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Applied Clay Science 42 (2008) 189 – 193

www.elsevier.com/locate/clay

Calcination of art paper sludge waste for the use as a supplementary

cementing material
Moisés Frías a,⁎, Rosario García b , Raquel Vigil b , Sergio Ferreiro a
a
Instituto Eduardo Torroja, CSIC, C/ Serrano Galvache, 4, 28033 Madrid, Spain
b
Dpto de Geología y Geoquímica, Facultad de Ciencias, Universidad Autónoma, 28049 Madrid, Spain
Received 9 August 2007; received in revised form 22 January 2008; accepted 23 January 2008
Available online 1 February 2008

Abstract

This study shows the effect of calcination clay wastes from an art paper sludge for the use as supplementary cementing materials in blended
cements.
The starting clay sludge rich in kaolinite and talc was calcined at 600, 650 and 700 °C between 2 and 5 h, kaolinite was transformed into
amorphous metakaolinite.
This study reveals that calcination at 650 °C for 2 h is recommended to obtain a good supplementary cementing material for manufacture of
blended cements.
© 2008 Elsevier B.V. All rights reserved.

Keywords: Art paper sludge; Clay minerals; Thermal activation; Metakaolinite; Supplementary cementing material

1. Introduction with some degree of order. In metakaolinite, the Si–O network

The use of supplementary cementing materials for the
manufacture of blended cements is well known during the last
decades. According to the existing standards UNE-EN 197-1
(2005), these additions are generally natural pozzolans from
volcanic and by-products like fly ash, silica fume, blast furnace
slag. However, the thermally activated clayey minerals in
cement manufacture are not used although they have excellent
qualities. Furthermore, the previous researches are focused,
mainly on kaolinite (Ambroise et al., 1985; Taylor, 1997;
Palomo et al., 1999; Moropoulou et al., 2004; Ali and Wahid,
2006).
The reactivity of metakaolinite varies with thermal treatment
(Rocha and Klinowski, 1990) during calcination (450 °C–
600 °C) and turns into metakaolinite (Grim, 1968), a material
⁎ Corresponding author. Fax: +34 91 3020700.
E-mail address: mfrias@ietcc.csic.es (M. Frías).
0169-1317/$ - see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2008.01.013
remains largely intact while the structure of Al–O network is
reorganized, metakaolinite offers good properties as supple-
mentary cementing material. It reacts particularly well with lime
and forms hydrated compounds of Ca and Al silicates in water
(Frías et al., 2000; Sabir et al., 2001; Frías and Sánchez de
Rojas, 2003; Moropoulou et al., 2004; Saikia et al., 2006; Singh
and Garg, 2006; Frías, 2006; Bacolas et al., 2006).
From the environmental point of view, paper sludge wastes
should be recycled obtain metakaolinite. Previous studies have
shown the good qualities of these calcined clay wastes as highly
pozzolanic materials (Pera and Amrouz, 1998; Frías et al., 2004;
Banfill and Frías, 2007; Vegas et al., 2006).
Due to the chemical and mineral composition of these clayey
paper wastes, products calcined at 700–800 °C showed decreased
reactivity as a consequence of the combination of three fun-
damental aspects: decarbonation, formation of new phases and
less reactive surface (Vigil et al., 2007).
As no reports are available on the activation of this type of clay
waste under 700 °C, the present study shows the morphological
and mineralogical changes of the clay minerals 600–700 °C
during 2 and 5 h.
190 M. Frías et al. / Applied Clay Science 42 (2008) 189–193

2. Materials and experimental methods

2.1. Art paper sludge

The starting clay waste was an art paper sludge from the Holmen Paper
Madrid, S.L. This European industry is the only one that uses 100% the recycled
paper as raw material.
The dry art paper sludge after 24 h at 105 °C has been calcined in a laboratory
programmable furnace at 600, 650 and 700 °C during 2 and 5 h. The calcined
products were ground in a mortar and then sieved below 45 μm. The samples were
designed such as 600/2 (sample calcined at 600 °C from 2 h), 600/5 (sample calcined
at 600 °C from 5 h) 650/2 (sample calcined at 650 °C from 2 h), 650/5 (sample
calcined at 650 °C from 5 h) and 700/2 (sample calcined at 700 °C from 2 h).

2.2. Chemical, mineralogical and textural characterization

Chemical characterization was carried out by X-ray fluorescence (Philips

PW 780, an anticathode tube of rhodium of 4 kW). The loss of ignition (L.O.I.) Fig. 1. XRD pattern for the starting art paper sludge.
was calculated according to the existing European standard (EN 196-2, 1996).
The mineralogical composition was studied by X-ray diffraction (XRD)
using random powder of the bulk sample and oriented slides of the b2 μm loss was of 55.7% and the rest of oxides were below 1% in
fraction (Moore and Reynolds, 1997). The X-ray diffractometer was a weight. Traces of chloride ions (0.06%) could be detected in the
SIEMENS D-500 (Cu anode, 30 mA, 40 kV) the procedure proposed by starting paper sludge, depending on the origin of the recycled
Schultz (1964) was used to quantify the components.
paper.
Morphological characterizations were done using a SEM-EDX devise
(PHILIPS XL30, W source, DX4i analyser and Si/Li detector). The analyser According to the XRD patterns (Fig. 1) and chemical
was calibrated with a multimineral sample: The USGS standard ADV-1 composition, the clayey waste was mainly formed by kaolinite
(Govindaraju, 1994). The chemical composition was obtained by an average (12.3%) and calcite (43%) and, in minor proportions some
value of ten analyses for each sample. phyllosilicates such as chlorite, micas and talc (with a total
percentage of 7.1%). An organic matter content of 34.9% was
2.3. Pozzolanic activity method
determined.
An accelerated method was used to study the pozzolanic activity of calcined
sludge. The test consisted of introducing these calcined clay wastes in a saturated
lime solution at 40 °C for 1, 7, 28 and 90 days. At the end of each period, the CaO
concentration in the solution was analysed (Frías et al., 2004). The adsorbed lime
(mMol/L) was obtained as difference between the concentration in the saturated
lime control solution and the CaO found in the solution in contact with the
sample. A commercial metakaolinite was also used as reference.

3. Results and discussion

3.1. Chemical and mineralogical composition of starting paper

sludge

The starting paper waste was composed mainly of SiO2

(10.7%), Al2O3 (6.7%) and CaO (24.2%) (Table 1). The ignition

Table 1
Chemical composition of starting and calcined art paper sludges by XRF
Composition Raw 600 °C/ 600 °C/ 650 °C/ 650 °C/ 700 °C/
(%) sludge 2h 5h 2h 5h 2h
SiO2 10.69 20.24 20.65 21.06 21.44 22.32
Al2O3 6.74 13.11 13.38 13.58 13.87 14.55
Fe2O3 0.41 0.52 0.52 0.54 0.54 0.56
CaO 24.15 36.39 37.20 37.81 38.55 40.21
MgO 0.96 2.15 2.20 2.24 2.30 2.35
SO3 0.30 0.28 0.28 0.29 0.29 0.32
K2O 0.22 0.34 0.34 0.35 0.35 0.37
Na2O 0.24 0.08 0.08 0.09 0.09 0.09
TiO2 0.21 0.24 0.25 0.25 0.25 0.26
P2O5 0.16 0.17 0.17 0.17 0.18 0.18
Fig. 2. A) Cellulose fibbers, kaolinite and micas in the raw sludge. B) Talc
L.O.I. 55.71 26.24 24.68 23.36 21.93 18.52
crystals in the raw sludge.
 M. Frías et al. / Applied Clay Science 42 (2008) 189–193 191

Fig. 3. XRD patterns for the calcined products.

3.2. Morphology of raw clay sludge

The components observed in the initial clay sludge by SEM

were fibbers of cellulose assorted (organic component),
kaolinite aggregates and micas (Fig. 2A). The calcite appeared
as isolated crystals or aggregates. Chlorite and talc crystals are
also shown (Fig. 2B).

3.3. Chemical and mineralogical composition of activated clay

sludges

As it was expected, the chemical composition between raw

and activated clay sludge was remarkably different. This fact is
related to the presence of organic matter in the raw sludge. In the
case of activation the paper sludge at different conditions, a light
increase in oxides content is observed as a consequence of the
decrease of loss of ignition (L.O.I.).
The sample 600/2 consisted of calcite and talc (reflection at
2θ = 9.40°; 19.0° and 28.68°) by XRD (Fig. 3) but the initial

Table 2
Chemical analysis by EDX of the samples at 600 °C/2 h
% oxides Metakaolinite aggregates Talc Talc aggregates
MgO 3.27 ± 1.18 25.92 13.35 ± 2.76
Al2O3 21.85 ± 4.65 5.54 12.07 ± 1.83
SiO2 34.73 ± 5.97 58.83 48.64 ± 2.94
K2O – – –
Na2O – – –
CaO 40.15 ± 10.34 9.71 25.94 ± 5.68
TiO2 – – –
Fe2O3 – – –
Fig. 4. A) Metakaolinite and calcite from calcined sludge at 650 °C after 5 h.
Total 100 100 100
B) Talc, metakaolinite and calcite from calcined sludge at 650 °C after 5 h.
192 M. Frías et al. / Applied Clay Science 42 (2008) 189–193

Table 3
Chemical analysis by EDX of the samples at 650 °C/2 h
% oxides Metakaolinite Metakaolinite Talc Calcite
aggregates (1) aggregates (2) aggregates
Na2O – 1.40 ± 0.02 – –
MgO 2.80 ± 1.93 1.62 ± 0.25 31.40 2.13 ± 1.60
Al2O3 23.87 ± 1.65 23.77 ± 0.76 0.86 13.95 ± 4.69
SiO2 34.75 ± 2.91 35.83 ± 2.69 63.59 19.36 ± 7.09
K2O – 0.58 ± 0.02 – –
CaO 38.58 ± 4.67 36.89 ± 3.53 2.12 64.55 ± 10.79
Fe2O3 – – 2.03 –
TiO2 – – – –
Total 100 100 100 100

Fig. 5. Pozzolanic activity evolution versus reaction time.

kaolinite (reflection peaks at 2θ = 12.36° and 24.99°) trans-
formed into metakaolinite observed by SEM (Fig. 4A).
The hexagonal metakaolinite particles formed small aggre- 3.4. Pozzolanic activation
gated ones with very rich in calcium (Table 2). Fibrous forms
rich in magnesium were also identified, corresponding to talc Vigil et al. reported the importance of calcination conditions
(Fig. 2B). Residual cellulose is also observed. on the activation process of clayey material. When a kaolinite
SEM after 5 h of treatment showed metakaolinite plates. In based paper sludge was heated between 700 and 800 °C, the
general, when the time of thermal treatment was increased, we metakaolinite presented a loss of activity and specific surface
observed both bigger aggregates and higher crystallinity. area with increasing temperature. These data are in agreement
Calcination at 650 °C did not change the mineralogical with the data reported by Frías et al. (2004).
composition as observed at 600 °C. In this case, mineralogical The results obtained for the combination of lime with
transformation processes were detected such as the intensity of calcined sludges (accelerated pozzolanic test) are shown in
calcite decreased and chlorite at 14 Å increased (Brown and Fig. 5. After 24 h of reaction, the different calcined products
Brindley, 1984). SEM analysis showed aggregates of calcite showed a high pozzolanic activity, since these activated sludges
with a bigger size. The compact metakaolinite aggregates had had fixed significant amounts of lime, and these values are close
a wide range of sizes with different sodium and potassium to the combined lime in reference silica fume (SF) (Table 5), an
concentrations (Table 3) (Fig. 4B). Talc formed massive ag- industrial by-product with the highest pozzolanic activity of all
gregates and their reflections were very high indicating high pozzolans blended with Portland cement.
crystallinity (Chopin, 1981). The cellulose fibbers disappeared. In general, the results show that there is no relation between
The results obtained after 5 h are very similar to those the calcining conditions and the calcined sludge activation to
obtained after 2 h. Calcite due to decarbonation and mica show obtain highly active products in the interval 600–700 °C.
low crystallinity (Fig. 4B). However, our results show less differences ( Fig. 5 and Table 5).
The results for the calcination at 700/2 show portlandite At low temperatures (600–650 °C), the lime fixed by calcined
(CaO) formation and the alteration compound Ca(OH)2 at the clay products increased with temperature. From 650 °C and 5 h
atmosphere (reflections at 2θ = 18.01° and 34.19°). SEM of retention time, this effect was contrary. The calcined clay
revealed metakaolinite aggregates and calcite with a very products at 700 °C and 2 h showed the lowest pozzolanic
porous surface (Table 4). activity. Therefore, an inflexion point in the pozzolanic activity
development can be detected at 650 °C and 2 h of retention. For
this reason, these conditions are suggested to get the maximum
activation of paper sludge waste.
A possible explanation to this slight decrease of fixed lime
Table 4 from 650 °C and 2 h could be related to the combination of two
Chemical analysis by EDX of the samples at 700 °C/2 h
effects: 1) The decrease of reactive specific surface area of
% oxides Metakaolinite aggregates Calcite aggregates Talc aggregates
MgO – 0.17 ± 0.05 2.45 ± 0.12
Al2O3 6.39 0.80 ± 0.14 1.04 ± 0.11 Table 5
SiO2 48.56 7.28 ± 1.67 77.09 ± 0.75 Fixed lime values at 28 and 90 days of reaction
Na2O – – –
Fixed SF 600 °C/2 h 600 °C/5 h 650 °C/2 h 650 °C/5 h 700 °C/2 h
K2O 0.52 – –
lime
CaO 43.76 91.75 ± 1.88 18.03 ± 1.11
(%)
TiO2 – – –
Fe2O3 0.77 – 1.39 ± 0.60 28 days 88.4 86.7 88.4 90.1 88.4 82.8
Total 100 100 100 90 days 88.4 91.4 93.0 93.0 91.4 86.2
 M. Frías et al. / Applied Clay Science 42 (2008) 189–193
metakolinite and, 2) the beginning of decarbonation of calcite.
This is in agreement with the results obtained previously by
Vigil et al. (2006) in the temperature range between 700 and
800 °C.
4. Conclusions
Mineralogically, these paper wastes are formed by a mix of
organic matter and different inorganic minerals (kaolinite, calcite
and others phyllosilicates such as talc, chlorite and micas).
During calcination the temperature modifies the starting paper
sludge's structural components. At 600 °C and 2 h of retention,
cellulose fibbers are still observed. In all cases, kaolinite was
disappeared and it has been transformed into metakaolinite. The
crystallinity of talc was increased in the mentioned thermal range.
All products calcined between 600 and 700 °C showed high
pozzolanic activity. The fixed lime values are similar and very
close to those obtained for silica fume, an industrial by-product
very often used in the manufacture of cement and concrete.
From the results of this study, calcination at 650 °C for 2 h is
recommended because organic matter was totally decomposed
and kaolinite transformed into metakaolinite.
The observations support the viability of recycling art paper
sludge waste in order to obtain metakaolinite as an alternative to
calcined kaolin for technical and environmental benefits.
Acknowledgements
This research has been supported by the Autonomy Com-
munity of Madrid (project ref: GR/AMB/0448/2004) and, to
Holmen Paper Madrid Company and T S Laboratory of Lafarge
Cements (Toledo, Spain) for its technical support.
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