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Eduardo Torroja Institute (CSIC), C/Serrano Galvache n.4, 28033 Madrid, Spain
y
In other papers, the pozzolanic properties of waste clay materials have been analyzed.810 The impact of the temperature at
which the waste is obtained has likewise been studied. When the
ring temperature is inappropriate (under- or over-red material) the chemical and mineralogical composition of the waste
varies signicantly with respect to the product obtained under
optimum ring conditions. But in any event the temperature
used (around 9001C) is sufcient to activate the clay and provide
the discarded material with pozzolanic properties. The morphology of clay tileportland cement pastes is similar to the morphology of the pastes containing other pozzolanic materials.11
Specically, the object of the above studies was the manufacture of concrete roof tiles. The authors showed that waste
clay brick could be used as a raw material in the manufacture of
concrete roong tiles, either as a replacement for cement, exploiting its pozzolanic properties, or as part of the aggregate.12
The present study addresses the re-use of waste clay brick and
block to produce concrete roof tiles, exploring the microstructure and morphology of the resulting concrete and their impact
on product properties.
I. Introduction
SiO2
Al2O3
Fe203
CaO
MgO
Na2O
K2O
SO3
LOI
SiO21Al2O31Fe2O3
C. Jantzencontributing editor
Manuscript No. 23106. Received April 19, 2007; approved June 15, 2007.
This research was funded by the Interministerial Commission on Science and Technology
(CICYT) under Research Project AMB96-1095 and could be conducted thanks to the
co-operation of the Group Uralita Tiles and Roong Division.
w
Author to whom correspondence should be addressed e-mail: srojas@ietcc.csic.es
3559
67.03
19.95
6.29
0.11
1.37
0.21
3.54
0.79
0.47
93.27
3560
Mu = Muscovite
Q = Quartz
H = Hematite
M = Microcline
Trial
M
Q
Q
Q
H
Mu
M
Mu
H
M M
Q
M
M Mu
Q H
10
15
20
25
30
35
40
45
50
55
60
2 - Theta
Values
T-0 (control)
T-1
T-2
T-3
T-4
T-5
T-6
T-7
Mu
20 MPa
42.5 and r62.5 MPa
60 min
10 mm
4.0%
0.10%
0
5
10
15
5
10
15
20
F1:
F1:
F1:
F2:
F2:
F2:
F2:
3500 cm2/g
3500 cm2/g
3500 cm2/g
3200 cm2/g
3200 cm2/g
3200 cm2/g
3200 cm2/g
The tiles, together with their molds, are placed in special containers and run through continuous accelerated curing tunnels,
followed by a 912-h cycle under controlled temperature and
humidity conditions, in which the temperature may reach up to
401C and relative humidity up to 100%, to harden the tiles
enough for demolding.
These concrete roof tiles met European Standard EN 49016
requirements, measuring 420 mm 330 mm, weighing 4.3 kg
and having a curved prole with 30-mm side locks; 10.5 tiles
cover one square meter of roof.
(B) Materials and Dosing: The discards were ground to
the two different specic surfaces specied above, i.e., F1 and
F2, and added to the mix in place of 5%, 10%, or 15% of the
cement. The discards ground to neness F2 were also added to
the mix in a proportion of 20%.
These two neness were selected in order to check their effect
on the concrete properties, having discarded bigger neness to
keep the water/cement ratio (W/C) ratio and workability without incorporation of admixtures. For the same reason the replacement of 20% was not studied with neness F1. The
experimental batches produced are listed in Table III.
(1) Porosity
Morphology, particularly as regards porosity, is closely associated with material permeability. Authors reporting a relationship between pore size distribution and permeability to
water17,18 found that pores of over 1000 A (0.1 mm) had the
greatest impact on this parameter.
The mercury porosimetry technique was used to ascertain the
effect of waste red clay on total porosity, apparent density, and
average pore diameter (Table IV) in concrete tiles made according to the industrial procedures dened above. These tests were
performed in a Micromeritics Pore Sizer 9500 (Norcross, GA)
using tiles taken from the demolding machine.
Table IV. Porosity: Total Porosity, Apparent Density, and
Median Pore Diameter
Tile
T-0
T-1
T-2
T-3
T-4
T-5
T-6
T-7
November 2007
0.01
T-0
T-1
T-2
0.01
T-3
0.005
0
1000
100
10
0.1
0.01
T-0 R
0
1000
0.001
T-0 V
0.005
100
10
0.1
0.01
0.001
0.01
0.001
T-0
T-4
T-5
T-6
0.01
Incremental volumen (mL/g)
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T-7
0.005
0
1000
100
10
0.1
0.01
0.001
T-3 R
T-3 V
0.005
0
1000
100
10
0.1
The porosity results show that the discarded materials did not
in general cause signicant differences in total porosity, apparent density, or average pore size. The main difference in total
porosity was observed in batch T-3, for both valleys and rolls
(Table IV).
Similar pore size distribution results were obtained for all of
the tiles, for both rolls and valleys, and no increase was found in
the proportion of the larger size pores (over 0.2 mm) that might
have adverse effects on permeability (Figs. 2 and 3). The pore
size curve for the batch T-3 tiles diverged more from the
curve for the T-0 control than from any of the other samples.
The differences were found in pores of around 0.1 mm in
diameter.
The results for roll and valley samples were not signicantly
different. The rolls for the T-0, T-5, T-6, and T-7 tiles had a
slightly higher proportion of 100 mm pores than the respective
valleys. This was not consistently the case, however, because in
the T-1 and T-3 trials the contrary was observed, whereas no
differences were found in the samples from tiles T-2 and T-4. In
Fig. 4, where the results for T-0 and T-3 tiles are depicted, these
variations can be seen to be minor.
0.01
T-0
T-1
T-2
T-3
0.005
0
1000
100
10
0.1
0.01
0.001
0.01
T-0
T-4
T-5
T-6
T-7
0.005
0
1000
100
10
0.1
0.01
0.001
3562
Fig. 6. Backscattered electron images of T-0 roll: hydration products: hydrated calcium silicates (A) and portlandite (B). Energy-dispersive X-ray
spectroscopy microanalysis.
ing of a plane surface for examination. A JEOL-5400 with energy-dispersive X-ray spectroscopy (EDX) was used.
No morphological variations were observed in concrete roof
tiles that could be attributed to the inclusion of waste red clay
material in their composition.
The most prominent nding in Fig. 5, corresponding to trial
T-0, is the existence of anhydrous particles; this is an indication
of incomplete hydration, in turn due to the low water/cement
ratio used during manufacture and curing. The smooth surface
on the numerous cenospheres, particles that pre-existed in the
CEM II/A-V cement and likewise visible in the microphotograph, is a sign of scant pozzolanic action.
During y ash hydration, cenosphere surfaces are generally
observed to be covered by a thin lm of calcium hydroxide and
calcium silicate hydrate (CSH) gel.19 This lm grows gradually thicker and denser due to continued deposition of these two
reaction products. According to some authors, the various layers of y ash progressively dissolve from the surface inward
during the pozzolanic reaction. The hollows or gaps formed in
the spaces once occupied by cenospheres as a result of this
process are not completely lled by the products of the pozzolanic reaction.20,21 Such developments were not observed in the
samples studied here; however, although embedded in the cement paste, the cenospheres did not react, corroborating the
foregoing ndings.
Other hydration products are also observed. EDX microanalysis of these compounds showed them to be aluminum-containing hydrated calcium silicates with a C/S ratio of 1.41.7 and
portlandite (Fig. 6).
The morphology of all the samples with waste red clay material in their composition was very similar to that found for the
T-0 specimen. The BSE image of samples with waste red clay
material presents unreacted cenospheres and calcium silicate hydrated (CSH) with a C/S ratio similar to T-0, unhydrated
grains of cement were detected too.
Morphological analysis of one of these samples, namely sample T-2, is given hereunder. As Fig. 7 shows, anhydrous products and unreacted cenospheres were also present. The
hydration products detected were essentially hydrated calcium
silicates with a C/S ratio of 1.5, similar to those found in trial T0 and portlandite (Fig. 8). Feldspar from the waste red clay
material was likewise identied, although in very small proportions (Fig. 9).
November 2007
3563
Fig. 8. Backscattered electron images of T-2 roll: reaction products surrounding y ash particles: hydrated calcium silicates (A) and portlandite (B).
Energy-dispersive X-ray spectroscopy microanalysis.
5000
4000
3000
2000
1000
0
T-0
9 hours
T-1
T-2
7 days
T-3
T-4
T-5
T-6
T-7
28 days
Fig. 9. Backscattered electron images of T-2 roll: feldspar from the clay waste (A). Energy-dispersive X-ray spectroscopy microanalysis.
15
12
9
6
3
0
3
6
T-1
T-2
T-3
T-4
T-5
T-6
T-7
17
2250
14
2100
11
1950
8
5
1800
T-0
T-1
T-2
T-3
T-4
T-5
T-6
Strength (N)
T-7
Porosity
4200
17
3900
14
3600
11
3300
Porosity (%)
Strength (N)
2400
Porosity (%)
3564
3000
T-0
T-1
T-2
T-3
T-4
T-5
T-6
T-7
Porosity
(4) Performances
Moreover, the concrete roong tiles manufactured with waste
red clay products met all the specications (Table V) laid down
in European standard EN 490,16 particularly the water- and
frost-proof requirements, when tested as described in standard
EN 49122; these ndings corroborate the results discussed in the
previous paragraphs.
Freezethaw cycles were performed according to EN 49122
specications and, after 25 cycles, ve tiles were tested for water
tightness and exural strength. An additional tile was subjected
to 100 cycles to ensure against structural aws.
Tiles from all batches passed the tests with no relevant differences.
IV. Conclusions
For its pozzolanic properties, industrial waste red clay material
can be used to partially replace cement in precast concrete products, particularly roong tiles. Moreover, as the inclusion of
Specication
Dimensions
74 mm; cover width 75 mm
Mass
710%
Mechanical
Minimum exural strength 2000 N
strength
Water-tightnessUnder water, no drops shall fall before 20 h
Durability
Conformity to water-tightness and
mechanical strength requirements after 25
freezethaw cycles 1201 to 201C
Nib support 1 min in vertical
Fire resistance Class A1 for re reaction; Broof for external
re resistance
References
1
November 2007
13
P. K. Mehta Pozzolanic and Cementitious By-Products in ConcreteAnother Look, Proceeding of the 3rd International Conference on Fly Ash, Silica
Fume, Slag and Natural Pozzolans in Concrete, Trondheim 1, 143, 1989.
14
L. B. Svatovskaya, M. Sychev, L. S. Geidarova, A. P. Komokhov, and D.
Rokhlin, Effect of Substances with the Characteristics of Hard Acids on Cement
Properties, Tsement, 3, 212 (1989).
15
European Standard EN 197-1:2000: Cement. Part 1: Composition, Specications and Conformity Criteria for Common Cements.
16
European Standard EN 491:2004: Concrete Roong Tiles and Fittings for
Roof Covering and Wall Cladding. Product Specications.
17
P. K. Mehta and D. Manmohan, Pore Size Distribution and Permeability of
Hardened Cement Pastes; Proceedings of the 7th International Congress on the
Chemistry of Cement, Paris, III, VII 15, 1980.
18
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