DIFFERENTIAL THERMAL ANALYSIS OF CLAYS AND CARBONATES

BY RICHARDS A. ROWLAND • *

ABSTRACT was developed by Hendricks (1946) ^ for use in stud}'-

Differential thermal analysis (DTA) began soon after the de- ing bauxite deposits in the field. The last development
velopment of the thermocouple. I t has progressed through the in the basic apparatus was the visual recording of the
systematic development of better equipment and the cataloguing DTA curves of a number of samples being heated in the
of typical DTA curves for a variety of materials until good
technique now requires control of the composition and pressure same furnace. Simultaneous development of DTA tech-
of the furnace atmosphere as well as consideration of the thermo- niques for the elementary study of carbonate minerals
dynamics and kinetics of the reactions involved. Although dif- took place in the U. S. A., Japan, and the IT. S. S. R.
ferential thermal analyses have been made for many materials,
the major applications have been concerned with clay and car- Reconsideration of the thermodynamics of the sys-
bonate minerals. tem gave rise to a very sensitive sample holder (Gruver,
In DTA curves for clay minerals the low-temperature endo- 1948) (Kaufman and Dilling, 1950) made of platinum
thermic loop associated with the loss of water, and the high- foil. Herold (1948) developed a thin sample holder half
temperature exothermic loop accompanying the formation of new
compounds, are changed in shape, temperature, and intensity by platinum and half platinum-10 percent rhodium in
the kind of exchange cations. The midtemperature-range endo- which the thermocouple junction, built into the sample
thermic loop has a temperature dependence on the partial pres- holder, was a ring around the middle of the cylindrical
sure of water in the furnace atmosphere.
For the anhydrous normal carbonates the dissociation tempera-
sample. Development of static atmosphere control within
ture and its dependence on the partial pressvire of CO2 are in the the furnace was introduced by Saunders and Giedroyc
decreasing order Ca, Mg, Mn, Fe, and Zn. The lower temperature (1950) and Rowland and Lewis (1951). Dynamic at-
loop of dolomite, the reaction for which must be preceded by an mosphere control within the sample was introduced by
internal rearrangement, is independent of the pressure of ('()•• but
may be shifted to a lower temperature by prolonged fine grinding Stone (1952)^ Presently the trend is toward atmosphere
which accomplishes a similar rearrangement. control at elevated pressures where DTA reactions begin
to approach equilibrium reactions. From the simple ap-
INTRODUCTION proximate measurement of the effective temperature dif-
Differential thermal analysis (DTA), although not a ference obtained by comparing the temperature of the
very accurate or definitive method, has found an impor- reaction of a sample in its own atmosphere with that of
tant place amon» techniques which allow the characteri- an inert standard, the technique has now progressed to
zation of materials. Limited only by the sensitivity of a consideration of the heat exchange under controlled
the apparatus, the differential thermal curves record all conditions of an inert atmosphere or of a participat-
transformations in which heat is taken up or given off. ing gas.
This includes the dehydration of clays, the decarbona- KINDS OF TRANSFORMATIONS
tion of carbonates, the reversible change from a- to The endothermic and exothermic deflections of a DTA
|3-quartz, the burning of materials, and the recombina- curve record many kinds of changes of state. The only
tion of elements into more stable forms. When employed
alone, the technique can be used to identify a number of limitation is that o^'^ the rate of change of enthalpy
reasonably pure compounds and to follow changes in
mixtures for control purposes. When used in eonjunc- (Afl"), be sufficient for the temperature difference to be
with X-ray diffraction, microscopy, and chemical analy- registered before dissipation in the system. First-order
sis, otherwise difficult identifications can be made. The phase changes, which involve discontinuities in volume,
technique is not easily standardized, however, and the entropy, and the first derivatives of the Gibbs function
factors which frequently make it difficult to compare (AF) are represented by two kinds: the reversible al-
DTA curves prepared in different laboratories are sum- lotropic inversion of alpha to beta quartz (Faust 1948)
marized by Ahrens (1950). (Grimshaw, et al. 1948) and the irreversible monotropie
The development of differential thermal analysis has change of aragonite to calcite (Faust 1950). The change
progressed through several stages. As early as 1887 from endellite to halloysite probably is a monotropie
le Chatelier described the use of his thermocouple as a phase change. Definite second-order phase changes, in
difference thermocouple and published DTA curves of which there is no discontinuous change in volume and
kaolinite. Prom that time until Orcel (1935) began the entropy while the second derivatives of the Gibbs func-
systematic differential thermal analyses of clays, about tion change diseontinuously, are rather rare. One which
twenty miscellaneous DTA papers appeared. Another is habitually recorded in DTA, employing a nickel block
stage began with the design of good furnaces, ssimple as a sample holder, is the change from ferromagnetic to
holders, and photographic recording equipment by paramagnetic nickel (Curie point) at 353°G.
Norton (1939) and Hendricks (1939). Refinements of Murray and White (1949) have discussed the kinetics
this design by Grim and Rowland (1942) were followed of thermal dehydration curves. Most of the chemical
by further developments by Berkelhamer and Spiel reactions recorded by DTA are first-order reactions in
(1944). Throughout this period many papers appeared which the rate of reaction is directly proportional to the
which repeated the thermal curves of the same clay concentration of the reacting substance. The dehydration
samples and related oxides, and a portable apparatus of clav minerals such as kaolinite and the dissociation of
* Publication No. 25, Kxploration and Production Technical Divi- 1 This apparatus is available commercially from the Eberbach Cor-
sion, Shell Oil Co., Houston, Texas. poration, Ann Arbor, Michigan.
** Senior Geologist, B^xploration and Production Technical Division, ^ Variable pressure DTA apparatus is available from Dr. Robert L.
Shell Oil Company, Houston 25, Texas. Stone, Austin, Texas.

(151)
132 CLAYS AND CLAY TECHNOLOGY [Bull. 169
carbonates are chemical reactions of this type. The very
poor curves obtained for museovite—because the rate of
dehydration for the usual heating rates is very slow—
also represent a first-order reaction. Second-order reac-
tions in which the rate depends on the concentration of
two molecules, and third-order reactions where the con-
centration of three molecules controls the rate, are not
common in the interpretable DTA reactions. Combina-
tions of first- and second-order reactions, and perhaps
some third-order reactions, probably take place after the
final breakdown of the clay mineral lattice when new
higli-temperature products are formed.
The kinetics and thermodynamics of the DTA method
are actually too complex to permit the application, in
any sense other than approximate similarity, of these
physical-chemical terms for better-known reactions. This
rather incomplete discussion of phase changes and order
of chemical reactions is included because it has become
increasingly popular to refer to DTA curve deflections as
representing a specific kind of chemical reaction or phase
change.

3 7 ATM

LINE FOR KAOLINITE

BASED ON SP HEAT
DATA

400
500' 600" 700" 800" 900" 1000 0

DTA CURVES OF SIDERITE

FIGURE 2

establish a relation between the differential temperature

TAKO a CORNWALL
KAOLINS
and the heat adsorption producing it. Valid results were
obtained for such widely differing processes as the melt-
1000 / ' K ing of stearic acid and the vaporization of water.
VAN'T HOFF LINES FOR SEVERAL M I N E R A L S
I f l F r L H STONE, J A CLW S J5, 19521 A highly significant contribution to the understanding
FIGURE 1 of differential thermal analysis was made by Murray and
White (1949). They point out that a Clausius-Clapeyron
T H E R M A L THEORY
Spiel (1945) and Kerr and Kulp (1948), by opposing
the thermal effects—the heat of the thermal reaction and
the differential heat flow between the block and the
sample—arrived at an expression to show that the area
enclosed by the loop and the base line is an approximate
measure of the total heat effect and, under certain condi-
tions, is proportional to the amount of thermally active
material in the sample. By making a set of calibration
curves with prepared mixtures of dolomite and calcite,
Rowland and Beck (1952) were able to show that this
relationship can bo used to determine dolomite in lime-
stone when as little as 0.3 percent is present (fig. 13).
Wittels (1951) varied both the heating rate and the
mass'of the sample to obtain an expression and calibra-
tion so that precise calorimetric measurements can be
obtained from DTA curves.
M. Void (1949) has derived equations for the calcula- DOLOMITE OTA CURVES AT I MM TO 760MM.C02 PRESSURE
tion of heats of transformation from differential heating (AFTER HAUL ft HEYSTEK. AMER. MIN. 37, 19521

curves, which are independent of external calibration, by

using the rate of restoration of a thermal steady state to FIGURE 3
Part III] METHODS OP IDENTIFYING CLAYS AND INTERPRETATION OF EESULTS 153
placed to a higher temperature. Except when the sample
RAW I N AIR well is covered, the pressure of the evolved gas probably
never attains one atmosphere pressure and is quickly re-
duced by diffusion to a mlieh lower concentration. These
atmospheric effects are not controlled but are a function
of the sample dissociation.
The atmosphere of a furnace may be maintained at
about one atmosphere partial pressure by allowing a gas
to flow through the furnace (Rowland and Lewis, 1951).
This technique is sufficient for many applications where
approximately one atmosphere of an inert gas, or a par-
ticipating gas, is required. A better technique, using a
sintered block for a sample holder, has been described by
Saunders and Giedroyc (1950). This method insures that
the gas surrounds the individual grain of the sample
from the beginning of the analysis. Neither of these
DTA OF ORGANIC-CLAY IN NITROGEN
methods permits control of the partial pressure of the
gas, and the composition is maintained only so long as
no air is swept in with the gas.
FIGURE 4
Actual control of the pressure within the furnace has
been used as a vacuum technique by Whitehead and
type equation can be reduced to a plot of In PH2O VS Breger (1950). A dynamic system for control of the
1/T to obtain a straight line of slope—AH/2B. By select- pressure and composition of the atmosphere surrounding
ing a number of partial pressures of H2O and observing the particles of the sample was described by Stone
from the DTA curve the value of ^ C . at which the loss (1952) who included the sample holder in the gas-
of hydroxyl water begins, Stone (1952) assembled data handling system. With this arrangement it is possible to
for a van't Hoff line from the slope of which the heat of maintain a continuous supply of fresh gas moving
reaction can be calculated (fig. 1). Comparison of through the specimen at a predetermined pressure.
these heats of reaction with values obtained from specific Atmosphere control can be used to eliminate unwanted
heat data shows that, for minerals of the kaolin group, exothermic reactions resulting from the burning of or-
the temperature at the beginning of the deflection of the ganic matter in clays (fig. 4). DTA curves of some car-
DTA curve is considerably higher than equilibrium tem- bonates, particularly calcite and dolomite, are greatly
perature up to a partial pressure of In p = 6.50 (665 improved by an atmosphere of CO2. From DTA curves
mm). Above In p = 6.50 better agreement is obtained. made in a dynamic steam atmosphere van't Hoff lines
For calcite, good agreement is obtained at In p =: 3.8 can be constructed. While van't Hoff lines constructed
(447 mm). Stone concludes from these experiments that from DTA curves only approximate equilibrium at ele-
at temperatures close to equilibrium in dry air the vated pressures, they are a summary of the DTA curves
kaolinite decomposition reaction must be very slow in- at several pressures and as such may be more charac-
deed. These experiments show that, even though the clay teristic of the material than the original DTA curve.
minerals have very similar structural arrangements,
their DTA hydroxyl-loss loops can be shifted selectively
DTA CURVES OF CLAYS
by control of the partial pressure of water vapor. Hence,
clay mineral DTA curves so obtained should resolve the Aside from a number of papers describing systematic
midrange endothermic loops which interfere when the studies of the collections of clays and carbonate minerals
furnace atmosphere is uncontrolled. to learn what differences could be observed by this tech-
nique, there have been a number of studies involving
ATMOSPHERE CONTROL the factors controlling the individual parts of the differ-
ential thermal analysis curves. The geometry of a differen-
Atmosphere control in differential thermal analysis has tial thermal curve of a clay is usually made up of three
taken several different forms. When a sample is heated distinct parts. The first is a low-temperature endothermic
in air, it builds up its own atmosphere, but not in excess loop which is registered when atmospheric water departs
of one atmosphere pressure. A typical example is the from the material. A second or midrange endothermic
dissociation of siderite (Rowland and Jonas 1949) loop accompanies the loss of bound water or the dissoci-
(fig. 2), in which the DTA curve is a compromise be- ation of hydroxyls from the lattice. The third is a high-
tween the endothermic effect of CO2 liberation and the temperature combination of loops accompanying the
exothermic effect of iron oxidation, until the COo evolu- final breakdown of the lattice and the formation of one
tion is violent enough to exclude oxygen and the endo- or more new materials.
thermic effect predominates. Oxidation resumes when
CO2 evolution slows down, and the endothermic loop is Low-temperature Loop. The low-temperature loop,
interrupted by an exothermic loop. A similar effect is which may cover the interval from 50°C. to about 240°C.,
shown by the DTA curve when dolomite is heated in air. is dependent on the kind of clay mineral for its pres-
The curve in air resembles the curve at about 360 mm of ence; on the type (bivalent-univalent) and amount of
CO2 (Haul 1951) (fig. 3). When a cover is used on the exchange cations for its shape; and on the moisture
sample holder, the main oxidation loop of siderite is dis- content, or the relative humidity surrounding the clay
154 CLAYS AND CLAY TECHNOLOGY [Bull. 169
of a number of different exchange cations on different
bentonites (fig. 5). In general, clays with monovalent
cations exhibit one endothermic loop at about 150°C;
most clays with bivalent cations have a second loop or
a shoulder on a loop similar to the monovalent loop at
a higher temperature (220°C.). Various organic com-
pounds, particularly those which blanket the space be-
tween the layers of the lattice, also have their particular
effect on the hydration loop, but this is frequentlj' ob-
scured by the immediate volatilization or burning of the
organic material.
As yet, no one has succeeded in making use of the
area of the low-temperature endothermic loop to deter-
mine either the total moisture content or to make a
quantitative estimate of the type and amount of exchange
cations on the clav.

5% 10% 25% 40% 50% 70% 90%

DTA CURVES OF MISSISSIPPI MONTMORILLONITE WITH
SEVERAL COMMON CATIONS AT DIFFERENT WATER
CONTENT (AFTER HENDRICKS, NELSON a ALEXANDER. J AC S 62,1940)

F U J U K K -"•

prior to analysis, for its size. In general, members of the

kaolinite group do not show a low-temperature peak. The o o
1 ss
exception is hydrated halloysite; its peak can be irre-
P,^,.760.
versibly destroyed by storage over a period of time in an
atmosphere of low relative humidity at room tempera-
ture, or by heating to slightly more than 100°C.
\M
The three-layer lattice clay minerals invariably have i«)
a low-temperature endothermic loop. Of these, the mont-
morillonite loops are the largest and most sensitive to
moisture content, humidity, and type and amount of
exchange cations. Although the illites also exhibit a low- DTA CURVES OF DiCKITE (OURAY, COLORADO) AT DIFFERENT
PRESSURES OF WATER VAPOR

temperature loop, the true micas, such as muscovite and (AFTER STONE,J A CER 5 J 6 , I 9 S 2 )

biotite, do not. Chlorite in clay-mineral particle size has FKU'RE 7

a low-temperature endothermic loop, but chlorite from
metamorphic rocks does not. The effect of exchange
cations on montmorillonites and illites is frequently High-temperature Loops. At the high-temperature
rather marked. Hendricks (1940) pointed out the effect end of the dift'erential thermogram most of the recorded
loops are the combined heat effect of several reactions,
both endothermic and exothermic in nature. Grim (1948)
WYOMING BENTONITE
and Stone (1952) have pointed out that, even in kao-
linite, a very small endothermic loop occurs and is inter-
rupted by the large exothermic loop usually associated
with the formation of mullite. The high-temperature
zone for members of the montmorillonite and illite
groups is largely controlled by the chemical composition
of the material. This involves the amount and kind of
isomorphic substitution within the lattice and the nature
of the exchange cations. Most of the three-layer lattice
clay minerals undergo an endothermic reaction associ-
ated with the final breakdown of the clay mineral lattice
(Grim, 1948) and with the loss of a small amount of
water which supposedly results from the loss of the last
hydroxyls. Different persons have different ideas as to
just what happens during this endothermic reaction.
MeConnell (1950) theorizes that tetrahedral hydroxyls
give rise to the small water loss, and occur in groups of
four, substituted for silicon in the tetrahedral layer.
It is also possible that the hydroxyls are supplied from
local substitution of magnesium in the octahedral layer.
While there appears to be no reason for one part of the
octahedral layer to retain its character at temperatures
FlGlUE C
Part III] METHODS OJ^ IDENTIFYING CLAYS AND INTERPRETATION OF RESULTS 155
TaWe 1. Firing products of several clays.

High alumina 900° C. 1000° C. 1100° C. 1200° C. 1300° C.

Kaoljnite mullite (a) mullite (a)

cristobalite (b)
Endellite muUite (a) mullite (a)
cristobalite (b)
Diaspore -.^ x-\UO, (a)
Gibbsite r-AhO, (a) a-AhOs (a)
Bauxite
(Kaolinito and gibbsite)
Montmorillonito group
Beidell, Colo._, mullite
cristobalite
Cheto 3-quartz (a) 3-quartz (a) cristobalite (a)
anorthite (?) (c) cristobalite (c) cordierite (a)
anorthite (?) (c)
Fairview, Utah.. _ mullite (a) mullite (a)
cristobalite (a)
spinel (b) cristobalite (a) cristobalite (a) cristobalite (a)
Harris Co., Tex cristobalite (c) spinel (a) spinel mullite (b)
mullite (b)
3-quartz (a) cristobalite (a) cristobalite (a) cristobalite (c)
Otay, Calif enstatite (c) 3-quartz (a) cordierite (a) cordierite (a)
enstatite (b) periclase (c)
spinel (a) spinel (a) cristobalite (a)
Palmer, Ark. quartz (c) spinel (a)
mullite (a)
spinel (a) cristobalite (a) cristobalite (b)
Pontotoc Co., Miss a-quartz (b) spinel (a) cordierite (b)
spinel (a) cristobalite (a) cristobalite (a) cristobalite (a)
spinel (a) spinel (a) cordierite (a)
Sierra de Guadalupe cordierite (b)
0-quartz (b) cristobalite (a)
mullite (b)
Tatatila, Vera Cruz cordierite (b)
spinel (a) spinel (a) spinel (a) mullite (b)
a-quartz (b) cristobalite (b)
Upton, Wyo cristobalite (a) cristobalite
spinel (b)
Wagon Wheel Gap, Colo.. mullite (b)
spinel (c)
Woody nontronite mullite
cristobalite
spinel

Parenthetic letters signify: (a) important, (b) moderate, and (c) minor. (After Bradley & Grim, 1951.)

higher than that attained by other parts of the same peratures somewhat higher than encountered in mate-
layer, it is still possible to draw the parallel between rials consisting primarily of aluminum in the octahedral
the temperature at which gibbsite loses its hydroxyls layer.
versus the temperature at which brucite loses its hy- Bradley and Grim (1951) have described many of
droxyls. Other magnesium-bearing minerals, such as talc the factors controlling the nature of the immediate high-
and chlorite, seem also to lose their hydroxyls at tem- temperature products (table 1). They point out that the

DAYS - — MONTMORILLONiTE
STANDING

200 400 600 800 -ENGLISH KAOLIN

-DICKITE
STEAM INJECTION
DTA CURVES OF SODIUM MONTMORILLONITE A F T E R AT 115° C
HEATING TO INDICATED TEMP. FQR \ HOUR AND DTA SHOWING EFFECT OF STEAM INJECTION
STANDING FOR DIFFERENT PERIODS ON DRIED CLAY MINERALS
|4FTEfl STONE, J A . C C B - S 3 5 , 1952)
(AFTER GRIM 9 BRADLEY, AMER MIN 3 3 , 1 9 4 8 )

F10IKE 8 FIGURE 9
156 CLAYS AXD CLAY TKCIIXOLOGY [Bull. 169

exchange cations can give rise to a variety of spinels PERCENT CAUCITE

100 300 500 700 900'C

and cordierite. When the exchange ion between the layer

positions is blanketed with an organic compound so that
r
at elevated temperatures the only exchange cation
present is hydrogen, the formation of mullite occurs
even with a three-laj-er lattice clay mineral. In figure 6
the exothermic loop at 930°C. accompanies the formation
of a spinel in the untreated sample, mullite and spinel
in the NH4 sample, and mullite in the remaining sam-
ples. In some cases where there is a return to the base- • - v ^

line between the endothermie and exothermic reactions

and where lithium is present in the elay mineral, the
accompanying excess silica appears in the form of beta
quartz instead of cristobalite.
Midrange Loop. The endothermie loop occurring at
midtemperature range and associated with the major EFFECT OF DILUTION — DTA CURVES OF CALCITE
ALUNDUM MIXTURES
loss of hydroxyls from the octahedral layer varies con- [AFTER KULP, KENT KERR, AMER. MIN. 36,1951)
siderably from clay to claj^ In the kaolinite group this
is an intense reaction which probably starts at a much KiGX'KK n
lower temperature but is sufficiently strong to cause
deflection at about 450°C. and to peak at about 600°C. organized montmorillonites. In sediments which may
Dickite, the most highly organized member of the kaolin- contain both illite and montmorillonite, it is seldom pos-
ite group, has a slightly different differential thermal sible to distinguish betAveen montmorillonite and illite
curve through the range of loss of hydroxyls. The low- with differential thermal curves. In fact, the shales and
temperature side of this loop is quite steep, while the clays of the Gulf Coast, at least to the base of the Terti-
high-temperature side is at a somewhat lesser slope. The arjT, appear to contain both an illite and a very poorly
result is a loop skewed toward the low-temperature end. organized montmorillonite which may be in effect a de-
The starting and peak temperatures of the midrange graded illite in which a large portion of the potassium
loop of both dickite and kaolinite can be shifted by has been lost.
PH20 of the furnace atmosphere (fig. 7). Wyoming Previously this loss of hydroxyls was considered to be
bentonite and other bentonitie materials in which the an irreversible reaction. However, Grim and Bradley
order of stacking and the organization of the crystals (1948) (fig. 8) demonstrated that clays heated to a
are very good, have a loop beginning at about 575°C. temperature just below the end of their differential
and peaking at about 700°C. When the organization is thermogram dehydration loop will reabsorb a consider-
poor, as is the case with most sediments containing mont- able amount of moisture as hydroxyls when exposed to
morillonite, this loop is approximately 100°C. lower. The an average relative humidity over a period of time. From
loop for nontronite, the iron analog of montmorillonite, his experiments using steam atmospheres, Stone suggests
also occurs at a somewhat lower temperature. (fig. 9) that more rehydration may be obtained at ele-
Members of the illite group lose their hydroxyls over vated steam pressures.
the same approximate range as do some of the less well-
D I F F E R E N T I A L T H E R M A L ANALYSIS OF T H E
CARBONATE MINERALS
SMITHSONITE
The carbonate minerals are especially amenable to dif-
ferential thermal analysis. Normal anhydrous carbonates
undergo dissociation in an atmosphere of CO2 at progres-
sively lower temperatures in the order Ca, Mg, Mn, Fe,
and Zn (fig. 10). The temperature of the dissociation of
calcite is very sensitive to the partial pressure of CO2.
In the absence of CO2 in the surrounding atmosphere the
dissociation starts at about 500°C. When one atmosphere
of CO2 surrounds the sample, the dissociation starts at
about 900°C. The other normal carbonates are much less
sensitive to change in pco2- Rowland and Lewis (1951)
have shown that the order of decreasing sensitivity to
change in pco2 is also Ca, Mg, Mn, Fe, and Zn. DTA
curves of the anhydrous normal carbonates, with expla-
nations of the reactions represented, have been published
bv Cuthbert and Rowland (1947), Kerr and Kulp
(1948), Gruver (1950), and Beck (1950). In addition to
DTi CURVES FOB SOME RHOMBOHEDRAL CARBONATES the normal anhydrous carbonates, Beck included DTA
(AFTER KERR 8 KULP, AMEft. MIN. 3 3 , 1948)
curves of samples representative of most of the other
FlOURF. 10 carbonate minerals.
Part III] [METHODS OF IDENTIFYING CLAYS AND INTERPRETATION OF RESVLTS 157
end of the endothermic peak. Kulp attributes this peak
to the presence of small amounts of iron substituted
in the lattice. It may also be the heat effect accompany-
ing the organization of magnesium oxide as periclase.
Siderite. Cuthbert and Rowland (1947), Kerr and
Kulp (1947), Frederickson (1948), and Rowland and
Jonas (1949) have discussed the DTA curve of siderite.
Diluted and lieated in air, this carbonate yields a small
exothermic loop (fig. 2). In an atmosphere of CO2 the
loop is large, endothermic, and at the proper tempera-
ture for the Ca, Mg, Fe, Mn, and Zn series. Undiluted
and heated in air, the curve first swings in the exother-
mic direction until enough CO2 has been liberated to
DTA CURVES OF CALClTE ARAGONITE MIXTURES prevent oxidation of the iron. The dissociation of CO2
"{AFTER FAUST, AMER. MIN 35, 19501
is tlien registered by an endothermic loop which is in-
FiCii'Ric 12 terrupted by an cxothermie loop representing the oxida-
A review of the interpretations of DTA curves indicates the tion of the FeO when the back pressure of CO2 begins
necessity for : (1) determining by other methods, usually X-ray, the to subside. At a higher temperature the partially oxi-
nature of the product formed by each reaction; (2) establishiufi dized iron is completely oxidized to hematite.
whether each thermal loop represents a single change or is a
compromise heat effect resulting from several reactions; (3) in-
vestigating the effect of varying the gas pressure within the sample
to establish the temperature dependence of the reaction on the gas
phase. The data from (3) when plotted as van't Hoff lines almost
uniquely describe the thermal character istics of the materials.

Calcite. The dissociation of calcium carbonate is used

in physical chemistry as a classic example of the effect of
the partial pressure of a participating gas on heterogene-
ous equilibria. Perhaps it is for this reason that very
little attention has been given to the DTA curves of cal-
cite. Faust (1950) and Kulp, Kent, and Kerr (1951)
have shown that the peak temperature and the initial
decomposition temperature of pure caleite decrease when
the sample is ground to an extremely fine particle size.
Kulp et al. (1951) (fig. 11), also show a drop in both
temperatures when the sample is highly diluted with
alundum. These results were obtained in an ambient fur-
nace atmosphere without control of the CO2 and are
therefore not definitive. Dilution reduces the opportunity
for the buildup of a back pressure of CO2 and conse-
quently lowers the dissociation temperature. This effect
is frequently observed in unwashed Ca-clay samples
which have been allowed to stand in water open to the
atmosphere. The DTA curves exhibit a small endothermic
peak at about 750°C., resulting from the calcium car-
bonate formed from calcium in the solution and CO2
dissolved from the air.
DTA curves of the aragonite -^ calcite transformation
have been examined by Faust (1950) (fig. 12), who has
pointed out that this monotropic transformation does not
take place at a constant temperature, and is subject to
further variations resulting from the presence of barium,
strontium, lead, and perhaps zinc. The transformation
temperatures range from 387°C to 488°C at a heating
rate of 12°C per minute.
Magnesite. DTA curves of magnesite have been pub-
lished by Cuthbert and Rowland (1947), Faust (1949),
Gruver (1950), Beck (1950), and Kulp, Kent, and Kerr
(1951). Pure coarsely crystalline magnesite heated in
air yields a simple endothermic peak at 680 to 700° C.
DTA Calibration Curves of SmaiI Percentages of
The temperature of the peak varies somewhat in the Bureau of Standards Doiomite and iceiand Spar Calcite
presence of impurities. The magnesite from Stevens
County, "Washington, shows an exothermic peak at the FICIKK l."
158 CLAYS AND CLAY TECUXOLOGY [Bull. 169

dissociate before the more coarse-grained ealcite frag-

ments.
Berg (1943) and Graf (1952) have shown that the
presence of soluble salts such as encountered in brines
will materially affect the shape and size of the first loop
of the dolomite curve. In addition, the presence of a
sericite-like mica will completely eliminate the second
or calcium carbonate peak in a CO2 atmosphere.
228 HOURS

MISCELLANEOUS APPLICATIONS OF DTA

Soaps. Void and Void (1941) established that, in-

stead of melting directly from crystal to liquid, sodium
salts of long-chain fatty acids pass through a series of
EFFECT OF PROLONGED GRINDING
forms, each constituting a definite stable phase existing
ON DTA OF DOLOMITE IN COa over a definite range of temperature. They calculated
ATMOSPHERE
heats of transition from the DTA curves of these soaps
FIGURE 14 U and have since (Void, Grandine, and Void, 1948) de-
lineated the polymorphic transformations of calcium
Dolomite. Of all of the carbonate minerals of the stearate and calcium stearate monohydrate by their
Ca-Mg-Fe group (Kulp, Kent, and Kerr, 1951) dolo- technique.
mite has received the most attention. Berg (1945) at- Greases. By the same technique Void, Hattiangdi,
tempted to use the areas under the loops as a quantita- and Void (1949) have delineated the phase state and
tive expression of the amount of dolomite in the sample. thermal transitions of numerous samples of aluminum,
Rowland and Beck (1952) (fig. 13) succeeded in doing barium, calcium, lithium, sodium, and mixed base com-
this for samples heated in an atmosphere of CO2. Haul mercial greases, and of the corresponding oil-free soaps.
and Heystek (1952) (fig. 3) have shown that DTA
curves for dolomite have only one loop at 1 mm pcoz, CONCLUSION
two loops, resembling the curve made in air, at 300
mm pco2, and two distinctly separated loops at one Differential thermal analysis is well established as a
atmosphere of CO2. This is accomplished entirely by technique for the characterization and control of ma-
shifting of the second or CaCOs peak. The apparent terials which undergo characteristic changes on heating.
immobility of the first peak leads them to suggest that It is less well established as a method for investigating
this peak is formed only after a certain amount of the products obtained when such a material is heated,
diffusion of lattice constituents has taken place. The since equilibrium is an inherent impossibility of the
requirement for this activation energy explains the method. However, the latter is not an obstacle when
formation of this peak at a higher temperature than thermodynamic considerations control the design of the
the peak for magnesite dissociation. apparatus and when good recording equipment is em-
Actually, the first dissociation peak of dolomite is ployed. With the addition of dynamic atmosphere con-
not immobile. Bradley, Burst, and Graf (1952) (fig. 14) trol much useful information about the products of heat-
have shown that during prolonged grinding (250 hours) ing can be assembled in a short time.
there first appears another peak about 100°C. lower, Because differential thermal analysis is most useful
which grows in size until the usual first peak is ex- when the apparatus is designed so that several different
hausted. At any stage the ratio of the sum of the areas techniques can be employed, there should be no
of these two peaks to the area of the ealcite is constant. standardization of materials, heating rates, etc. Instead,
These authors demonstrate by X-ray diffraction studies a flexibility should be maintained so that due considera-
that, by a process of twin gliding and translation glid- tion can be given to the details of the kind of change
ing, the Ca and Mg of the dolomite lattice which at being analyzed, and these considerations must be pre-
first occupied alternate positions around any CO3 group sented as a part of the data.
have now been rearranged so that most of the Mg has
magnesium for its nearest neighbors and vice versa. DISCUSSION
Hence, the temperature delay required to activate these J. A. Pask:
atoms to sufficient mobility so that dissociation can occur In the DTA curves of montmorillonite Rowland mentioned that
is no longer required. The first loop of a dolomite DTA the exothermic loop at 930°C. is accompanied by the formation
of a spinel in the untreated material, mullite and spinel in the
curve is the algebraic sum of the AH required to dis- NHi^-saturated samples, and mullite in the methylamine-saturated
sociate both MgCOs and CaCOs (endothermic), to re- samples. Could this be discussed?
form most of the CaCOs (exothermic), and perhaps to
R. A. Rowland:
form perielase and some calcium oxide (exothermic).
I believe the explanation lies in the nature of the exchangeable
Dolomite furnishes an excellent example of the effect cation. When the exchangeable cations are Ca++ and Mg++, spinel
of small crystallites (not fine grain size) on DTA curves. is formed, but when these are completely absent, as in the case of
In figure 13 the endothermic loop beginning at 925°C is the methylamine-saturated samples, mullite is formed. The forma-
preceded by a small shoulder. This shoulder accompanies tion of both spinel and mullite in the NH4+-saturated .sample would
indicate that the sample was not completely saturated with XH4+;
the dissociation of the extremely fine crystallites of some of the original exchangeable cations must have remained on
CaCOa formed from the products of the first loop which the clay.
Part III] METHODS OF IDENTIFYING CLAYS AND INTERPRETATION OF R E S U L T S 159

J. A. Pask: Beck, C. W., 1950, An amplifier for differential thermal analysis :

Is the spinel formed by a combination of the exchangeable Am. Mineralogist, v. 35, pp. 508-524.
cation and the aluminum of the lattice? Beck, C. W., 1950a, Differential thermal analysis curves of
carbonate minerals: Am. Mineralogist, v. 35, pp. 985-1013.
R. A. Rowland: Beck, W. R., 1949, Crystallographic inversions of the aluminum
This appears to he so from the series of curves which I sliowed orthophosphate polymorphs and their relation to those of silica :
and from other curves run in similar fashion. Am. Ceramic Soc. Jour., v. 32, pp. 147-151.
Belyankin, D. S., and Deodot'ev, K. M., 1949, The heating curve
G. W. Brindley: of kaolin in a new light: Doklady Akad. Xauk. ( U S S R ) , v. 65,
1 feel that progress can lie made in the use of the various pp. 357-360.
methods of clay identification and estimation by a cooperative Berg, L. G., 1943, Influence of salt admixtures upon dissociation
effort whereby type mineral specimens would l)e examined liy the of dolomite: Dokladv Acad. Sci. ( U S S R ) , v. 38, pp. 24-27.
various methods by those persons who have had a great ch'al of Berg, L. G., Nikolaiev, V. I., and Rode, E. Y., 1944, Thcrmo-
experience with a given method. graphia: Acad. Sci. ( U S S R ) , v. 25.
Berg, L. G., 1945, On area measurements in thermograms for
J. A. Pask: quantitative estimations and the determination of heats of re-
I think that any one of the methods for clay identification is as action : Doklady Acad. Sci. ( U S S R ) , v. 49, pp. 648-651.
good and as useful as any other, provided the operator is thoroughly Berg, 1J. G., and Rassonskaya, I . S., 1950, Rapid thermal
familiar with the method which he uses. analysis: Doklady Akad. Nauk. ( U S S R ) , v. 73, pp. 113-115.
Berg, U. G., and Rassonskaya, I. S., 1951, Thermographic
Isaac Barshad: analysis under elevated pressures: Doklady Akad. Nauk. ( U S S R ) ,
Each method yields data which another method does not. That V. 81, pp. 855-858.
is i)recisoly why the various methods of analysis were developed. Berkelhamer, L. H., 1944, Differential thermal analysis of
Thus, while X-ray analysis is indispensable for crystal structure quartz : U. S. Bur. Mines Rept. Inv. 3763, 18 pp.
analysis, DTA is undispensable for recording changes which occur Berkelhamer, L. H., 1945, An apparatus for differential thermal
in a mineral during the course of heating. I t woidd be practically analysis : U. S. Bur. Mines, Tech. Paper 664, pp. 38-55. . . . 1944,
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minerals in a clay sample derived from a soil unless various
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analysis : Mine and Quarry Eng., v. 10, pp. 273-279.
This discussion has further indicated the need for additional
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1413.
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