Clay Minerals (1996) 31, 253-261

I N F L U E N C E OF M E T A K A O L I N I Z A T I O N T E M P E R A T U R E
O N THE F O R M A T I O N OF Z E O L I T E 4 A F R O M K A O L I N

S. C H A N D R A S E K H A R

Clays and Clay Minerals Section, Regional Research Laboratory, Thiruvananthapuram - 695019, India

(Received 16 June 1995; revised 8 November 1995)

A B S T R A C T : Kaolin has been used as an alternative cheap raw material for the synthesis of
zeolite 4A. Two steps are involved in the reaction: (1) dehydroxylation of kaolin at 550-900~ to
form an activated X-ray amorphous material called metakaolin; (2) hydrothermal treatment of
metakaolin with aqueous alkali to form the zeolite. The inherent colouring impurities in kaolin,
especially the Fe minerals, affect the brightness of metakaolin and the resultant zeolite. The
dehydroxylation temperature is found to have a significant influence on the kinetics of zeolite
formation as well as on the brightness of zeolite. The present investigation deals with the preparation
of metakaolins from a good quality kaolin at different temperatures and their characterization by
XRD, IR, TGA, MAS NMR and brightness measurements. Hydrothermal reactions of these
metakaolins with aqueous alkali have been conducted. The residual Fe in the mother liquor has been
estimated. The improvement in brightness and change in reactivity of the metakaolin, difference in
the kinetics of its conversion to zeolites and dissolution of Fe during zeolite formation have been
correlated with the calcination temperature. A calcination temperature of 900~ (1 hr) is the
optimum for this clay to change into a reactive metakaolin which gives detergent grade zeolite 4A of
high crystallinity and maximum brightness.

Clay minerals have been used as a combined source
for A1203 and SiO2 for the synthesis of zeolites
(Barrer, 1978, 1982). Kaolinite (A1203.2SiO2.2H20)
with a Si/A1 ratio of 1, is the principal mineral in
china clay and is ideally suited for the synthesis of
zeolite 4A which also has a Si/A1 ratio of 1. Other
low silica zeolites like NaX and NaY have also
been conveniently prepared from kaolin (Breck,
1974). The reactions involved are: (1) calcination of
kaolin at 550-900~ to give a dehydroxylated,
X-ray amorphous, reactive product called meta-
kaolin; and (2) hydrothermal treatment of meta-
kaolin with aqueous NaOH to give zeolite 4A.
Many patents and research papers have been
reported dealing with the synthesis of zeolite 4A
from kaolin (Fitton & Fiore, 1978; Madani et aL,
1990; Rocha et al., 1991). The thermal activation
temperature of kaolin is found to influence the
nature of the product formed during the hydro-
thermal treatment with alkali.
Certain properties of metakaolin such as (a)
short-range disorder as measured by infrared fiR)
s p e c t r o s c o p y ; (b) d i s o r g a n i z a t i o n factor as
measured from the dissolution kinetics in dilute
HF; (c) pozzolanic reactivity as estimated by the
reaction with Ca(OH)2 and water; and (d) the
dissolution enthalpy in concentrated HF, are
directly related to the disordered structure and
chemical reactivity of metakaolin (Murat &
Bachiorrini, 1982; Bachiorrini & Murat, 1986;
Murat et al., 1987; Murat & Driouche, 1988).
The maximum values of these parameters are
r e p o r t e d for the m e t a k a o l i n p r e p a r e d at
720-750~ The variation in the tetra-, penta-
and hexa-coordinated A1 populations vs. the
temperature of kaolin treatment has been studied.
The tetra- and penta-coordinated A1 was found to
be at a maximum at 7 5 0 - 8 0 0 ~ (Rocha &
Klinowski, 1990). The yield of zeolite NaX
synthesized from metakaolin is influenced by the
firing temperature of the kaolin precursor (Howell
et al., 1965). It has recently been reported that the
thermal activation temperature is dependent on the
crystallinity and mineralogical composition of the
kaolin (Murat et al., 1992). A well crystallized
kaolin with a low impurity level has a higher
activation temperature than a poorly crystallized
sample.

9 1996 The Mineralogical Society

254 S. Chandrasekhar

In the present paper, an attempt has been made to High-resolution solid-state magic angle spinning
study the metakaolins prepared from a locally nuclear magnetic resonance (MAS NMR). The 29Si
available china clay at various temperatures and 27A1 MAS NMR spectra were recorded in a
(500-950~ with respect to their brightness and Bruker MSL 300 multinuclear NMR spectrometer
r e a c t i v i t y towards aqueous N a O H to form with an FT unit at 59.63 and 78.21 MHz,
zeolite 4A. These two properties become significant respectively. A rotor spinning speed of 4 - 4 . 5 kHz
in the synthesis of zeolite 4A for detergent and radio frequency pulses equivalent to 4 0 - 5 0 ~
applications where high calcium binding capacity pulse angle with a 5 - 8 s recycle delay was applied
(CBC) /> 160 mg CaO/g and brightness >90% ISO for Si. The rotor speed was 9.5-10.5 kHz and radio
are of particular importance. High CBC is easily frequency pulse equivalent to 9 ~ pulse angle with
achieved for clay-based zeolite 4A whereas the 0.25 s recycle delay for A1. Measurements were
level of brightness is always low. carried out at room temperature with tetra methyl
silane (TMS) for Si and Al(H20)6 for A1 as external
standards.
EXPERIMENTAL
Thermogravimetric analysis (TGA). Thermal
Analyst 2000, Du Pont was used to perform TGA
Synthesis and characterization
of dried (110~ 2 h) samples. Nearly 5 mg of the
A china clay from the Thiruvananthapuram sample was heated at a rate of 10~ in an
district of Kerala, India, with a fairly good atmosphere of air.
crystallinity, Hinckley Index = 0.79 (Hinckley, Brightness. The colour of the samples was
1963), was used for this study after processing by examined by measuring brightness with a Carl
size fractionation and chemical bleaching. Zeiss Photo electric r e f l e c t i o n p h o t o m e t e r
The metakaolins MK 500 to MK 950 were (ELREPHO) with BaSO4 as standard.
prepared by heating the kaolin at 500, 600, 700,
800, 900 and 950~ for 1 h in a muffle furnace.
The clay and the metakaolins were characterized by
XRD, IR, MAS NMR, TGA and brightness TABLE 1. Properties of kaolin.
measurements. The metakaolins were hydrother-
really treated with aqueous NaOH to form
Chemical constituents in wt% (by wet chemical
zeolite 4A. The molar ratios during the reaction
analysis)
were maintained at SiO2/Al203 = 2.0, Na20/SiO2 = 2.5
and H20/Na20 = 40. Reactants in identical sealable
SiO2 45.9
polythene tubes were kept in an oven at 85 ___ I~ AI203 38.9
and samples were taken out after definite intervals. Fe203 0.51
The product was filtered and washed with water to TiO2 0.49
remove excess alkali until the pH of the filtrate CaO 0.05
became 9 - 1 0 . The samples were dried at 85 __+ I~ MgO 0.04
for 24 h and rehydrated by storing over the water Na20 0.08
K20 0.03
vapour from saturated NaCI solution to attain their
Loss on ignition 13.8
equilibrium water content. The crystallinity was
measured by XRD. The Fe content of the filtrates
after 5 h of reaction of the metakaolins was Particle size distribution in % (Sedigraph 5000 D)
estimated by colorimetry. Microns +45 0.8
X-ray diffraction. Powder XRD patterns were Microns -45 +10 2.5
Microns - 1 0 +2 16.7
recorded on a Siemens D500 automated powder Microns - 2 80.0
diffractometer using Cu-K~ radiation. A scanning
speed of 0.12~ per min was used for the
Mineralogical analysis (XRD)
semiquantitative measurement of crystallinity.
Infrared (IR). The IR spectra of samples were Kaolinite Major
Quartz and mica Minor
recorded using a Perkin Elmer 1720 FTIR
Brightness (% ISO) 87.3/4.3
Spectrometer and caesium iodide wafer technique
(2 mg sample in 250 mg CsI).
 Formation of zeolite 4A from kaolin
I I I I
65 55 45
~
FIG. 1. X-ray diffraction patterns of kaolin and metakaolins. Cu-K~ radiation.
RESULTS AND DISCUSSION
The properties of the china clay under investigation
are given in Table 1. The clay is kaolinitic with
minor impurities of mica and quartz.
X R D analysis
The XRD patterns of the clay and metakaolins
are given in Fig. 1, the clay showing all the
characteristic peaks of kaolinite. On calcination,
these peaks disappear giving a featureless band of
X-ray amorphous metakaolin. The incomplete
metakaolinizatlon is indicated only in MK 500.
TGA analysis
The measurement of weight loss on heating the
clay shows that it loses N13.9% weight in the
range 4 5 0 - 5 5 0 ~ which is mostly due to combined
water in the structure of the kaolinite mineral. More
than half of this water remains in sample MK 500
and only ~ 20% of it in MK 600. Afterwards, the
drop is gradual as the calcination temperature
increases (Table 2). It is reported that metakaolinite
255
MK7
I I 1
35 25 15 5
has a structure containing ~ 1 1 % of the total
hydroxyls in the clay over most of its stability range
(Brown et al., 1985). The weight losses of samples
MK 700 and MK 800 fall in this range indicating
their closeness to the ideal metakaolinite structure.
The lower value of water content in MK 900 shows
that some structural changes have taken place.
Brightness measurements
Brightness is the ratio expressed as a percentage
of the radiation reflected by a body to that reflected
by a perfectly reflecting diffuser measured at an
effective wavelength of 457 nm. The reflection at
570 nm is also measured and the difference
between these values is termed as yellowness
(Jepson, 1988). The international standards
mention brightness as an important property for
zeolite 4A to be used in the detergent industry
(Degussa, 1987). Zeolite 4A prepared from pure
chemicals has a brightness value which is always
>90% (ISO). However, it is difficult to obtain a
zeolite of this brightness from clay. The colouring
impurities such as organic matter and ferruginous
minerals in clay influence the zeolite brightness.
256 S. Chandrasekhar
TABLE 2. Properties of kaolin, metakaolins and zeolites.
Temp. of Wt. loss %
calcination ~ (TGA)
0 13.8
500 8.0
600 2.75
700 1.75
800 1.25
900 0.98
950 0.82
The metakaolinization step eliminates the organics
to a great extent whereas the Fe minerals are
oxidized to give coloured ferric compounds. Most
of the external Fe in clay can be removed by
various beneficiation techniques whereas structural
Fe removal is difficult without structural break-
down. During metakaolinization, the kaolinite
structure is destroyed and both the free and
structural Fe are oxidized to coloured ferric
compounds, thus reducing the brightness. There is
a further decrease in brightness during zeolitization
(Table 2) which can be attributed to the liberation
of partially soluble Fe hydroxide/oxide during the
reaction with alkali. However, it has been reported
that the brightness of zeolite is directly related to
that of the metakaolin (Ferris, 1981).
The effect of different mineralogical forms of
free and structural Fe on the brightness of kaolin
has been studied in detail (Stoch, 1987). The
brightness of clay decreases initially on heating
and then increases as the temperature increases
from 500 to 1350~ This has been explained as
being due to a change in the position of Fe, i.e.
cluster formation during dehydroxylation of kaolin
and its incorporation into the structure of mullite. In
the present investigation, the brightness of the
sample decreases on heating to 500~ and later
increases with the temperature of calcination
(Table 2). The initial decrease is due to the
oxidation of external Fe minerals, partial liberation
and oxidation of structural Fe and incomplete
burning of organic matter. The gradual increase
thereafter can be attributed to the complete burning
of organics and also to a change in the position of
Fe as explained by Stoch (1987). The sample MK
900 is in a transition state and partial formation of
Al-spinel is possible. Part of the Fe may go into the
spinel structure (replacing A1) causing a decrease in
Brightness/yellowness %
Kaolin Zeolite 4A
(5 h reaction)
87.3/4.3 -
81.6/6.4 79.2/10.5
82.2/6.3 79.8/9.8
84.3/6.8 80.5/9.0
84.6/5.9 81.2/8.8
87.4/4.7 83.5/7.8
88.3/4.1 -
the electronic transitions. The brightness improve-
ment may be due to this phenomenon. Further
studies are essential to confirm this.
MAS NMR studies
The 29Si and 27A1 NMR spectra of the kaolin and
metakaolins are given in Fig. 2. The 29Si spectrum
of kaolin shows a single component at - 9 1 . 4 ppm,
characteristic of Si atoms of Si(1A1) environment.
During dehydroxylation, these Si atoms experience
a range of environments of differing distortion.
Broadening of the silicon line to the range - 9 9 to
- 1 0 2 p p m in the metakaolins is attributed to these
variations in the S i - O - S i ( A 1 ) bond angles
(MacKenzie et al., 1985). The upfield shifting of
Si resonance is explained as being due to a decrease
in the number of A1 groups bonded to silicate
groups, i.e. separation of SiO2 from the alumino-
silicate phase (Meinhold et al., 1985). In the present
study, as the temperature of calcination increases
from 500 to 900~ a change in the chemical shift
of the Si line is observed (Fig. 2a). The sample MK
900 has a line nearer to -110.5 ppm which is
characteristic of pure silica polymorphs. Hence,
partial release of silica at 900~ is evident and A1-
spinel may be forming simultaneously.
The unique sharp line of AI(VI) is present at
- 3 . 3 ppm in the 27A1 spectrum of kaolin whereas
broader signals are observed for metakaolins.
However, MK 500 has a distinct line at - 2 . 5 ppm
indicating the presence of AI(VI). As the tempera-
ture of metakaolin increases, this line becomes
weaker giving a broad spectrum with a small line
near 26 ppm and a shoulder near 48 ppm. The
sample MK 900 is found to have its maximum
population of A1 atoms between the AI(V) and
AI(IV) states. The T G A studies indicate the
 Formation of zeolite 4A from kaolin 257

I ~ N I v l R (78.21MHz)

, , . I 9 r , i . , , i . i . i I l l l l l l l . l I i i t i I , ~ | I
1 , 1 . L

0 -50 -60 -70 -80 -90 -100 -110-120-130-140 lOO 0 -100

ppm ppm

FIG. 2. (a) 29Si and (b) 27A1 MAS NMR spectra of kaolin and metakaolins.

presence of hydroxyls proving the presence of some
AI(VI) in MK 900. These residual hydroxyls,
attached to the AI(VI) atoms which are randomly
distributed throughout the structure, are difficult to
remove (Fig. 2b).
It is well known that nearly 90% of the total A1
signal is lost during metakaolinization resulting in
broadening of the signal and sharp decrease in
intensity (Meinhold et al., 1985). The detectable A1
atoms of metakaolin give broad spectra with
shoulders corresponding to AI(VI), AI(V) and
AI(IV). However, due to the second-order quadru-
pole interaction, the observed chemical shifts for A1
are field dependent and interpretation must be made
with caution.
IR spectral measurements
The mid-IR spectra of kaolin and metakaolins are
given in Fig. 3 and the band assignments in
Table 3. The spectra of kaolin show all the
typical bands of kaolinite (Percival et al., 1974).
After calcination, the intensities of these bands
(938, 914 and 540 cm -1) decrease and new bands
of metakaolin appear at 816 cm -1. The presence of
weak bands of (A1-O)-H at 910 cm -1, an A 1 - O
band at 540 cm -1 and an S i - O band at 693 cm - l
indicates that traces of the kaolinite structure are
retained in the metakaolins. The appearance of a
new band at 875 cm -I of S i - O in MK 900 may be
due to a change in the Si environment, i.e. partial
liberation of SiO2 prior to mullite formation.
Isolated SiO4 groups give a characteristic band at
901 cm -1. This observation supplements the 29Si
NMR data.
Zeolite f o r m a t i o n
Hydrothermal reaction of all the metakaolins with
alkali has been studied and Fig. 4a,b shows the
zeolite formation curves. The sum of intensities of
five strong peaks at 20 values of 21.6, 23.9, 27.1,
29.9 and 34.1 ~ was taken as a measure of
crystallinity of the product and the highest value
258 S. Chandrasekhar

(Mole, 1989; Dyer, 1988). Formation of the gel

a
from sodium aluminate and sodium silicate in
KAOLIN presence of aqueous NaOH is followed by an
l..tJ induction period during which nucleation takes
z
or place. The length of this induction period depends
I-- on temperature, gel composition and origin of the
I-- reactants. This is followed by a period of rapid
crystal growth which ends when the nutrients begin
to get exhausted and crystal growth becomes
difficult to maintain.
I--- When kaolin is used as the starting material, the
i i reaction is quite different. It has been reported that
1200 900 600 300 kaolin gives hydroxy sodalite, calcined kaolin
(500-900~ gives zeolite 4A and kaolin calcined
CM-I at a temperature above 900~ gives zeolite NaP
when hydrothermally treated with alkali (Madani et
al., 1990; Murat et al., 1992). Our previous studies
show that formation of zeolite 4A from metakaolin
is slow compared to the gel route (Rees &
Chandrasekhar, 1993). This is because of the
longer induction period due to slow dissolution of
metakaolin to form the gel. It has been pointed out
by Rocha & Klinowski (1990) that chemical
reactivity of metakaolinite is dependent on the
temperature of calcination and is at a maximum at
750-800~ According to these authors, the
~_s MK7 metakaolin prepared at this temperature range has
minimum AI(VI) and maximum AI(V) and AI(1V)
populations indicated by 27A1 MAS NMR study.
However, this thermal activation temperature is
again dependent on the crystallinity/presence of
ancillary minerals in the kaolin (Murat et al., 1992).
The kaolin under study is found to have maximum
reactivity in terms of zeolite formation when it is
calcined at 900~ for 1 h, the soaking period
1200 800 250 playing an important role. Samples MK 500 and
C M "I MK 600 have significant amounts of AI(VI) which
subsequently decrease as the calcination tempera-
FIG. 3. Mid-IR spectra of (a) kaolin and (b) metakaolin. ture increases. The minimum AI(VI) population in
the most reactive MK900 is substantiated by the
TGA, IR and NMR studies which agree with the
was taken as 100%. It is observed that after an earlier observation that the reactivity of metakaolin
induction period of 2 h, the rate of zeolite is inversely related to amount of AI(VI) (Rocha &
crystallization increases for the samples MK 500 Klinowski, 1990).
to MK 900. Zeolite 4A of good crystallinity and
CBC is formed within 3-4 h by MK 900 whereas a
D i s s o l u t i o n o f Fe
longer reaction time is required for others. The
sigmoidal curve for crystallinity in Fig. 4b is typical Variations in the dissolution enthalpy of kaolinites
of zeolite crystallization in the case of MK 900 and calcined at different temperatures in hydrofluoric
MK 800. acid have been reported and the value is maximum
Crystallization of zeolite 4A from sodium for a temperature of 800~ (Murat et al., 1987). In
aluminosilicate gel has been studied in detail the present study also, the calcination temperature is
 Formation of zeolite 4A .from kaolin 259

a b
8h 100
8O

:~ 6 0 : ~ ~ . . _ ~ /h/ i=_- 60

o 40
o
t ooo
20

2h
0 0
500 600 700 600 900 2 4 6 B
Calcination temperature of metakaolin ~ Reaction time (h)

FXG. 4. Crystallization of zeolite 4A from metakaolins prepared at various temperatures.

TABLE 3. Assignments of IR band wave numbers (cm-l).

Si-O bond (AlVI-O)-H bond AIvI-O bond AlIV-o bond

Sample from from from from
SiO4 AI[O(OH)]6 AI[O(OH)]6 A104

Kaolin 1114m, s; 1096m, sh 938m, sh 540s

i072s, br; 1060s, sh
1035s, 1012s 914ms, 789m, sh
794m, 752m, 693m
471s, 430m, 411m,w

MK 500 1067s, br 910w, sh 539 w 815m, br

467m, 692sh

MK 600 1089s, br; 692sh 539w, br 816m, br

458m

MK 700 1097s, br; 692sh 818m, br

464m

MK 800 1100s, br;

692w, sh; 460m m
819m,br

MK 900 1092s, br; m

816m, br
692vw sh
875vw br; 467m

s - strong; m - medium; br - broad; sh - shoulder; w - weak.

260 S. Chandrasekhar
TABLE 4. Amount of Fe leached from 100 g
metakaolin during zeolitization.
SI.No. Metakaolin Fe (mg)
1 MK 500 1.787
2 MK 600 2.620
3 MK 700 2.075
4 MK 800 1.865
5 MK 900 1.548
found to have some influence on the solubility of
metakaolin in a solution of NaOH during the
hydrothermal reaction. Table 4 indicates the
amount of Fe retained in the filtrate after zeolite
formation from the metakaolins. A sharp increase in
the quantity is observed when the temperature
changes from 500 to 600~ After that, a decreasing
trend is found in the solubility of Fe. The initial
sharp increase can be attributed to an effective
structural breakdown of kaolinite at 600~ as is
evident from the XRD, IR, MAS NMR and TGA
studies. The maximum dissolution of Fe in the alkali
during the reaction of MK 600 reflects on the
presence of maximum free Fe in the system which
decreases gradually as the temperature of calcination
increases. It may be due to the fact that more Fe is
going into the structure of metakaolin/zeolite and the
electronic transitions causing light absorptions in the
visible range are reduced resulting in the improve-
ment in brightness. These facts are consistent with
the increased brightness of metakaolins prepared at
high temperatures. A calcination temperature of
950~ has resulted in a metakaolin which on
treatment with NaOH gave more zeolite NaP than
4A. The temperature of 900~ and soaking time of
1 h seems to be crucial for this particular variety of
clay for the synthesis of zeolite 4A.
CONCLUSIONS
(1) The optimum temperature of dehydroxylation of
the kaolin under study to give detergent grade
zeolite 4A of satisfactory properties is 900~ (1 h).
(2) Zeolite 4A of 80% crystallinity and good
brightness is formed from MK 900 within 4 - 5 h on
alkali treatment under the conditions described.
(3) Almost the same crystallinity (90-95%) is
achieved for zeolite irrespective of the metakaoli-
nization temperature (500-900~ when the reac-
tion is carded out for an extended period of 8 h.
However, it varies in the initial stages indicating
differences in the kinetics for each metakaolin.
(4) During metakaolinization at high tempera-
tures, i.e. at ~700~ part of the Fe goes into the
structure and hence the brightness increases. The
amount of Fe leached out during zeolitization
decreases with increase in the metakaolinization
temperature. The zeolite brightness is found to have
a corresponding increase.
ACKNOWLEDGMENTS
The author is grateful to Prof. L.V.C. Rees, Imperial
College, London, for his permission to carry out part of
this work in his laboratory and to Dr Patrick Barrie,
University College London, for providing the MAS
NMR spectra. Thanks are also due to Mrs Rugmini
Sukumar and Mr V.S. Prasad of this laboratory and
M/S English Indian Clays Ltd for Fe estimation, TGA
and brightness measurements, respectively. Helpful
discussions with Dr M. Lalithambika and Mr P.
Raghavan and encouragement from our Director are
also gratefully acknowledged.
REFERENCES
BACH1ORRINIA. & MURATM. (1986) Infrared absorption
spectroscopy applied to the characterisation of the
amorphisation state of metakaolinite. C. R. Acad. Sc.
303, Ser. II, 1783-1786.
BARRER R.M. (1978) Zeolites and Clay Minerals as
Sorbents and Molecular sieves. Academic Press,
London.
BARRER R.M. (1982) Hydrothermal Chemistry of
Zeolites. Academic Press, London.
BRECK D.W. (1974) Zeolite Molecular Sieves -
Structure, Chemistry and Uses. Pp. 313-320 and
731-738. John Wiley & Sons Inc, New York.
BROWN I.W.M., MACKENZIEK.J.D. & MEINHOLDR.H.
(1985) Outstanding problems in the kaolinite-mullite
reaction sequence investigated by 29Si and 27AI solid
state NMR: High temperature transformation of
metakaolinite. J. Am. Ceram. Soc., 68, 298-301.
DEGUSSA(1987) Technical Bulletin Pigments Wessalith
for Detergents No. 71. Germany.
DYER A. (1988) An Introduction to Zeolite Molecular
Sieves. John Wiley & Sons, New York.
FERRIS A.P. (1981) Improvements in or relating to
zeolites. Br. Pat. l, 603,084.
FITTON R.C. & FIORE B.A. (1978) Preparation of
Improved Zeolites. US Pat. 4, 075,280.
HINCKLEY D.N. (1963) Variability in "Crystallinity"
values among the kaolin deposits of the coastal
plains of Georgia and South Carolina. Clays Clay
Miner. 11, 229-235.
 Formation of zeolite 4A from kaolin
HOWELL P.H., ACARA N.A. & TOWNE M.K. Jr. (1965)
Production of molecular sieve adsorbents from
kaolin minerals. Br. Pat. No, 980,891.
JEPSON W.B. (1988) Structural Fe in kaolinites and in
associated ancillary minerals. Pp. 467-536 in: Iron
in Soils and Clay Minerals (J.W. Stucki, editor), D.
Riedel Publishing Company, Netherlands.
MACKENZIE K.J.D., BROWN I.W.M., MEINHOLD R.H. &
BOWDEN M.E. (1985) Outstanding problems in the
kaolinite - mullite sequence investigated by 29Si and
/7Al solid state NMR: 1 metakaolinite. J. Am.
Ceram. Soc., 68, 293-297.
MADANIA., AZNARA., SANZ J. 8z SERRATOSAJ.M. (1990)
29Si and 27A1 NMR study of zeolite formation from
alkali leached kaolinites - influence of thermal
preactivation. J. Phys. Chem. 94, 760-765.
MEINHOLD R.H., MACKENZIE K.J.D. & BROWN I.W.M.
(1985) Thermal reactions of kaolinite studied by
solid state 29Si and 27A1 NMR. J. Mat. Sci. Lett., 4,
163-166.
MOLE V.C. (1989) Improved Zeolite Builders for
Detergents. PhD thesis, Univ. London, UK.
MURAT M. & BACHIORRINIA. (1982) Correlations entre
l ' e t a t d ' a m o r p h i s a t i o n et l ' h y d r a u l i c i t e du
metakaolin. Bull. Mineral. 105, 543-555.
MURAT M. & DRIOUCHE M. (1988) Conductimetric
investigations on the dissolution of metakaolinite in
dilute hydrofluoric acid. Structural implications.
261
Clay Miner. 23, 55--67.
MURAT M., MATHURIN D. & CHBIHIEL M. (1987)
Enthalpie de dissolution de differentes kaolinites et
metakaolinites dans l'acide fluorhydrique, Influence
des caracteristiques crystallochimiques.
Thermochim. Acta, 122, 79-85.
MURAT M., AMOKRANEA., BASTIDEJ.P. & MONTANARO
L. (1992) Synthesis of zeolites from thermally
activated kaolinite - - some observations on nuclea-
tion and growth. Clay Miner. 27, 119-130.
PERCIVAL H.J., DUNCAN J.F. & FOSTER P.K. (1974)
Interpretation of the kaolinite-mullite reaction se-
quence from infra red absorption spectra. J. Am.
Ceram. Soc. 57, 57-61.
REES L.V.C. & CHANDRASEKHARS. (1993) Formation of
zeolites from the system NazO-SiOz-A12Oa-H20 in
alkaline medium (pH 10). Zeolites, 13, 524-533.
ROCnA J. & KLINOWSKI J. (1990) Solid state NMR
studies of the structure and r e a c t i v i t y of
metakaolinite. Angew. Chem. Int. Ed. Engl. 29,
553-554.
ROCHA J., KLINOWSKIJ. & ADAMSJ.M. (1991) Synthesis
of Zeolite 4A from metakaolinite - revisited. J.
Chem. Soc. Faraday Trans. 87, 3091-3097.
STOCH L. (1987) Iron in kaolins - Mineralogical
crystallo-chemical and technological aspects.
Interceram. 6, 21-25.