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5

Chapter 1

THERMOANALYTICAL METHODS IN CLAY STUDIES


Robert C. MACKENZIE
The Macaulay Institute for Soi Research, Craigiebuckl er , Aberdeen , Scot1and , UK.
1.1 INTRODUCTION
There is nothing new in the thermal study of clays. Indeed, as early as about
315 BC, Theophrastus refers to the effect of "fire" (i.e. heat) on talc (as
steatite) and on palygorskite (as "mountain wood") (Eichholz, 1965) and
development in the use of heat as a discriminator can be traced from that time
on (Mackenzie, 1981a). Even evolved gas analysis, which would be considered by
some as a relatively recent technique for clays, has its roots in the eighteenth
century, when the Rev. Stephen Hales (1727) found that "a cubick inch of fresh
u n t r i e d earth" (his italics) yielded "43 cubick inches of air" on heating and
Josiah Wedgwood (1782) detected only carbon dioxide on firing china clay in a
closed system, the evolved water having condensed and gone unnoticed.
The first thermoanalytical study of clays was performed in 1887, when Henri
Le Chatelier recorded what were essentially heating-rate curves for halloysite,
allophane, kaolinite, pyrophyllite and montmoril lonite, over the approximate
temperature range 20-llOOC, in an attempt to use their behaviour on heating as
a classificational criterion. His results suggest that the samples used were
remarkably authentic - surely a tribute to the mineralogists o f the time who had
none of the modern methods of diagnosis available to them. Despite the
differences observed, 1 ittle advance, apart from the pub1 ication of some so-called
"dehydration curves" (Samoilov, 1909) and some heating curves (e.g. Mellor and
Holdcroft, 1911; Ashley, 1911; Brown and Montgomery, 1912), occurred until Wallach
in 1913 first applied differential thermal analysis (DTA) to clays. Even this,
however, seems to have elicited little response and, although the OTA studies o f
Satoh (1918, 1921) aroused more attention, it was not until the early 19405,
subsequent to the detailed studies of Norton (1939) and Hendricks and Alexander
(1939), that DTA blossomed forth as an investigational technique. The reason is
simple: at that period clays excited much interest as the general structure of
the clay minerals had been establisned and the species collected into groups, with
the reLult that methods of identification and estimation additional or complementary
to X-ray diffraction were being sought. Unfortunately, the indiscriminate
application of DTA to problems that it could not possible solve,and even the use
of unsuitable equipment and technique, led to the method being discarded by some
as useless in clay mineralogy. However, by no means all clay mineralogists were

6
so d i s i l l u s i o n e d and much p a i n s t a k i n g work over t h e years (by e.g.

Ralph E. G r i m ,

Paul F. Kerr, Toshio Sudo and o t h e r s ) g r a d u a l l y demonstrated t h a t DTA d i d have a


place i n c l a y m i n e r a l o g i c a l studies.

A t t h i s p o i n t t h e reader m i g h t w e l l ask why t h e r m o a n a l y t i c a l s t u d i e s (discussed


i n t h e paragraph above) should be separated from p u r e l y thermal s t u d i e s ( r e f e r r e d
t o i n the f i r s t paragraph).

The reason i s t h a t thermal methods have t o s a t i s f y

c e r t a i n c r i t e r i a before they can be termed thermoanalytical.

These c r i t e r i a ,

some o f t h e thermoanalytical techniques c u r r e n t l y a v a i l a b l e and t h e i r a p p l i c a t i o n


and/or a p p l i c a b i l i t y i n c l a y i n v e s t i g a t i o n s a r e t h e s u b j e c t o f the remainder o f
t h i s paper.

1.2

THERMAL ANALYSIS
Over t h e past f i f t e e n years much a t t e n t i o n has been devoted t o nomenclature,

d e f i n i t i o n and c l a s s i f i c a t i o n o f thermoanalytical techniques w i t h t h e r e s u l t t h a t


the methods included can now be c l e a r l y recognized and named.
According t o t h e I n t e r n a t i o n a l Confederation f o r Thermal A n a l y s i s (ICTA),
thermal a n a l y s i s covers (Lombardi,

1980):

"A group o f techniques i n which a p h y s i c a l p r o p e r t y o f a substance and/or i t s


r e a c t i o n products i s measured as a f u n c t i o n o f temperature, w h i l s t t h e substance
i s subjected t o a c o n t r o l l e d temperature programme".
The t h r e e c r i t e r i a t h a t d i s t i n g u i s h a t h e r m o a n a l y t i c a l method are, t h e r e f o r e ,
t h a t a p h y s i c a l p r o p e r t y i s measured as a f u n c t i o n of t e m p e r a t u r e under a
c o n t r o l l e d t e m p e r a t u r e programme.

Thus, a s i n g l e isothermal d e t e r m i n a t i o n i s n o t

thermoanalytical b u t assessment o f the r e s u l t s o f a s e r i e s o f isothermal


determinations a t d i f f e r e n t temperatures as a f u n c t i o n o f temperature i s .
S i m i l a r l y , non-thermal methods, such as X-ray d i f f r a c t i o n , performed under a
c o n t r o l l e d temperature programme become t h e r m o a n a l y t i c a l determinations.

I n the

account t h a t f o l l o w s , however, o n l y those methods normally i n c l u d e d i n thermal


a n a l y s i s w i l l be considered:

i t should be observed t h a t c l a s s i c a l c a l o r i m e t r y i s

excluded, d e s p i t e i t s c l o s e r e l a t i o n s h i p t o some thermoanalytical methods.

1.2.1

A v a i l a b l e t h e r m o a n a l y t i c a l techniques.

A general c l a s s i f i c a t i o n o f methods c u r r e n t l y recognized as t h e r m o a n a l y t i c a l


i s given i n Table 1.1 along w i t h t h e p h y s i c a l p r o p e r t y on which they depend and,

'for common methods where i t i s g e n e r a l l y i n use, t h e acceptable a b b r e v i a t i o n


(Lombardi, 1980).

Most o f t h e techniques can be d e f i n e d i n e x a c t l y t h e same way

as thermal a n a l y s i s , t h e p h y s i c a l p r o p e r t y i t s e l f

"mass" f o r thermogravimetry,

"an e l e c t r i c a l c h a r a c t e r i s t i c " f o r "thermoelectrometry':


"a physical p r o p e r t y " i n t h e d e f i n i t i o n .
wording i s necessary.

etc.

r e p l a c i n g t h e words

I n some instances, however, more p r e c i s e

For example, s i x methods a r e l i s t e d as being dependent on

change i n mass, b u t o n l y two a r e so dependent d i r e c t l y : i s o b a r i c mass-change

TABLE 1.1
Classification of thermoanalytical techniques
Physical property

Derived techniques

Mass

Isobaric mass-change determination


Thermogravimetry
Evolved gas detection
Evolved gas analysis
Emanation thermal analysis
Thermoparticulate analysis
Heating-curve determination*
Differential thermal analysis
Differential scanning calorimetry?
Thermodilatometry
Thermomechanical measurement+
Thermosonimetry5
Thermoacoustimetryg
Thermoptometry
Thermoel ectrometry
Thermomagnetometry

Temperature

En tha 1 py
Dimensions
Mechanical characteristics
Acoustic characteristics
Optical characteristics
Electrical characteristics
Magnetic characteristics

Abbreviation
TG
EGD
EGA

DTA

osc

I n t h e c o o l i n g mode t h i s becomes Cooling-curve determination.

Two t y p e s , Power-compensation DSC and Heat-flux DSC, can be d i s t i n g u i s h e d .

T e s t s under o s c i l l a t o r y l o a d come under t h e heading Dynamic thermomechanical

measurement.

5 Thermosonimetry r e f e r s t o sound e m i t t e d by t h e sample whereas


Thermoacoustimetry i n v o l v e s measurement o f changes i n t h e c h a r a c t e r i s t i c s o f
imposed a c o u s t i c waves p a s s i n g through t h e sample.

determination, which covers equilibrium techniques, such as the once common


"dehydration curves" under a constant partial pressure of water vapour, and
thermogravimetry- (TG), which uses a dynamic temperature programme. Evolved gas
detection (EGO) and evolved gas analysis (EGA) are secondary techniques whereby
materials evolved during heating are detected or analysed, respectively, and the
remaining two, emanation thermal analysis and thermoparticulate analysis, are
tertiary techniques, being special instances of EGA related to radioactive
emanation and particulate matter, respectively. A common method that is not
listed i n Table 1.1 is derivative thermogravimetry (DTG), the reason being that
derivative curves can be calculated for most measurements and it would be invidious
to include only one. Attention should also be drawn to the distinction between
derivative and differential, the former applying to the mathematical process and
the latter being used only as the adjectival form of "difference" (Lombardi, 1980).
Thus, in "differential thermal analysis" (and "differential scanning calorimetry")
the "difference in temperature between" (and "the difference in energy inputs
into"), "a substance and a reference material is measured". Moreover, heating

a
curves

i.e.

derivatives
(T)
T

curves f o r sample temperature against tlme

- "heating-rate

curves", where

dT/dt

- give r i s e t o

two

i s p l o t t e d against temperature

o r time ( t ) , and "inverse heating-rate curves" where

dt/dT

i s p l o t t e d against

o r t: both these have been e x t e n s i v e l y used i n the past.


The i n f o r m a t i o n given above, together w i t h t h a t i n Table 1.1, i s probably

adequate t o a l l o w appreciation o f t h e enormous s t r i d e s t h a t have been made over


the past decade o r so i n o b t a i n i n g i n t e r n a t i o n a l agreement on a general nomenc l a t u r e and c l a s s i f i c a t i o n system f o r thermoanalytical techniques.

This e f f o r t ,

however, has covered n o t o n l y nomenclature o f methods b u t a l s o t h a t o f components


o f equipment, o f aspects o f experimental" technique, o f c r i t i c a l p o i n t s on curves

and o f symbols (Lombardi, 1980) and has been f o r t u n a t e enough t o r e c e i v e the


backing o f n a t i o n a l and i n t e r n a t i o n a l standards i n s t i t u t i o n s , such as AFNOR, ASTM
and ISO, as w e l l as o f major i n t e r n a t i o n a l bodies such as IUPAC (1974, 1980).
Moreover, t h e recommendations i n English have been converted i n t o forms acceptable
i n many other language-speaking areas (Lombardi, 1980; Mackenzie, 1981b), since
d i r e c t t r a n s l a t i o n i s n o t always p o s s i b l e because o f already accepted conventions
i n other languages.
1.2.2
Simultaneous techniques
I t i s o f t e n convenient t o make two o r more measurements on one sample a t the
same time, leading t o "simultaneous determinations" such as DTA-EGA, TG-EGA,
DTA-TG-DTG,

etc.

This has advantages and disadvantages, and one has t o study n o t

only t h e bases o f the techniques themselves b u t a l s o t h e nature o f t h e samples


involved before deciding on t h e i r use. For example, EGA i s most p r o f i t a b l y
employed i n conjunction w i t h DTA o r TG, as one can then r e l a t e the evolved
v o l a t i l e s t o s p e c i f i c changes i n t h e sample; s i m i l a r l y , by comparing simultaneous
DTA and DTG curves one can r e a d i l y r e l a t e r e a c t i o n s i n v o l v i n g mass change w i t h

s p e c i f i c enthalpy changes.

And, o f course, t h e r e i s a considerable saving i n

both time and m a t e r i a l .

The major disadvantage i s t h a t optimum c o n d i t i o n s f o r


one technique may n o t necessarily be those f o r another. However, t h i s can be
f o r example, i n
minimized by c a r e f u l s e l e c t i o n of experimental c o n d i t i o n s

simultaneous DTA-TG, by using a small sample and/or employing a slow heating r a t e .


1.2.3

Standardization o f techniques

Since thermoanalytical r e s u l t s can vary w i t h experimental technique, t h e


Standardization Committee o f ICTA have published a code o f p r a c t i c e l i s t i n g t h e
i n f o r m a t i o n t h a t should be supplied w i t h every curve published: they have a l s o
been instrumental i n p r o v i d i n g m a t e r i a l s f o r temperature c a l i b r a t i o n o f apparatus
(Lombardi, 1980). These aspects should be thoroughly studied by anyone considering
a p p l i c a t i o n o f thermal analysis.

9
1.3

APPLICATIONS TO CLAYS
Emphasis in this article I ' s , quite deliberately, on the applications or
potential applications of the various techniques now available to clays. It is,
therefore, impossible to deal adequately with Instrumentation, experimental
technique, or even with some basic principles, although all these are critical in
determining the quality of thermoanalytical results. To overcome this deficiency
the reader is referred to the books of Daniels (1973) and Wendlandt (1974) and to
the excellent reviews that have appeared biennially in A n a l y t i c a l C h e m i s t r y
Fundamental R e v i e w s (e.g. Murphy, 1978) for a considerable period.
In the account that follows, clay mineralogical applications take priority,
but due consideration must also be given to the wider field of applications to
clays and clay rocks of technological or industrial importance and to accessory
minerals, since the presence or absence of these may well determine the suitability
of a clay for a particular application. With this wide field in mind, it will be
appreciated that the references given are illustrative only: an exhaustive study
of all published work would be inordinately long.
1.3.1

IIsobaric) mass-change determination


In isobaric mass-change determination the sample is heated at each selected
temperature until there is no further mass change and the e q u i l i b r i u m mass is
plotted against the temperature: the partial pressure o f the evolved volatile
(e.g. water or carbon dioxide) is maintained constant throughout the determination
An excellent description of the technique has been given by Weiser and Milligan
(1939).

In the past this technique, although not perhaps in an isobaric mode, was
widely applied to clays in the derivation of so-called "dehydration curves". An
excellent collection of these was given by Nutting (1943) and the technique was
still employed for characterization purposes in the 1950s (see e.g., Mackenzie,
1957a). It is rather time-consuming and with the advent of thermogravimetry
seems to have fallen into disuse. However, families of isothermal mass-change
curves, particularly in their isobaric mode, can probably yield more reliable
information on the kinetics of reactions than the TG curves so commonly in use
(see below).
1.3.2

Thermogravirnetry (TG)
Although DTA has been the most widely used technique in clay mineralogy, the
use o f TG and DTG has grown markedly, particularly since the introduction of the
Derivatograph, which provided simultaneous DTA-TG-DTG curves, and its commercial
production in Hungary in the mid-1950s. This instrument, which is by far the
most widely used, and apparently the only one comnercially produced in eastern
Europe, has been upgraded several times and now has various optional additional

i 0
attachments f o r thermodilatometry, EGA, etc.

( P a u l i k and Paulik, 1978).

I t s value

i n c l a y mineralogy i s r e a d i l y assessed from t h e simultaneous curves f o r a l a r g e


number o f c l a y s and c l a y m i n e r a l s published by Langier-Kuzniarowa (1967).

Out-

s i d e e a s t e r n Europe, thermogravimetry was s t i m u l a t e d by t h e commercial p r o d u c t i o n


o f t h e r o b u s t Stanton thermobalance i n 1954 and simultaneous techniques by t h e
i n t r o d u c t i o n o f the M e t t l e r Thermoanalyzer (Wiedemann, 1964).

A wide range o f

thermobalances and simultaneous DTA-TG instruments s u i t a b l e f o r c l a y s t u d i e s can


now be purchased (e.g.

Dunn, 1980). t h e number o f the l a t t e r tending t o increase

as a v a i l a b l e s e n s i t i v i t y has increased.

O f the various types of balance system

used (Keattch and Dollimore, 1975), t h e n u l l - p o i n t e l e c t r o b a l a n c e now seems t h e


most common.

When simultaneous equipment i s n o t used and a comparison i s made

between DTA and DTG curves, g r e a t care must be taken t o ensure t h a t a l l experimental
v a r i a b l e s are i d e n t i c a l f o r b o t h determinations

f o r example, use o f a d i f f e r e n t

h e a t i n g r a t e can d i s p l a c e peaks and even a l t e r peak shape a p p r e c i a b l y ( A l i e t t i ,


B r i g a t t i and Poppi, 1979).
The main uses o f TG add DTG (which must be considered t o g e t h e r ) i n c l a y
mineralogy have been i n determining t h e reasons f o r DTA peaks, assessing t h e range
over which r e a c t i o n s occur and o b t a i n i n g q u a n t i t a t i v e i n f o r m a t i o n .

The methods

a r e n o t p a r t i c u l a r l y s u i t a b l e f o r i d e n t i f i c a t i o n studies, although t h e occurrence


o f one o r two peaks on a DTG curve, and the r e l a t i v e s i z e s o f t h e two peaks when
they appear, can apparently be employed i n c h a r a c t e r i z i n g s e r p e n t i n e m i n e r a l s
(Morandi and F e l i c e , 1979) and t h e disappearance o f the hygroscopic m o i s t u r e peak
a f t e r K - s a t u r a t i o n can be used t o d i s t i n g u i s h h y d r o b i o t i t e from m o n t m o r i l l o n i t e

i n some s o i l s (Ryzhova, 1980).

These must be regarded as r a t h e r i s o l a t e d instances

and t h e main use o f the techniques has undoubtedly been t o o b t a i n q u a n t i t a t i v e


i n f o r m a t i o n on evolved v o l a t i l e s , e t c .

I n such a p p l i c a t i o n s , however, g r e a t care

must be exercised, as t h e mass change, during, f o r example, a d e h y d r o x y l a t i o n


r e a c t i o n , could be s e r i o u s l y affected iff e r r o u s i r o n i n t h e l a t t i c e were
simultaneously o x i d i z e d t o f e r r i c .

For t h i s reason too, q u a n t i t a t i v e determina-

t i o n o f m i n e r a l s by DTG (Smalley and Xidakis, 1979) should be undertaken o n l y


when s u f f i c i e n t c o n f i r m a t o r y evidence t h a t n o t h i n g l i k e l y t o i n t e r f e r e w i t h t h e
DTG peak area i s present and when comparison can be made w i t h a mineral t h a t i s

i d e n t i c a l w i t h t h a t i n the c l a y .

I t i s noteworthy i n t h i s respect t h a t even t h e

s a t u r a t i n g c a t i o n o f m o n t m o r i l l o n i t e a f f e c t s t h e c h a r a c t e r and temperature o f
the DTG dehydroxylation peak (Schomburg and S t b r r ,

1978a).

TG has proved

valuable i n e l u c i d a t i n g t h e nature of DTA peaks f o r p a l y g o r s k i t e and s e p i o l i t e


(Fernandez Alvarez, 1978) and f o r m o n t m o r i l l o n i t e ( I l i u t a , Drimus and Preda, 1978)
and OTG i n r e v e a l i n g m u l t i p l e r e a c t i o n s n o t obvious on t h e TG curve (e.g.
Rautureau and Fornes, 1978).

Mifsud,

Changes i n t h e temperature range and magnitude o f

t h e step on t h e TG, o r peak on t h e DTG, curve can p r o v i d e v a l u a b l e c o n f i r m a t o r y


evidence f o r a p a r t i c u l a r phenomenon, such as t h e occurrence o f NH,+

i n some

11

Japanese dioctahedral micas (Higashi, 1978): the presence o f t h i s i o n not o n l y


moves t h e dehydroxylation r e a c t i o n t o a lower temperature b u t a l s o increases t h e
mass l o s s because o f the e v o l u t i o n o f NH,.
TG and DTG also y i e l d useful i n f o r m a t i o n on accessory minerals.

Thus, t h e

dehydroxylation o r decarbonation o f accessory hydroxide o r carbonate minerals i s


u s u a l l y obvious on TG and DTG curves (e.g. Iwasa, 1978) and, provided c a r e f u l
c a l i b r a t i o n i s performed i n advance, even s a l t s , such as sodium carbonate and
sodium c h l o r i d e , can be q u a n t i t a t i v e l y determined i n s a l i n e c l a y s (Asomoza et ai.,
1978).
TG has been e x t e n s i v e l y i n v e s t i g a t e d as a means f o r studying t h e k i n e t i c s o f
r e a c t i o n s because ( a ) determinations are l e s s time-consuming than isothermal
i n v e s t i g a t i o n s , (b) w i t h isothermal methods, some r e a c t i o n occurs before the
temperature o f i n t e r e s t i s reached and ( c ) the whole temperature range i s covered
w i t h o u t any missing regions (see Sharp, 1972).

While these comments are c o r r e c t ,

actual l i m i t a t i o n s on the d e r i v a t i o n o f k i n e t i c parameters are formidable, n o t


o n l y because o f the occurrence of temperature gradients w i t h i n t h e sample but
a l s o because o f other more fundamental aspects d e a l t w i t h below.

Most methods

f o r i n t e r p r e t i n g TG curves are based on t h e simple r a t e equation


da/dt

k(1

- a)"

(where a i s the f r a c t i o n decomposed i n time t , n the order o f r e a c t i o n and

the

r a t e constant) combined w i t h t h e Arrhenius equation


(2)

k = Aexp (-E/RT)

(where A i s t h e pre-exponential f a c t o r , E the a c t i v a t i o n energy and R the gas


constant), t h e temperature

(where

T~

being defined by

i s the i n i t i a l temperature and 8 , = d T / d t , the heating r a t e ) : note t h a t

the heating r a t e i s assumed t o be c o n s t a i t .

The two usual procedures are then

e i t h e r t o f o l l o w t h e d i f f e r e n t i a t i o n method o f Freeman and C a r r o l l (1958) o r the


i n t e g r a t i o n method o f Coats and Redfern (1963).

The l a t t e r i s generally regarded

as y i e l d i n g most r e l i a b l e r e s u l t s - see, f o r example, t h e recent study o f Boy and


BMhme (1979) and compare t h e i r r e s u l t s f o r t h e dehydroxylation o f k a o l i n i t e w i t h
those determined by a v a r i e t y o f experimental methods (Sharp, 1972).
I n a l l these studies approximations a r e involved and, although the d i f f i c u l t i e s
inherent i n dealing w i t h a dynamic system (see Sharp, 1972) are imnense, other
more fundamental aspects must a l s o be remembered.

One need o n l y consider t h e

1 2

equations above.

The f i r s t two a r e gas-phase equations and t h e r e i s no guarantee

they would apply t o a s o l i d : moreover, one could j u s t i f i a b l y query t h e physical


s i g n i f i c a n c e o f the derived "order o f r e a c t i o n " and " a c t i v a t i o n energy" when so
applied. Indeed, recent EGA studies have shown t h a t decomposition r e a c t i o n s can,
n o t unexpectedly, change mechanism during the r e a c t i o n (Garn, Kawalec and Chang,
1978; P r i c e e t al., 1980).

Moreover, many s o l i d - s t a t e decompositions i n powder

systems a r e d i f f u s i o n c o n t r o l l e d ( s e n s u l a t o , covering both i n t e r - and i n t r a p a r t i c l e d i f f u s i o n ) , o r f o l l o w some o t h e r law, so t h a t t h e "order o f r e a c t i o n " i s


r a t h e r meaningless (Sharp, 1972).

Consequently, Garn (1979) has q u i t e r i g h t l y

suggested t h a t t h e term " a c t i v a t i o n energy" should be replaced by "temperature


c o e f f i c i e n t o f reaction".

While t h e use o f small samples and/or o f a constant

temperature regime over the decomposition i n t e r v a l (Rouquerol, 1970; P a u l i k and


Paulik, 1972) would reduce temperature gradients t h a t i n t e r f e r e w i t h i n t e r p r e t a t i o n , these v a r i a n t s do n o t o b v i a t e t h e more fundamental o b j e c t i o n s and much
study i s s t i l l r e q u i r e d d e s p i t e t h e l a r g e numbers o f papers t o be found i n t h e
J o u r n a l of Thermal A n a l y s i s , Thermochimica A c t a and Thermal A n a l y s i s A b s t r a c t s

over the past decade.

It should be noted, however, t h a t the basic o b j e c t i o n s

r a i s e d above do n o t necessarily mean t h a t t h e numerical vaiues obtained f o r c e r t a i n


k i n e t i c parameters have no p r a c t i c a l value.
1.3.2.1

Evolv-d gas d e t e c t i o n (EGD)

I n EGD one determines whether o r n o t gas e v o l u t i o n i s associated w i t h a thermal


effect.

I t i s customary, therefore, t o use i t i n conjunction w i t h DTA (mass loss

being adequate i n d i c a t i o n o f gas e v o l u t i o n i n TG) and t h e s i m p l e s t method i s t o


i n s e r t a thermal c o n d u c t i v i t y c e l l i n the c a r r i e r gas stream coming from t h e
equipment (Ingraham, 1967), although several o t h e r methods are a l s o a v a i l a b l e
(Daniels, 1973).
An EGD technique t h a t has proved very useful i n studying polymer degradation
on heating i s thermal v o l a t i l i z a t i o n a n a l y s i s (McNeill, 1977).

I n t h i s t h e sample

i s heated i n a high vacuum chamber connected t o a vacuum pump though a t r a p cooled


i n l i q u i d nitrogen, the pressure between t h e sample and the t r a p being measured
by a P i r a n i gauge.

Whenever t h e sample decomposes, the pressure increases and

the decomposition o f the polymer can thus be followed.

The method i n t h i s form

does n o t g i v e any i n d i c a t i o n o f t h e v o l a t i l e products formed b u t t h e equipment


has been modified so t h a t the condensed v o l a t i l e s i n t h e c o l d t r a p b o i l o f f as
t h e t r a p i s allowed t o heat up.

Since t h e b o i l i n g p o i n t permits each component

t o be i d e n t i f i e d (McNeill, 1980), t h e method i s upgraded t o EGA

- always

assuming

t h e r e i s no i n t e r a c t i o n between condensed v o l a t i l e s .

A method f o r simultaneous DTA and EGD by measuring the i n t e n s i t y o f a l a s e r


beam t r a v e r s i n g t h e sample c e l l above the sample has r e c e n t l y been described i n
N e t s u s o k u t e i (1980).

Although a p p l i e d t o d e r i v e the phase diagram o f a known

13
b i n a r y l i q u i d system, t h e method i s c l e a r l y non-specific and could probably be
adapted t o DTA-EGD o f clays o r clay-organic complexes: i t s advantage l i e s i n t h e
f a c t t h a t i t gives a very sharp i n f l e c t i o n immediately vapour e v o l u t i o n commences
even w i t h very slow heating rates.
1.3.2.2

Evolved g a s a n a l y s i s (EGA)

EGA i s much more useful, and indeed

usual, than EGD, since i t enables

determination o f t h e i d e n t i t y and/or amount o f the evolved v o l a t i l e material.

It

i s normally employed along w i t h DTA, TG o r DTA-TG-DTG, thus enabling q u a n t i t a t i v e


e v a l u a t i o n q f the e f f e c t s on t h e curves i n terms o f s p e c i f i c v o l a t i l e s .
Basic i n f o r m a t i o n on various methods o f EGA, such as mass spectrometry, gas
chromatography, i n f r a - r e d absorption and s e l e c t i v e sorption, w i l l be found i n the
books o f Lodding (1967), Mackenzie (1970-72), Daniels (1973) and Wendlandt (1974),
i n t h e Proceedings o f the various I n t e r n a t i o n a l Conferences on Thermal Analysis
(Redfern, 1965; Schwenker and Garn, 1968; Wiedemann, 1972, 1980; B U Z ~ S , 1975;
Chihara, 1977), i n t h e Proceedings o f the F i r s t European Symposium on Thermal
Analysis (Dollimore, 1976) and i n various s c i e n t i f i c j o u r n a l s .
B r i e f l y , t h e methods of EGA f a l l i n t o two classes: ( a ) those f o r which
p r i o r knowledge of t h e nature o f the v o l a t i l i z e d m a t e r i a l i s unnecessary and
( b ) those f o r which such knowledge i s essential. While the former, which
i n c l u d e mass spectrometry and gas chromatography, are by f a r the most generally
useful, t h e l a t t e r have a d e f i n i t e place i n studies, such as those on clays, where
a l i m i t e d number of v o l a t i l e m a t e r i a l s are t o be expected. Both have indeed been
a p p l i e d i n c l a y studies: f o r example, Mhller-Vonmoos and M h l l e r (1975) have
demonstrated how mass spectrometry combined w i t h DTA can reveal the presence o f
organic carbon, p y r i t e and various carbonate minerals i n a clay, whereas Morgan
(1977) has used DTA and separate detectors t o determine when and how much water,
carbon d i o x i d e and- sulphur d i o x i d e (from o x i d a t i o n o f p y r i t e ) a r e evolved from
clays, shales and s c h i s t s and P a u l i k and P a u l i k (1978) have used t h e i r technique
o f thermal gas t i t r i m e t r y (i.e.

sorption o f the v o l a t i l e i n a suitable solution

o r solvent f o l l o w e d by t i t r a t i o n ) along w i t h DTA-TG-DTG t o determine the amounts


o f contaminating a l u n i t e and c a l c i t e i n bauxites.
The optimum technique depends on circumstances

and, n o t infrequently,on

finance.

While a s e r i e s o f detectors s p e c i f i c f o r one v o l a t i l e o n l y can be r e a d i l y


and r e l a t i v e l y cheaply purchased and attached i n s e r i e s t o a s u i t a b l e thermal
analysis instrument, t h e more f l e x i b l e and universal system using mass spectrometry i s expensive.

I n s e t t i n g up equipment and assessing r e s u l t s several important


aspects must be kept i n mind: for example, t h e free, volume around the sample must

be r e l a t i v e l y small t o avoid undue d i l u t i o n o f evolved m a t e r i a l w i t h c a r r i e r gas,


t h e i n t e r f a c e between a mass spectrometer and t h e thermal analysis instrument
must be chosen w i t h care so t h a t one v o l a t i l e i s n o t p r e f e r e n t i a l l y enriched a t

1 4
t h e expense o f another, and t h e l i k e l i h o o d of two v o l a t i l e s r e a c t i n g b e f o r e
measurement must be assessed.

A v a r i a n t o f EGA, pyrolysis-gas chromatography-mass spectrometry, which was


developed m a i n l y f o r t h e study o f s y n t h e t i c polymers, has proved extremely u s e f u l
i n t h e i n v e s t i g a t i o n and c h a r a c t e r i z a t i o n o f s o i l organic m a t t e r (Bracewell and
Robertson, 1977) and should a l s o be a p p l i c a b l e t o o r g a n i c m a t t e r i n c l a y deposits.
I n t h i s method the sample i s very r a p i d l y pyrolysed i n an i n e r t atmosphere, t h e
products being separated by gas chromatography and i d e n t i f i e d by mass spectrometry.
Such a procedure y i e l d s f a i r l y l a r g e fragments o f t h e o r i g i n a l molecules, thus
g i v i n g an i n s i g h t i n t o t h e n a t u r e o f t h e organic polymers present.

I n some

circumstances, and p a r t i c u l a r l y when i n t e r a c t i o n between products i s l i k e l y t o


occur, a p r e f e r a b l e system i s pyrolysis-mass spectrometry (Bracewell and Robertson,
1980), d e s p i t e i t s h i g h e r c o s t because o f t h e more e l a b o r a t e data h a n d l i n g system
required.
1.3.2.2.1
Ema n a t ion t h e r m a l a n a l y s i s . T h i s i s e s s e n t i a l l y a v a r i a n t o f EGA where
t h e r a d i o a c t i v e emanation evolved d u r i n g h e a t i n g o f t h e sample i s measured. While
t h i s d e f i n i t i o n would n o r m a l l y i n c l u d e o n l y radon isotopes, i n p r a c t i c e t h e method
has been extended t o non-radioactive i n e r t gases, such as argon, k r y p t o n o r xenon,
and t h e i r r a d i o a c t i v e isotopes: t h e r e i s thus a g r a d a t i o n i n t o normal EGA.

Materials

n o t c o n t a i n i n g i n e r t gas can be l a b e l l e d by d i f f u s i n g gas i n t o t h e s o l i d a t h i g h


pressures and temperatures, by i n c l u d i n g t h e gas d u r i n g synthesis o r by bombardi n g t h e s u r f a c e o f the sample w i t h a c c e l e r a t e d ions o f i n e r t gas.

Changes i n gas

r e l e a s e r a t e on h e a t i n g can then be c o r r e l a t e d w i t h dehydration, decomposition,


r e c r y s t a l l i z a t i o n , phase t r a n s i t i o n , s o l i d - s t a t e r e a c t i o n s and changes i n s u r f a c e
properties.

Development o f emanation thermal a n a l y s i s i n c o n j u n c t i o n w i t h DTA i s

due mainly t o Balek and h i s c o l l a b o r a t o r s i n Czechoslovakia and i n f o r m a t i o n on


theory, i n s t r u m e n t a t i o n and a p p l i c a t i o n s i s b e s t obtained from a r e c e n t exhaustive
review (Balek, 1977).

Although no s e r i o u s s t u d i e s seem y e t t o have been made on

c l a y s , accessory minerals such as i r o n oxides, q u a r t z and z e o l i t e s have r e c e i v e d


attention.

Several p o s s i b l e a p p l i c a t i o n s t o c l a y minerals, p a r t i c u l a r l y h o l l o w

f i b r o u s and h i g h l y disordered species, s p r i n g t o mind, b u t i t has y e t t o be


e s t a b l i s h e d whether t h e i n f o r m a t i o n obtained would be s u p e r i o r t o t h a t f r o m more
conventional methods.
So-called "temperature-programmed d e s o r p t i o n curves" might we1 1 be regarded
as r e l a t e d t o t h e above, even although t h e gases i n v o l v e d a r e n o t i n e r t .

Recent . _

work w i t h these (Criado et ai., 1980) has c l e a r l y shown t h e i r value i n s t u d y i n g


t h e k i n e t i c s o f d e s o r p t i o n o f sorbed gas.
1.3.2.2.2

T h e m o p a r t i c u l a t e a n a l y s i s . Since t h e degradation o f s y n t h e t i c polymers

y i e l d s condensation n u c l e i as w e l l as molecular species, t h e r m o p a r t i c u l a t e a n a l y s i s ,

1 5

whereby t h e amount (and sometimes i d e n t i t y ) o f such n u c l e i a r e measured as a


f u n c t i o n o f temperature, i s c l e a r l y c l o s e l y r e l a t e d t o EGA. P a r t i c l e s o f t h e
order o f 1-100 nm i n s i z e a r e i n v o l v e d and an e a r l y review o f equipment, technique
and a p p l i c a t i o n s was g i v e n by Murphy (1967).

A more r e c e n t v a r i a n t ( g i v e n various

names by i t s o r i g i n a t o r s ) i s a c l o s e r e l a t i v e o f EGD, s i n c e n e i t h e r the amount


nor i d e n t i t y o f t h e p a r t i c l e s i s measured, b u t when combined w i t h mass spectrometry
becomes again e s s e n t i a l l y EGA (see Smith, P h i l l i p s and Kaczmarek, 1976; Smith,
Meier and P h i l l i p s , 1977).
Although t h e technique has been a p p l i e d o n l y t o l a r g e organic molecules t h e r e
a r e p o s s i b i l j t i e s o f a p p l i c a t i o n i n c o n d i t i o n s where chemical t r a n s p o r t occurs.
Since chemical t r a n s p o r t has r e c e n t l y been observed on h e a t i n g c e r t a i n i r o n oxides

(E. Paterson, personal communication), i t i s , therefore,


applications e x i s t i n the c l a y f i e l d .
1.3.3

marginally possible t h a t

Heating curve determination

Heating curves and the two d e r i v a t i v e s , h e a t i n g - r a t e curves and i n v e r s e heati n g - r a t e curves, were a t one time w i d e l y used i n c l a y s t u d i e s : indeed, t h e f i r s t
thermoanalytical records f o r c l a y s were, as mentioned above, h e a t i n g - r a t e curves.
However, h e a t i n g curves f e l l i n t o disuse, as t h e low s e n s i t i v i t y o f r e c o r d i n g
necessary t o cover the whole temperature range o f i n t e r e s t precluded d e t e c t i o n
o f small thermal e f f e c t s , and i n t e r e s t i n t h e two d e r i v a t i v e curves waned as DTA
became established, s i n c e e s s e n t i a l l y t h e same i n f o r m a t i o n c o u l d be obtained more
readily.

So f a r as t h e author i s aware, no heating-curve determinations on clays

a r e now performed.

1.3.4
D i f f e r e n t i a l thermal a n a l y s i s (DTA)
DTA i s by f a r t h e best known and most w i d e l y used thermoanalytical technique
i n c l a y studies, whether on i t s own o r simultaneously w i t h o t h e r methods such as

TG, EGA, e t c .

I t s main uses a r e i n " f i n g e r - p r i n t i n g " specimens, i n d e t e c t i n g

c e r t a i n accessory m i n e r a l s and "abnormal" species o f c l a y minerals, i n d e t e c t i n g


changes i n mineralogy w i t h depth o r distance, i n q u a n t i t a t i v e (or, more f r e q u e n t l y ,
s e m i - q u a n t i t a t i v e ) s t u d i e s and i n determining heat s t a b i l i t y o r t h e occurrence o f
solid-state reactions.

L i m i t a t i o n s imposed by i n s t r u m e n t a t i o n , technique and

n a t u r a l v a r i a t i o n s i n m i n e r a l s make accurate q u a n t i t a t i v e work d i f f i c u l t and


preclude i t s use d i a g n o s t i c a l l y , except i n s p e c i a l circumstances.

A s these d e t a i l s

and p o s s i b l e methods o f m i n i m i z i n g l i m i t a t i o n s a r e so wel1,known (see Mackenzie,


1957b, 1970-72),

t h e method w i l l n o t be d e a l t w i t h here a t any g r e a t l e n g t h and

reference w i l l be made o n l y t o some r e c e n t developments.


Commercial equipment design has improved enormously over t h e p a s t decade and,
although t h e r e may n o t be so many instruments on t h e market now as a few years
ago, those companies t h a t c u r r e n t l y manufacture equipment have introduced many

16
improvements,

While no instrument i s u n i v e r s a l and t h e instrument must be chosen

having regard t o t h e proposed a p p l i c a t i o n s , t h e general t r e n d towards t h e use o f


small samples o f o n l y a few m i l l i g r a m s i s t o be welcomed, as i t minimizes e r r o r s
due t o thermal g r a d i e n t s and, provided r e c o r d i n g s e n s i t i v i t y i s adequate, enables
simultaneous DTA-TG t o be v a l i d l y used.

The f a c t t h a t two markedly d i f f e r e n t DTA

instruments y i e l d e s s e n t i a l l y t h e same curves f o r a d e h y d r o x y l a t i o n r e a c t i o n when


sample s i z e i s l e s s than 30 mg (Broersma et ai.,
very small samples.

1978) confirms t h e value o f using

Many manufacturers a l s o produce several types o f specimen

holders f o r e a c h instrument ,so t h a t t h e optimum (Wilburn, 1972) can be selected,


and c o n t r o l o f atmosphere around the Sample i s now u n i v e r s a l .

These advances i n

i n s t r u m e n t a t i o n enable DTA t o be much more w i d e l y and v a l i d l y used i n c l a y s t u d i e s


than ever before.
An advance i n methodology has been the i o t r o d u c t i o n o f stepwise h e a t i n g (Staub
and Perron, 1974; Simonsen and Zaharescu, 1979), by which temperature i s increased
i n small steps (0.5-10C,

depending on t h e r e a c t i o n ) i n s t e a d o f continuously,

e q u i l i b r i u m being a t t a i n e d a t each step.

This i s e s s e n t i a l l y e q u i v a l e n t t o

o b t a i n i n g a s e r i e s o f isothermal measurements d u r i n g one d e t e r m i n a t i o n w i t h t h e


r e s u l t t h a t heats o f m e l t i n g , t r a n s i t i o n , etc.,

can be determined more a c c u r a t e l y .

To t h e a u t h o r ' s knowledge, t h i s technique has n o t y e t been a p p l i e d t o clays: t h e r e


i s no reason t o suppose i t i s i n a p p l i c a b l e , although any apparent advantages would
have t o be c r i t i c a l l y checked.

The sample c o n t a i n e r can sometimes have an undesir-

a b l e e f f e c t ( M a r t i n V i v a l d i , G i r e l a V i l c h e z and F e n o l l Hach-Ali, 1964; D o l l i m o r e


and Mason, 1981): t o prevent c o n t a i n e r e f f e c t s i n m e t a l l u r g y , electromagnetic
l e v i t a t i o n of the sample has been introduced (Jorda, F l U k i g e r and MUller, 1978)
b u t t h i s would u n f o r t u n a t e l y be impossible w i t h c l a y s and t h e m a t e r i a l o f the
specimen holder must be c a r e f u l l y selected.

The n e c e s s i t y f o r care i n sample

p r e p a r a t i o n has been emphasized by work on q u a r t z (Moore and Rose, 1979), where


small exothermic peaks observed a f t e r g r i n d i n g i n s t e e l and agate v i b r a t i o n m i l l s
have been a t t r i b u t e d t o o x i d a t i o n o f contaminating i r o n and r e l e a s e o f s t o r e d
energy, r e s p e c t i v e l y .

On t h e o t h e r hand, t h e doubling o f t h e d e h y d r o x y l a t i o n

endotherm o f g o e t h i t e on g r i n d i n g has been a t t r i b u t e d t o p a r t i c l e s i z e e f f e c t s


(Murad, 1979).

The value o f c o n t r o l l e d atmosphere has been confirmed by s t u d i e s

on carbonate minerals, which show t h a t i n a carbon d i o x i d e atmosphere t h e m i n e r a l s


present can be i d e n t i f i e d and t h e amounts estimated f o r o n l y 0.125 mg i n a 50 mg
sample (Warne and M i t c h e l 1 , 1979).
The main use o f DTA i n c l a y studies, r e c e n t l y as i n t h e past, has been as an
a d j u n c t t o o t h e r techniques i n c h a r a c t e r i z a t i o n s t u d i e s .

Yet some i n v e s t i g a t i o n s

r e v e a l t h e value o f the technique i n i t s own r i g h t , and i t may be a p p o s i t e t o


c i t e some examples.

Thus, peak temperature o f the low-temperature endotherm f o r

H-saturated allophane and t h a t o f the high-temperature exotherm f o r Na-allophane


increases and decreases, r e s p e c t i v e l y , w i t h i n c r e a s i n g SiO,:Al,O,

r a t i o (Henmi,

17
1980).

Moreover, t h e exotherm o f allophane i s lowered i n temperature and

broadened on admixture w i t h i r o n o x i d e g e l s o r hydrous i r o n o x i d e minerals,


whereas i t i s u n a f f e c t e d by oxide m i n e r a l s such as hematite o r maghemite (Suzuki
and Satoh, 1980).

For d i c k i t e s , i n c r e a s i n g breadth o f t h e dehydroxylation

endotherm seems t o be approximately associated w i t h i n c r e a s i n g degree of disorder,


although some exceptions suggest t h i s r u l e i s n o t r i g i d ( B r i n d l e y and P o r t e r ,
1978).

I t i s w e l l knownthat DTA curves o f i n t e r s t r a t i f i e d m i n e r a l s a r e d i f f i c u l t

to interpret

presumably because d e h y d r o x y l a t i o n o f one l a y e r n e c e s s a r i l y a f f e c t s

t h a t o f neighbouring l a y e r s whether o r n o t they a r e o f the same t y p e

b u t i t has

r e c e n t l y been shown t h a t the shape and s i z e of t h e hygroscopic m o i s t u r e peak f o r


Sr-saturated mica-montmorillonites can be used t o assess t h e p r o p o r t i o n o f expansi b l e l a y e r s present (Inoue, Minato and Utada, 1978).

Since s o l i d - s t a t e r e a c t i o n s

t h a t occur between carbonate minerals, s o l u b l e s a l t s and mica on h e a t i n g a l s o take


place w i t h m i c a - m o n t m o r i l l o n i t e b u t n o t w i t h p a l y g o r s k i t e (Mashhady et al., 1980)
and manganese oxides r e a c t w i t h k a o l i n i t e i n t h e s o l i d s t a t e a t e l e v a t e d temperatures
(Holland and Segnit, 1976), c a r e must be taken i n i n t e r p r e t i n g curves f o r systems
I n p o l l u t i o n studies, t h e area o f t h e dehydroxylation

c o n t a i n i n g such mixtures.

endotherm o f c h y s o t i l e can a p p a r e n t l y be used t o assess asbestos content (Menis,


Mackey and Garn, 1978).

The e f f e c t s o f sorbed organic m a t e r i a l s on DTA curves

f o r c l a y m i n e r a l s have been examined by, i n t e r alia, Hllbner (1927) and Eltantawy


(1979), w h i l e c l a y - o r g a n i c r e a c t i o n products have been i n v e s t i g a t e d by Kuroda and
Kato (1979).
Although DTA has been w i d e l y used i n s t u d y i n g t h e k i n e t i c s o f r e a c t i o n s , t h e r e
i s no doubt t h a t t h e techniques used a r e f r a u g h t w i t h even more d i f f i c u l t i e s than
mentioned above f o r TG (Sharp, 1972).

However, a considerable p r o p o r t i o n o f

thermoanalytical papers do deal w i t h t h i s s u b j e c t and a t r e a t i s e on non-equilibrium


k i n e t i c s has appeared (Koch, 1977).

As mentioned above under TG, i t i s u n l i k e l y

t h a t decomposition o f s o l i d s f o l l o w s t h e same k i n e t i c s throughout t h e whole range


from a = 0 t o a = 100 (where a i s t h e f r a c t i o n reacted) and thus t h e best t h a t
can be expected would be t o deduce values f o r a l i m i t e d a range.
1.3.5

D i f f e r e n t i a l scanning c a l o r i m e t r y (DSC)

Two types o f DSC a r e recognized, power-compensation DSC and h e a t - f l u x DSC


(Table 1.1). The r e l a t i o n s h i p s between these and DTA have r e c e n t l y been discussed
i n d e t a i l (Mackenzie, 1980) and need n o t be repeated here.

It need only be

mentioned t h a t DSC was o r i g i n a l l y l i m i t e d t o a maximum temperature o f about 450C


because o f t h e i n c r e a s i n g importance above t h a t temperature o f r a d i a t i v e heat
t r a n s f e r : however, r e c e n t t e c h n o l o g i c a l advances have enabled t h e temperature
range t o be extended t o about 750-800C so t h a t a l i m i t e d a p p l i c a t i o n i n c l a y
mineralogy i s now possible.
The main advantage o f DSC over DTA i s t h a t i t i s i n h e r e n t l y q u a n t i t a t i v e f o r

18
change i n enthalpy, heat capacity, e t c .

Consequently, i t can, f o r example, be

used t o determine n o t o n l y t h e enthalpy change o c c u r r i n g d u r i n g a r e a c t


a l s o t h e t o t a l energy r e q u i r e d t o f i r e a c l a y over any s p e c i f i c temperatur,
up t o about 750C.

The method has, however, n o t been w i d e l y used i n t h e study

0,

clays, although i n v e s t i g a t i o n s on m o n t m o r i l l o n i t e (Homshaw and Chaussidon, 1979),


on smectites, z e o l i t e s , h a l l o y s i t e and opal (Eger, Cruz-Cumplido and F r i p i a t , 1979)
and on s y n t h e t i c g o e t h i t e (Paterson, 1980) suggest i t can y i e l d v a l u a b l e r e s u l t s ,
both q u a l i t a t i v e and q u a n t i t a t i v e , i n connection w i t h s o l v a t i o n problems.

I t has

a l s o been u s e f u l i n d e t e c t i n g d i f f e r e n t types o f surface hydroxyl groups on s y n t h e t i c


g o e t h i t e (Paterson and S w a f f i e l d , 1980) and i n r e v e a l i n g major d i f f e r e n c e s i n s o i l
and rock q u a r t z samples (Barwood and Hajek, 1979).
I n view o f these i n d i c a t i o n s , i t would appear t h a t DSC i s l i k e l y t o be increasi n g l y used i n c l a y s t u d i e s over t h e n e x t few years, p a r t i c u l a r l y i n q u a n t i t a t i v e
and surface i n v e s t i g a t i o n s .

An extension o f t h e c u r r e n t upper temperature l i m i t

would open even g r e a t e r prospects, b u t t h i s does n o t seem l i k e l y i n t h e near f u t u r e .


1.3.6

Thermodilatometry

I n thermodilatometry t h e volume or, more u s u a l l y , t h e l i n e a r dimensionsal


change on h e a t i n g i s s t u d i e d as a f u n c t i o n o f temperature under n e g l i g i b l e load.
The method i s an o l d one and indeed t h e o b s e r v a t i o n o f shrinkage o f c h i n a c l a y
on f i r i n g gave Wedgwood (1782) t h e idea f o r h i s famous pyrometer, which, although
g r o s s l y i n a c c u r a t e i n absolute terms, was t h e o n l y means a v a i l a b l e f o r a c c u r a t e l y
comparing h i g h temperatures f o r 50 years o r more from t h e 1780s.

Thermodilatometry i s a very common method i n ceramic technology, where a


knowledge o f t h e f i r i n g shrinkage o f c l a y i s e s s e n t i a l and where b l e n d i n g can be
used t o minimize such shrinkage.

I t has a l s o been a p p l i e d t o c l a y minerals, b u t

t h e determination i s so s e n s i t i v e t o degree o f o r i e n t a t i o n o f p l a t y minerals, t h e


nature and amounts o f accessories, etc.,
o f g r e a t value f o r i d e n t i f i c a t i o n ,

t h a t t h e r e s u l t s have n o t been considered

There have been r e c e n t i n d i c a t i o n s , however,

t h a t t h e method can have some l i m i t e d d i a g n o s t i c uses, s i n c e i t would appear t h a t


small amounts o f d i c k i t e o c c u r r i n g i n a k a o l i n can be i d e n t i f i e d by an expansion
e f f e c t a t about 650C t h a t i s p a r t i c u l a r l y s t r o n g f o r d i c k i t e (Schomberg and
Schtlrr, 1978b).

Thermodilatometry has a l s o r e c e n t l y been used t o o b t a i n informa-

t i o n on t h e mechanism o f i n i t i a t i o n o f t h e d e h y d r o x y l a t i o n and " m u l l i t i z a t i o n "


r e a c t i o n s o f k a o l i n i t e (Flank, 1979) and t h e r e i s no doubt t h a t , because o f i t s
s e n s i t i v i t y t o o r i e n t a t i o n e f f e c t s , i t has p o t e n t i a l a p p l i c a t i o n i n assessing the
degree o f o r i e n t a t i o n o f p l a t y p a r t i c l e s i n c l a y s t r a t a .
Thermodilatometers and d i f f e r e n t i a l thermodilatometers a r e r e a d i l y a v a i l a b l e
commercially and d e r i v a t i v e thermodilatometric curves can be e a s i l y recorded from
t h e r m o d i l a t o m e t r i c measurements.

When performed simultaneously w i t h DTA-TG,

thermodilatometry and d e r i v a t i v e thermodilatometry can y i e l d r e s u l t s t h a t h e l p t o

19

explain features on DTA and TG curves ( P a u l i k and Paulik, 1978). Such simultaneous
measurements may, therefore, be worthy o f f u r t h e r study by c l a y mineralogists.
1.3.7

Thermomechanical measurements

AS noted i n Table 1.1, thermomechanical measurements can be c a r r i e d out w i t h a

n o n - o s c i l l a t o r y (i.e.

s t a t i c ) o r w i t h an o s c i l l a t o r y ( i . e . dynamic) load. The


former, which are c u r r e n t l y commonly r e f e r r e d t o as "thermomechanical analysis"
o r "TMA" (despite t h e e r r o r o f using "analysis" i n such a connotation) can have
various modes depending on whether the s t r e s s applied t o t h e sample i s compression,
tension, f l e x u r e o r t o r s i o n and on whether deformation o r p e n e t r a t i o n i s measured
(Daniels, 1973). Clearly, t h i s technique i s c l o s e l y r e l a t e d t o thermodilatometry,
t h e d i f f e r e n c e being i n the use o f a f i n i t e load, whether p o s i t i v e o r negative:
indeed, t h e same equipment can be used f o r both measurements (see Flank, 1979)
and t h e r e i s some argument as t o whether thermodilatometry should be separately
recognized.

Dynamic thermomechanical measurements enable a d i f f e r e n t s e t o f

parameters, such as the. shear modulus, the mechanical damping index, the loss
tangent ( t a n 6 ) , etc.,

t o be measured as a f u n c t i o n o f temperature.

I t should

be noted t h a t i n d i v i d u a l isothermal measurements a r e n o t included.


Thermomechanical measurements, both s t a t i c and dynamic, f i n d extensive use i n
polymer science, b u t the p o t e n t i a l f o r t h e i r use i n c l a y mineralogy appears s l i g h t
although i t i s f a s c i n a t i n g t o speculate on the p o s s i b l e r e s u l t o f applying the
t o r s i o n a l pendulum (so-called " t o r s i o n a l b r a i d analysis"

- see Daniels,

1973) t o

c l a y samples.

I n c i v i l engineering and ceramic technology many o f the techniques


are, i n f a c t , applied, o f t e n i s o t h e r m a l l y b u t sometimes, as when t e s t i n g hightemperature r e f r a c t o r i e s , using a c o n t r o l l e d temperature programme.

I n ceramic

and r e f r a c t o r y studies, measurements may be made o f deformation under load, shear


modulus, modulus of e l a s t i c i t y , crushing strength, r e f r a c t o r i n e s s under load,
creep, s t r e s s r e l a x a t i o n and toughness and of t h e i r v a r i a t i o n w i t h temperature.
I n c i v i l engineering, load bearing properties, p e n e t r a t i o n measurements, etc.,
are u s u a l l y c a r r i e d o u t a t room temperature b u t may have t o be made over a l i m i t e d
temperature range.
Despite t h e i r p r a c t i c a l importance, these aspects are n o t s t r i c t l y w i t h i n the
province o f t h i s review
o r indeed o f the f i e l d o f experience o f the author

A much more r e l e v a n t a p p l i c a t i o n i s i n the


i n v e s t i g a t i o n o f o i l shales, where thermomechanical properties, such as deformation
on heating, anisotropy o f compressive strength, etc., a r e important i n determining
the release o f t h e o i l product i n the r e t o r t (Rajeshwar, Nottenburg and DuBow,
and w i l l n o t be f u r t h e r considered.

1979).

A t present, therefore, thermomcchanical measurements are o f use mainly

i n technology and i n d u s t r y r a t h e r than i n mineralogy.

20
1.3.8

Thermosonimetry and thermoacoustimetr,y

These techniques are q u i t e d i s t i n c t .

I n thermosonimetry one measures t h e

sound emitted by a sample on heating, whereas i n thermoacoustimetry one measures


t h e changes i n t h e c h a r a c t e r i s t i c s o f imposed sound waves caused by passage
through t h e sample. As w i t h t h e two types o f thermomechanical measurement, therefore, t h e type o f i n f o r m a t i o n gained i s d i f f e r e n t .
Sound emission from, o r d e c r e p i t a t i o n of, rocks was studied by Smith and Peach
i n 1949 and associated by Smith (1957) w i t h t h e i r p h y l l o s i l i c a t e components.

This

l e d t o a survey o f micas (Hutchison, 1966) t h a t detected two temperature ranges


o f sound emission

a t 305-340C associated w i t h trapped water and a t 600-1000C

associated w i t h p a r t i a l dehydroxylation.

The apparatus used i n these studies was

very simple and l i t t l e f u r t h e r ensued u n t i l L$nvik i n 1972 (see L l n v i k , 1974)


devised a much more r e f i n e d sound-measurement arrangement using a s p e c i a l l y designed
wave-guide system: sound emission was recorded e i t h e r as r a t e o r as amplitude
against temperature.

Although frequency analysis o f t h e emitted sound i s possible,

i t i s r a t h e r more d i f f i c u l t t o perform.

The method has more r e c e n t l y been taken

up by Clark (1978) and co-workers i n the UK, who have developed a concurrent ( n o t
simultaneous, as two samples a r e used) thermosonimetry-DTA apparatus (Clark and
Garlick, 1979).

A l e s s elaborate, b u t a l s o l e s s v e r s a t i l e , system has been

described by Poulou and Baudracco-Gritti

(1978) and a S o v i e t instrument, whereby

pressure changes i n h i g h vacuum are measured as t h e sample decrepitates, i s


comnercially a v a i l a b l e (Pawlikowski, 1979).

The l a s t i s s p e c i f i c a l l y designed

f o r measurement o f release o f m a t e r i a l from i n c l u s i o n s and i t i s doubtful whether


i t would p i c k up o t h e r causes o f sound emission such as s t r a i n release, microcrack

propagation, etc.
LBnvik (1974, 1978) has a p p l i e d the technique to, i n t e r alia, q u a r t z i t e s and
boehmite and has noted very s t r o n g sound emission associated w i t h phase t r a n s i t i o n s
and w i t h decomposition reactions.

C l a r k and G a r l i c k (1979), w i t h t h e i r combined

equipment, have come t o the conclusion t h a t maximum sound emission occurs a t t h e

extrapolated onset o f t h e DTA peak associated w i t h such processes


i.e. sound
emission i s v i r t u a l l y complete a t t h e p o i n t a t which measurable enthalpy changes
occur

- and have r e l e a t e d t h e emissionof

sound e s s e n t i a l l y t o t h e release o f s t r a i n :

once the s t r a i n i s released, through t h e commencement o f a phase change o r a


decomposition reaction, sound emission ceases.

A s i m i l a r mechanism would presumably

apply t o microcrack propagation b u t other r e l a t i o n s h i p s c o u l d w e l l h o l d f o r other


phenomena such as t h e release o f inclusions.
The r a p i d development i n t h i s f i e l d over t h e l a s t few years suggests t h a t t h e
time i s now r i p e t o apply i t t o c l a y minerals: i n i t s most advanced form i t might
w e l l h e l p t o e l u c i d a t e t h e mechanisms o f some r e a c t i o n s s t i l l i l l - u n d e r s t o o d .
Thermoacoustimetry has so f a r been a p p l i e d mainly t o polymers and, l i k e a l l
measurements i n v o l v i n g o s c i l l a t i o n o r waves, whether sound o r electromagnetic,

21

gives i n f o r m a t i o n on t h e shear modulus, t h e modulus o f e l a s t i c i t y , the l o s s tangent


and such l i k e .

An e x c e l l e n t d e s c r i p t i o n has been given by Perepechko (1975).

I t s a p p l i c a t i o n t o clays a t t h e moment i s uncertain: i t s most l i k e l y f i e l d would


be i n r e l a t i o n t o f i r e d c l a y products but, l i k e dynamic thermomechanical measurements and a l t e r n a t i n g e l e c t r i c a l measurements, i t has already found a p p l i c a t i o n
i n o i l - s h a l e technology (Mraz, Rajeshwar and DuBow, 1980).
1.3.9
Therrnoptornetry
Thermoptometry i s a wide term covering a whole range o f techniques, such as

thermophotometry (measurement o f t o t a l 1 i g h t ) , thermospectrometry (measurement of


l i g h t o f a s p e c i f i c wavelength), thermorefractometry (measurement o f r e f r a c t i v e
index) and thermomicroscopy f o r e i t h e r emitted o r r e f l e c t e d l i g h t .

Thermo-

luminescence i s a special case o f thermophotometry where emitted l i g h t only i s


measured a t temperatures below r e d heat.
Thermoluminescence i s probably t h e most widely used l o f thesetechniques,
having been widely a p p l i e d t o l u n a r and m e t e o r i t e samples (Nambi, Bhasin and
Bapat, 1978) as w e l l as t o c h a r a c t e r i z a t i o n o f marbles and limestones (Afordakos,
Alexopoulous and M i l i o t i s , 1974; Nambi and Mitra, 1978; Chistyakova, 1979).
i s a l s o used f o r age determination i n geology

It

f o r example, t o date the baking

o f a sediment (Huxtable, A i t k e n and Bonhommet, 1978)

and i n a,rchaeology

to

date ceramics and other a r t i f a c t s (Cairns, 1976). I t s r e l a t i o n s h i p t o DTA, DTG


and other techniques has been discussed by Chen (1976). Basic equipment f o r
simultaneous thermoluminescence-DTA has been described by David (1972) and the
more s e n s i t i v e and elaborate equipment used i n achaeological and chemical studies
by Cairns (1976) and Wendlandt (1980), r e s p e c t i v e l y . David (1972) reproduces a
glow curve f o r "a c l a y " (which from i t s DTA curve i s a g i b b s i t i c bauxite) and
Cairns (1976) discusses i n d e t a i l t h e o r i g i n o f thermoluminesce i n c l a y s and i n
ceramic and other materials.
Thermomicroscopy has been widely applied i n studies on glasses, r e f r a c t o r i e s
and ceramics, and neat instruments f o r simultaneous DTA, o r DSC, and thermomicroscopy have been described and successfully used ( M i l l e r and Sommer, 1966;
Sommer and Jochens, 1971; Kunihisa, 1979). Several standard hot-stage microscopes
w i t h temperature c o n t r o l are a l s o commercially a v a i l a b l e b u t clays as such,
presumably because o f t h e i r small p a r t i c l e size, have been r a t h e r neglected.
Equipment f o r use w i t h some o f the o t h e r techniques r e f e r r e d t o above w i l l be
found ( b u t n o t necessarily under t h e same names) i n standard t e x t s (e.g. Wendlandt
and Hecht, 1966; Wendlandt, 1974).

It seems t o t h e author t h a t some o f these

methods have as y e t untapped p o t e n t i a l i-n studying, f o r example, changes i n t h e


c o l o u r o f smectites on s a t u r a t i o n w i t h non-chromophoric ions and moderate heating.

2 2

Therrnoelectrometry
Like thermoptometry, thermoelectrometry i s essentially a portmanteau term
covering measurement of any e l e c t r i c a l property as a function of temperature.
Thus i t covers variations in resistance, conductance, inductance and capacitance,
f o r both d.c. and a.c., as well as variations in d i e l e c t r i c constants, thermoe l e c t r i c i t y , thermally stimulated current, etc.
The value of d.c. conductance (or resistance) in showing up decomposition
reactions, solid-state transitions, etc., was f i r s t appreciated by Berg and
Burmistrova (1960), who constructed an instrument f o r simul taneous d.c. conductance
measurement and DTA. Developments in :equipment and applications up t o 1974 have
been discussed by Wendlandt (1974): more recently, a.c. conductance measurements
have been favoured (Wendlandt, 1979). The terms "thermally stimulated conductivity"
and "thermally stimulated current" have come into very widespread use, particularly
in relation t o semi-conductor research: unfortunately, the f a c t t h a t both a r e
given the abbreviation "TSC" has led t o widespread confusion in indexing - even
in C h e m i c a l A b s t r a c t s .
Freund and co-workers, in t h e i r fundamental study of proton tunneling i n
hydroxides, have recently used d.c. conductance and thermally stimulated depolarization measurements t o provide evidence of the occurrence o f proton conductivity
and transitory HOH species in gibbsite, brucite and portlandite before the
comnencement of dehydroxylation (Freund and Wengeler, 1980; Wengeler, Martens and
Freund, 1980). In these studies, they observed t h a t the d.c. conductance depends
on the nature of the electrodes used and that thermopotential measurements are
sensitive t o electron acceptors or donors sorbed on p a r t i c l e surfaces. D.c.
conductance has also been used t o investigate water sorbed on goethite (Kaneko
and Inouye, 1979). Similar applications are likely with clays. In o i l shales,
the d.c. resistance decreases exponentially w i t h increasing temperature - an
observation attributed t o carbonate ions being the transporting species o r t o
breakdown of hydrocarbon units i n the trapped kerogen (Rajeshwar, Nottenburg and
DuBow, 1979). Such systems are extremely complicated and i t i s d i f f i c u l t t o
separate the effects due t o the clay matrix from those due to the kerogen. Attempts
have been made t o solve the problem using a.c. measurements involving conductance i.e. t h a t involve d i e l e c t r i c constant, d i e l e c t r i c loss factor and loss tangent and equipment for simultaneous and concurrent a.c. capacitance measurement and
DTA has been described (Rajeshwar, Nottenburg and DUBOW, 1978; Nottenburg e t ai.,
1979). The l a t t e r i s considered the more r e l i a b l e as the optimum sample s i z e f o r
DTA and for capacitance measurement i s quite different. I t seems t o the author
that examination of non-oil-bearing shales of similar mineralogical composition
could a s s i s t in resolving some of the d i f f i c u l t i e s of interpretation encountered,
b u t there may be practical d i f f i c u l t i e s related t o p a r t i c l e orientation, pore
space, etc.
1.3.10

23

Thermally stimulated c u r r e n t s have been r e l a t e d t o various types o f l a t t i c e


defects i n i o n i c c r y s t a l s and a review has been given by Radhakrishna and Haridoss
(1978).

These c u r r e n t s can a l s o be r e l a t e d t o thermoluminescence e f f e c t s ( F i e l d s

and Moran, 1974)

as, indeed, can thermally stimulated conductance (Chen, 1976;

Braeunlich, K e l l y and F i l l i a r d , 1979)

b u t no a p p l i c a t i o n t o clays can be traced.

I t may be o f i n t e r e s t t o some t o note t h a t values o f t h e thermoelectric power

( i n uV/"C against lead) have been measured by Lee (1973) f o r a considerable number
o f minerals, i n c l u d i n g some that, l i k e hematite, magnetite and ilmenite, can occur
as accessories i n clays: i n d i c a t i o n s are given o f t h e spread o f values f o r the
samples t e z t e d as w e l l as mean values.
I n conclusion, i t would appear t h a t some thermoelectrometric techniques may
have considerable p o t e n t i a l i n c l a y studies

e s p e c i a l l y i n r e l a t i o n t o water-

loss reactions and l a t t i c e d e f e c t i n v e s t i g a t i o n s

- q u i t e a p a r t from t h e i r p o t e n t i a l

value i n technological assessments.


Thermomagnetometry

1.3.11

The most common magnetic c h a r a c t e r i s t i c t o be measured as a f u n c t i o n o f


temperature i s magnetic s u s c e p t i b i l i t y , w i t h consequent d e r i v a t i o n o f t h e Curie
point
soils.

a parameter t h a t has proved extremely useful i n some studies on clays and


Thus, on t h e basis t h a t t h e very l a r g e v a r i a t i o n i n the Curie p o i n t o f

i l m e n i t e (below 77 K t o 841 K) can be c o r r e l a t e d w i t h i t s o r i g i n , i t has been


claimed t h a t samples w i t h a Curie p o i n t i n t h e r e g i o n 103-223 K are l i k e l y t o be
associated w i t h k i m b e r l i t e deposits (Garanin, Kudryavtseva and Soshkina, 1979).
Moreover, f o r red-yellow d e s e r t i c s o i l s , i t has been possible t o i n t e r p r e t Curie
p o i n t s i n terms o f the presence o f hematite and maghemite (Timofeev and Smirnov,
1980): i n t h i s study, non-coincidence of the thermomagnetic curve on a second
heating has been i n t e r p r e t e d as i n d i c a t i n g t h e presence o f f e r r i h y d r i t e

although

formation o f i r o n oxides from some other minerals present could p o s s i b l y a l s o


contribute.

Be t h a t as i t may, i t would seem t h a t thermomagnetometry may w e l l

have s i g n i f i c a n t a p p l i c a t i o n s i n c l a y mineralogy, e s p e c i a l l y i n the i n v e s t i g a t i o n


o f c e r t a i n accessory minerals.
1.4

CONCLUSIONS

From the above account, i t i s evident t h a t , although TG and DTA a r e by f a r the


most widely used thermoanalytical techniques i n c l a y mineralogy a t present, many
o t h e r methods t h a t can e l u c i d a t e s p e c i f i c features o r behaviour a r e available.
Thus, EGA and DSC a r e p r e s e n t l y r e c e i v i n g greater a t t e n t i o n and thermosonimetry
along w i t h some thermoptometric, thermoelectrometric and thermomagnetic methods
deserve consideration i n t h e f u t u r e .

Methods using o s c i l l a t i o n s o r waves t h a t

j i v e i n f o r m a t i o n on t h e shear modulus, the modulus o f e l a s t i c i t y , etc.,

are

r e l e v a n t e s s e n t i a l l y t o technology and industry, although t h e i r possible uses i n

24
more fundamental studies should not be neglected.
All-in-all, however, thermoanalytical methods are not in themselves necessarily
good in mineral identification: theirforte is in yielding information on
characteristics or detail that it would be difficult, if not impossible, to obtain
by any other method.
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