are those due
to a quartz, and the spottiness indicates that the crystallites are larger than 10-3 cm (Fig. 2).
It has been stated [4] that 'bone-china' consists of whitlockite and anorthite (calcium
aluminium silicate, CaO. A1203 . 2SiO2, A.S.T.M. 10-379) in a siliceous glassy matrix; no
evidence for the presence of anorthite has been found in the X-ray diffraction patterns of
bone-ash porcelains, but the diffraction patterns of two samples of modern bone-china
show a pair of diffuse lines corresponding to spacings of 3-62 and 3-78A, which may be due
to the presence of anorthite. However, because of the relatively low intensity of these lines
it would be unwise to rely on them to distinguish between the two types of bone porcelain.

CONCLUSION

X-ray powder diffraction provides a quick and economical method of c

body. However, it does not replace chemical analysis, since it gives
the minor and the non-crystalline constituents; quantitative analysis sh
in addition, if circumstances permit.

ACKNOWLEDGEMENT

The author wishes to thank Dr A. E. Werner of the Research Laborator

Dr G. F. Claringbull of the British Museum (Natural History), an
of the General Electric Company Ltd for their help.

REFERENCES

1 BRONGNIART, A., Traite' des Arts Ceramiques, B6cher Jeune, 2nd

461.
2 Du HALDE, J. B., Description geographique, historique, chronologique et physique de l'Empire de
la Chine et la Tartarie Chinoise, Paris 1735.
* This sample was excavated by G. Hood on the site of the manufactory founded by Bonnin and Morris
at Philadelphia in 1769.

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 88 M. Bimson

3 Josiah Wedgwood's Ex
Barlaston.

4 ST. PIERRE, P. D. S., 'Constitution of Bone China', J. Am. Ceram. Soc., 37 (1954), no. 6,
243-258.

Received 17/10/68

M. BIMSON, born 1925. A Fellow of the Society of Antiquaries of London and Senior Experimental Officer
in the Research Laboratory of the British Museum.

Author's address: Research Laboratory, The British Museum, London W.C.1, Great Britain.

Abstrait-L'utilisation de la diffraction des rayonsX (Debye-Scherrer) pour l'identification des

constituants cristallins de ceramiques, surtout de la porcelaine, permet d'obtenir une masse
abondante d'informations sur un tres petit 6chantillon. Le mineral caracteristique dans les
porcelaines dures, les poteries en gres et les faTences cuites 'a haute temperature, se r6vele tre
le mullite, un silicate d'aluminium, 3A1203.2Si0O2, (A.S.T.M. 15-776); lorsque la teneur en
calcium est 6lev6e, des silicates d'aluminium de calcium peuvent se produire, par exemple
l'anorthite, CaO . A1203.2SiO2, (A.S.T.M. 10-379) et le gehlenite 2CaO . A1203. Si02,
(A.S.T.M. 9-216). Parmi les porcelaines tendres, le whitlockite, 3 orthophosphate de calcium,
Ca3(PO4)2, (A.S.T.M. 9-169) est typique pour celles contenant des cendres d'os, et l'enstatite,
un m6tasilicate de magnesium, MgO . Si02 (A.S.T.M. 7-126) est typique pour celles contenant
de la steatite. Les porcelaines a verre fritt6 contiennent g6neralement un silicate de calcium, le
wollastonite ou pseudowollastonite, CaO . Si02 (A.S.T.M. 10-487 et 10-486). De plus, des
elments siliciques - sous forme de a quartz ou de cristobalite - peuvent se presenter en
diverses proportions dans tous ces articles.

Kurzfassung-Debye-Scherrer-Pulver-Diagramme erm6glichen die Identifizierung der kristal-

linen Bestandteile von Keramik, insbesondere von Porzellan. Man erhilt auf diese Weise von
einer sehr kleinen Proben, deren Entnahmestelle mit blol3em Auge kaum sichtbar ist, eine
betrdichtliche Anzahl von Informationen. Als charakteristisches Mineral in Hartporzellanen,
Steingut und hochgebranntem Tonzeug wurde Mullit, ein Aluminiumsilikat 3A1203 . 2SiO2
(A.S.T.M. 15-776) gefunden. Bei hohem Calciumgehalt k6nnen unter anderem Anorthit,
CaO . A1203 .2Si0O2 (A.S.T.M. 10-379) und Gehlenit, 2CaO. A1203 . Si02 (A.S.T.M. 9-216)
auftreten. Unter den Weichporzellanen ist Whitlockit, if-Calciumorthophosphat Ca3(PO4)2
(A.S.T.M. 9-169) typisch fir jene die Knochenasche enthalten, und Enstatit, Magnesium-
metasilikat MgO. Si02 (A.S.T.M. 7-216) typisch fUir solche die Speckstein enthalten. Glas-
fritten-Porzellane enthalten im allgemeinen ein Calciumsilikat, Wollastonit oder Pseudo-
wollastonit, CaO . Si02 (A.S.T.M. 10-487 und 10-486). Zusitzlich kann in all diesen Keramik-
k6rpern Siliziumdioxid, entweder als a Quarz oder als Cristobalit vorliegen.

Estratto-Adoperando la diffrazione dei raggi X (Debye-Scherrer) per l'identificazione dei

componenti di
considerevole cristallini in ceramiche,
informazione specialmente
da un minuscolo campione.porcellane,
11 mineralesicaratteristico
pub ottenere una quantita.
in porcel-
lana dalla pasta dura, in maioliche ed in terracotta fatta ad alta temperatura, risult6 essere
la mullite, un silicato di aluminio, 3A1203.2SiO2, (A.S.T.M. 15-776); quando e presente un
alto contenuto di calcio, si possono incontrare silicati di calcio-aluminio come p.e. anorthite
CaO . A1203 . 2Si02, (A.S.T.M. 10-379) e gehlenite 2CaO . A1203 . SiO2, (A.S.T.M. 9-216). Tra le
porcellane dalla pasta molle, la whitlockite, 3 ortofosfato di calcio Ca3(PO4)2, (A.S.T.M. 9-169)
e caratteristica per quelle contenenti la cenere di ossa mentre la enstatite, metasilicato di
magnesio MgO . Si02 (A.S.T.M. 7-216) e caratteristica per quelle contenenti la steatite. Le
porcellane a fritta vitrea di solito contengono un silicato di calcio, la wollastonite o la pseudo-
wollastonite, CaO. SiO2, (A.S.T.M. 10-487 e 10-486). In tutte queste sostanze, inoltre, la
silice - sia come x quarzo o come cristobalite - pub essere presente in proporzioni variabili.

Extracto-Usando difracci6n de los rayosX (Debye-Scherrer) para identificar los constituyen-

tes cristalinos de cerimica, especialmente porcelana, puede obtenirse una cantidad considerable
de informaci6n con una muestra muy pequefia. Se ha demonstrado que el mineral caracteristico

Studies in Conservation, 14 (1969), 83-89

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 The examination of ceramics by X-ray powder diffraction 89

en porcelanas de pasta dura, greses y loza de barro de fuego alto es mullita, un silicato de
aluminio, 3A1203 . 2SiO2, (A.S.T.M. 15-776); donde existe un contenido alto de calcio pueden
ocurir silicatos de calcio-aluminio, par ejemplo anorthita CaO. A1203 . 2SiO2, (A.S.T.M. 10-
379) y gehlenita 2CaO. A1203 . SiO2, (A.S.T.M. 9-216). Entre las porcelanas de pasta blanda,
whitlockita, P3 calcio ortofosfato, Ca3(PO4)2, (A.S.T.M. 9-169) es tipico para aquellas con-
teniendo ceniza de hueso, y enstatita, magnesio metasilicato MgO. SiO2 (A.S.T.M. 7-216) es
tipico de aquellas conteniendo esteatita. Las porcelanas fritas-vidriosas generalmente contienen
un calcio silicato, wollastonita o pseudo-wollastonia, CaO. SiO2, (A.S.T.M. 10-487 y 10-486).

Adem.s, silice
variables - oestos
en todos comocuerpos.
oc-cuarzo o como cristobalita - puede ocurir en proporciones

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