Applied Clay Science 44 (2009) 194–200

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Influence of degree of dehydroxylation on the pozzolanic activity of metakaolin

Ch. Bich, J. Ambroise, J. Péra ⁎
Laboratoire de Génie Civil et Ingéniérie Environnementale (LGCIE), Domaine Scientifique de la Doua, 12, Avenue des Arts, Bâtiment Joseph Tuset,
Institut National des Sciences Appliquées de Lyon, 69621 Villeurbanne Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: Three kaolins were heated between 500 and 850 °C. The samples were tested by X-ray diffraction (XRD),
Received 10 June 2008 differential thermal analysis (DTA), and Infra-Red (IR) spectroscopy in order to determine their mineralogical
Received in revised form 21 January 2009 composition and degrees of crystallinity and dehydroxylation. The reactivity of the heated samples was
Accepted 23 January 2009
evaluated by the determination of the residual quantity of Ca(OH)2 by differential thermal analysis (DTA)
Available online 7 February 2009
performed on hydrated mixtures of 50% metakaolin and 50% Ca(OH)2. There was no direct relationship
Keywords:
between the pozzolanic activity of metakaolin and the degree of dehydroxylation. Highest activity was
Dehydroxylation obtained when the degree of dehydroxylation was N 95%.
Metakaolin © 2009 Elsevier B.V. All rights reserved.
Pozzolanic activity

1. Introduction 2. Experimental procedure

Metakaolinite is obtained by heating kaolinite at 700–850 °C. It
is a poorly crystalline transition phase which behaves as highly
reactive artificial pozzolan. Nowadays, the properties of calcined
clays are widely discussed in cement literature for their pozzolanic
properties (Saad et al., 1982; Ambroise et al., 1986; Sayanam et al.,
1989; Da Silva and Glasser, 1990; Dunster et al., 1993; Wild and
Khatib, 1997; Curcio et al., 1998; Péra et al., 1998; Wild et al., 1998;
Frias and Cabrera, 2000; Sabir et al., 2001). Metakaolinite reacts
2.1. Characterization of raw materials
The raw materials investigated were three specimens of kaolin
(Tables 1 and 2). All samples presented about the same particle size
distribution (D50), but K3 showed a higher BET specific surface area
Table 1
Chemical composition of the kaolins (mass %).

with calcium hydroxide and water to yield hydrated compounds of Oxides K1 K2 K3

Ca and Al silicates. The pozzolanic activity of metakaolinite is SiO2 57.61 47.41 47.15
related to the cristallinity of the original kaolinite (Gniewek, 1987; Al2O3 29.54 35.98 34.55
Martin-Calle, 1989; Ambroise et al., 1992; Kakali et al., 2001; Bich, TiO2 0.89 0.46 1.88
Fe2O3 0.78 1.16 1.31
2005).
MgO 0.13 0.2 –
This paper deals with the influence of degree of dehydroxylation K2O – 1.43 0.98
on the pozzolanic activity of metakaolinite. Three kaolins of different P2O5 0.06 0.09 0.13
mineralogical composition and crystallinity were heated in a fixed- LOI 10.88 12.92 13.55
bed electrical furnace at different temperatures and for different times Total 99.94 99.68 99.51

to obtain different degrees of dehydroxylation. Heated samples were

characterized by X-ray diffraction (XRD), differential thermal analysis Table 2
(DTA), and Infra-Red (IR) spectroscopy. Their pozzolanic activity was Mineralogical composition, crystallinity and physical properties of the kaolins.

evaluated by the determination of the residual quantity of Ca(OH)2 by Mineral K1 K2 K3

DTA performed on hydrated mixtures of 50% metakaolin and 50% Ca Kaolinite (mass %) 75.0 79.0 87.3
(OH)2. Quartz (mass %) 23.0 5.1 6.5
Illite (mass %) – 12.4 –
P0 1.4 1.4 0.68
P2 0.5 0.5 –
SR 0.95 0.95 2.05
D50 (µm) 8 9 9
⁎ Corresponding author. Tel.: +33 4 72438296; fax: +33 4 78949807.
SBET (m2/g) 9.9 7.3 30.5
E-mail address: Jean.Pera@insa-lyon.fr (J. Péra).

0169-1317/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2009.01.014
 C. Bich et al. / Applied Clay Science 44 (2009) 194–200 195

Fig. 1. XRD of raw samples (K: kaolinite; I: illite; Q: quartz).

Fig. 4. IR spectra of raw materials (zone: 1 400–450 cm− 1).

(Table 2). The mineralogical composition of kaolins was assessed by

X-ray diffraction (XRD), differential thermal analysis (DTA), and
Fourier transform infra-red spectrometry (FTIR).
XRD (Fig. 1) showed the presence of kaolinite and quartz in each
sample, K2 contained some illite. DTA (Fig. 2) showed the decom-
position of kaolinite into metakaolinite at 500–650 °C, and the
formation of mullite between 950 and 1000 °C. Sample K3 presented
the highest content of kaolinite (87.3%). Sample K1 contained higher
amounts of quartz than samples K2 and K3. The FTIR analyses,
Fig. 2. DTA curves of raw samples. performed using a Spectrum-One Fourier Transform IR Perkin Elmer
spectrometer (Figs. 3 and 4) showed the characteristic bands of
kaolinite (Russel, 1987):

– OH−: 3700, 3670, 3650, 3620 cm− 1

– Al–OH: 913 cm− 1
– Si–O: 1115, 1032, 1008, 469 cm− 1
– Si–O–AlIV: 789, 754 cm− 1
– Si–O–AlVI: 538 cm− 1.

Fig. 3. IR spectra of raw materials (zone: 3800–3520 cm− 1). Definition of P0 and P2. Fig. 5. Definition of the slope ratio SR (Liétard, 1977).
196 C. Bich et al. / Applied Clay Science 44 (2009) 194–200

Table 3
Conditions of calcination and degree of dehydroxylation.

Parent Metakaolin Calcination Calcination Degree of

kaolin temperature (°C) period (min) dehydroxylation (%)
K1 M1S1 650 30 50
M1S2 650 45 71
M1S3 850 30 97
M1S4 650 60 97
M1S5 650 300 100
M1S6 750 300 100
M1S7 850 300 100
M1S8 650 900 100
M1S9 700 900 100
M1S10 750 900 100
M1S11 850 900 100
K2 M2S1 650 15 50
M2S2 650 45 95
M2S3 650 300 100
M2S4 850 300 100
M2S5 650 900 100
M2S6 850 900 100
K3 M3S1 500 60 50
M3S2 650 3 62
M3S3 650 10 80
M3S4 650 30 95
M3S5 650 45 100
M3S6 650 300 100
M3S7 850 300 100
M3S8 650 900 100
M3S9 850 900 100

The three kaolinites showed different degrees of order (Worral,

1986), (Table 2). IR spectra give qualitative information about the order
or the disorder of the structure. For kaolinite, there is a group of
absorption peaks between 3500 and 3700 cm− 1, which is due to the
stretching frequencies of the OH groups. The inner OH groups attached
to aluminum and oxygen atoms within the gibbsite layer have a
characteristic stretching frequency of 3620 cm− 1. The inner surface OH
groups which are the boundary of the gibbsite layer and able to form
hydrogen bonds with the adjoining silica layers are 3700, 3670 and

Table 4
Physical properties of the metakaolins.

Parent kaolin Metakaolin D50 (µm) SBET (m2/g)

K1 M1S1 6.9 8.3
Fig. 6. Relationship between degree of dehydroxylation (D) and D50.
M1S2 7.0 8.4
M1S3 8.2 7.4
M1S4 8.1 8.5
M1S5 8.8 7.3
M1S6 7.6 7.2 3650 cm− 1, which are susceptible to disturbances of hydrogen bonding
M1S7 6.4 7.6 associated with ab displacements or isomorphous substitutions.
M1S8 7.8 7.3 Two indices were defined (Fig. 3): P0 and P2. P0 is the ratio
M1S9 7.6 7.6
M1S10 7.5 7.3
between the intensities of the bands observed at 3620 cm− 1 and
M1S11 6.5 7.4 3700 cm− 1. P2 is the ratio between the intensities of the bands at
K2 M2S1 9.2 6.3 3670 cm− 1 and 3650 cm− 1. According to Ambroise et al. (1992),
M2S2 10.0 6.7 Meinhold et al. (1992), and Russel (1987), kaolinite is well ordered
M2S3 9.7 6.7
when: P0 N1 and P2 b1. When kaolinite is disordered, the band at
M2S4 9.4 6.8
M2S5 9.7 7.0 3670 cm− 1 disappears and P2 cannot be defined. Kaolinite K3 was
M2S6 9.0 7.0 disordered whereas kaolinites K1 and K2 were well ordered (Table 2).
K3 M3S1 10.1 31.8 The slope ratio (SR) is the ratio between the slope of the
M3S2 12.2 31.9 descending branch of the dexhydroxylation peak in the DTA curve
M3S3 9.1 31.1
M3S4 9.3 31.4
and the slope of the ascending branch of this peak (Fig. 5) (Liétard,
M3S5 8.6 31.9 1977). The slope ratio characterizes the presence of surface defects.
M3S6 8.7 30.7 When SR = 1, the peak is symmetric and kaolin does not present many
M3S7 8.5 29.1 surface defects. When SR = 2, many surface defects are present. Thus
M3S8 8.4 29.1
K1 and K2 contained small amounts of defects, K3 high amount of
M3S9 7.8 28.9
surface defects (Table 2).
 C. Bich et al. / Applied Clay Science 44 (2009) 194–200 197

– kaolin K3 is a disordered kaolin, presenting high amounts of

surface defects and a high BET specific surface area.

2.2. Calcination of the kaolins

Different calcined products were obtained varying the tempera-

ture (between 500 °C and 850 °C) and the time (between several
minutes and hours) (Table 3).
The degree of dehydroxylation was assessed by DTA (Ambroise,
1984), measuring the residual peak of kaolinite dehydroxylation on
the heated product. The degree of dehydroxylation (Table 5) was
calculated as follows:

SK − SMK
DðkÞ = × 100
SK

with:

– D (%): degree of dehydroxylation,

– SK: area of the endothermal peak corresponding to the
dehydroxylation of kaolinite,
– SMK: area of the residual peak of remaining kaolinite in
metakaolin.

2.3. Pozzolanic activity of the metakaolins

The pozzolanic activity of the metakaolins was measured after

different time periods (7, 28, and 90 days) on pastes composed of 50%
calcium hydroxide and 50% metakaolin, hydrated at normal consis-
tency, according to the French standard NFP 15-402 (Ambroise, 1984).
Mini-cylinders of paste were cast in Plexiglas moulds (ϕ = 20 mm,

Fig. 7. Relationship between degree of dehydroxylation (D) and BET specific surface area.

We conclude:

– kaolins K1 and K2 are well-crystallized samples, presenting low

amounts of surface defects and a relatively low BET specific surface
area;

Table 5
Crystallinity of incomplete dehydroxylated kaolins.

Parent kaolin Metakaolin Degree of dehydroxylation (%) SR P0 P2

K1 M1S1 50 0.81 1.0 0.5
M1S2 71 0.96 1.0 0.6
M1S3 97 0.92 0.98 0.6
M1S4 97 0.96 0.85 0.6
K2 M2S1 50 0.85 1.0 0.5
M2S2 95 0.97 0.98 0.6
K3 M3S1 50 2.1 0.65 –
M3S2 62 2.3 0.65 –
M3S3 80 2.6 0.65 –
M3S4 95 2.6 0.57 –
Fig. 8. Relationship between degree of dehydroxylation (D) and slope ratio (SR).
198 C. Bich et al. / Applied Clay Science 44 (2009) 194–200

Fig. 9. IR spectra of kaolin K1 and metakaolins M1S1 to M1S5.

h = 40 mm) and kept at 20 °C until the day before the desired time
period. Then, they were dried at 50 °C for one night and ground to get
particles b100 µm. The powders were subjected to DTA, and the
pozzolanic activity was defined as the calcium hydroxide consump-
tion versus time measured by the residual DTA peak of calcium
hydroxide.

3. Results and discussion

3.1. Characterization of the metakaolins

The physical parameters (D50 and BET specific surface area) of

metakaolins remained very close to those of the starting kaolins
Fig. 11. Relationship between degree of dehydroxylation (D) and index of crystallinity (P0).
(Table 4). There was no general trend of D50 versus the degree of
dehydroxylation (Fig. 6): D50 remained constant for metakaolins K1, it

Fig. 10. IR spectra of incompletely dehydroxylated metakaolins (M1S1 to M1S4).

 C. Bich et al. / Applied Clay Science 44 (2009) 194–200 199

Fig. 13. Relationship between the lime consumption after 7 days and degree of
dehydroxylation.

According to the conditions of thermal treatment, the degree of

dehydroxylation varied from 50 to 100% (Table 3). Total dehydroxyla-
tion occurred for the following conditions:

– K1: calcination at 650 °C for 5 h;

– K2: calcination at 650 °C for 5 h;
– K3: calcination at 650 °C for 45 min.
The disordered kaolinite was more easily dehydrated.
For degrees of dehydroxylation b100%, the slope ratio SR and
indexes P0 and P2 were calculated (Table 5).
Fig. 8 shows the relationship between the degree of dehydroxyla-
tion (D) and the slope ratio (SR). The general trend was: the higher the
degree of dehydroxylation the higher the slope ratio. Higher degree of
dehydroxylation increased the quantity of surface defects in the
remaining kaolinite. Nevertheless, the correlation was less adequate
for well-crystallized metakaolins (K1 and K2), R2 = 0.68 instead of
0.90.
When total dehydroxylation was not reached (D b 100%), the
characteristic IR bands of kaolinite were still present in calcined
samples (Fig. 9). The dehydroxylation of kaolinite was indicated by the
progressive decrease in intensity of the doublet at 3700 cm− 1 and
3620 cm− 1. The structure became more and more amorphous. The
doublet disappeared at total dehydroxylation (sample M1S5). The
formation of metakaolin was also confirmed by the absence of Al–OH
bands at 920 and 940 cm− 1 (Fig. 10); the presence of the large band at
1100–1000 cm− 1 is assigned to amorphous silica. The ratio P0
decreased when the degree of dehydroxylation increased (Table 5
and Fig. 11), while P2 slightly increased, indicating that the crystal-
linity of the remaining kaolinite decreased. The correlation was less

Fig. 12. Lime consumption of metakaolins a) K1, b) K2, c) K3.

slightly increased for metakaolins K2, and decreased for K3. The BET
specific surface area (Fig. 7) decreased for metakaolins K1, and Fig. 14. Relationship between the lime consumption after 28 days and degree of
remained constant for other samples. dehydroxylation.
200 C. Bich et al. / Applied Clay Science 44 (2009) 194–200
pronounced for well-crystallized metakaolins (K1 and K2), R2 = 0.32
instead of 0.61.
Thus, when dehydroxylation was incomplete (D b 100%), some
kaolinite remained in the metakaolin and became less crystalline with
higher quantity of surface defects.
3.2. Pozzolanic activity of metakaolin
The pozzolanic activity of the different metakaolins is shown
in Fig. 12. Metakaolin M3S1 did not consume any calcium hydroxide
at any age. It presented a degree of dehydroxylation of 50% like M1S1
and M2S1, but was not heated long enough (500 °C for 1 h). As
the content of kaolinite was different in all samples (K3 N K2 N K1),
the consumption of calcium hydroxide was higher for metakaolins
K3, especially after 7 days. For example, for the same degree of
dehydroxylation (100%), and the same conditions of calcination
(650 °C for 5 h), the reactivity of metakaolins after 7 days was as
follows: M3S6 N M1S5 N M2S3. The reactivity was no longer different
after 28 days.
After 7 days (Fig. 12a), the highest calcium hydroxide consump-
tion was obtained by M1S4 (75%) in series M1Si, M2S2 and M2S6
(56%) in series M2Si, and M3S5 (98%) in series M3Si. The degree of
dehydroxylation of these metakaolins was N95%. M1S4 was heated
at 650 °C for 1 h; it presented a degree of dehydroxylation of 97%,
the highest slope ratio (SR = 0.96), and the highest BET specific
surface area of the M1Si series. M2S2 (650 °C for 45 min) presented
a degree of dehydroxylation of 95%, while that of M2S6 (850 °C for
15 h) was 100%. The degree of dehydroxylation of M3S5 was 100%;
it was heated at 650 °C for 45 min. Calcination times of 5 or 15 h
above 650 °C decreased the pozzolanic activity of metakaolins.
After 7 days, metakaolins K2 were generally less reactive than K1
and K3. There was no direct relationship between the pozzolanic
activity after 7 days and the degree of dehydroxylation (R2 = 0.36)
(Fig. 13).
After 28 days (Fig. 12b), calcium hydroxide consumption increased
for all specimens, and was N90% for samples with a degree of
dehydroxylation N95%. The correlation between the pozzolanic
activity and the degree of dehydroxylation was better after 28 days
than 7 days (Fig. 14). The influence of calcination times above 650 °C
on the lime consumption disappeared.
After 90 days (Fig. 12c), samples with a degree of dehydroxylation
b80% (M1S1, M1S2, M2S1, M3S2, M3S3) showed incomplete lime
consumption. Therefore, it is necessary to reach nearly total
dehydroxylation (D ≥ 95%) for complete calcium hydroxide consump-
tion, even after long times. Of course, this conclusion is only valid for
the type of heat treatment adopted in the present study.
4. Conclusions
When dehydroxylation was incomplete (D b 100%), some kaolinite
remained in the metakaolin and became less crystalline with higher
quantity of surface defects.
When kaolin was heated in a fixed-bed electrical furnace, a degree
of dehydroxylation N95% had to be achieved to yield highly reactive
metakaolin.
Long calcination times (5 or 15 h above 650 °C) decreased the
pozzolanic activity after 7 days. This phenomenon disappeared at later
time periods (28 or 90 days).
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