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Journal

J. Am. Ceram. Soc., 90 [11] 35593565 (2007)


DOI: 10.1111/j.1551-2916.2007.01944.x
r 2007 The American Ceramic Society

Properties and Performances of Concrete Tiles Containing Waste Fired


Clay Materials
M. I. Sanchez De Rojas,w,z F. P. Mar n,y M. Fr as,z and J. Riveraz
z

Eduardo Torroja Institute (CSIC), C/Serrano Galvache n.4, 28033 Madrid, Spain
y

Group Uralita, S.A., C/Mejia Lequerica, 10, 28004 Madrid, Spain

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.

Industrial waste red clay materials, which are good pozzolans,


can be used in place of cement in the manufacture of precast
concrete products. This paper analyzes the use of industrial
waste red clay as pozzolanic materials for the manufacture of
concrete roong tiles, exploring the microstructure and morphology of the resulting concrete and their impact on product
properties and performance. All trials and measurements were
taken on an industrial ceramic product subsequently used in a
second industrial process to manufacture concrete tiles, which
were found to meet market standards. Porosity was observed to
be greater in the waste red clay product in only one trial, while
the proportion of pores with larger diameters was found to
decline. The microstructural studies revealed the existence of
pozzolanic reaction products and an incomplete cement reaction,
as in the control specimens, due to the processing conditions.
This effect caused an increase in exural strength after 28 days.

I. Introduction

26 million tonnes of clay bricks, roof tiles, blocks, and


other such clay building products are manufactured yearly
in Spain. The percentage of products classied as not apt for
sale, and therefore discarded, depends on the type of facility and
product requirements. Waste from clay brick plants, known as
discards, is collected indiscriminately, irrespective of the reason
for discarding the respective products. Discarding may be due to
dimensional breakage and aws that have no effect on the intrinsic properties of the clay material and aws, more typical of
older kilns, caused by over- or underring that may affect the
physicalchemical properties of the product.
Ceramic products come from natural materials, which contain a large percentage of clayey minerals. The activation of clay
reaches by means of the des-hydration process, followed by the
separation of amorphous and active alumina. The clayey minerals such as kaolinite, montmorillonite, or mixtures between
them become pozzolanic materials by means of a controlled
calcination process. As the clays are illites or contain large
amount of vermiculite, chlorite and micas will be necessary to
use higher temperatures for its activation. Natural pozzolans in
the form of calcined earths blended with lime have been used to
procedure cementitious materials since ancient times; the Romans used ground waste bricks to manufacture hydraulic lime
mortars. Numerous papers on the pozzolanic activity of calcined
clays have been published,14 and the utilization of this clay, in
the form of metakaolin, as a pozzolanic material received signicant attention in recent years.57
VER

II. Experimental Procedure


(1) Materials
(A) Waste Fired Clay Material: All the discarded material was pooled for treatment as a single product, as most of the
rejects were due to breakage or dimensional aws and the
essentially negligible amounts of under- or overred discards
found in industrial facilities such as those used for this study,
with suitably controlled kilns, would generate no substantial
differences in the material as a whole.
Waste red clay material is readily crushed. In the present
experiment, the following equipments were used: Primary (o5
mm) jaw or hammermill crusher and secondary (o45 mm)
rotary or roll crusher. The samples were crushed to different
degrees of neness, expressed in terms of Blaine specic surface:
F1 (3500 cm2/g) and F2 (3200 cm2/g).
The chemical composition of these discards was similar to the
composition of other pozzolanic materials, i.e., highly acidic
compounds with a predominance of silica, alumina, and iron
oxide (Table I).
Table I. Chemical Composition
Majority constituent (%)

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

Waste red clay material

67.03
19.95
6.29
0.11
1.37
0.21
3.54
0.79
0.47
93.27

Journal of the American Ceramic SocietySanchez de Rojas et al.

3560

Table III. Experimental Batches

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

Fig. 1. X-ray diffraction of waste red clay material.

Their mineralogical composition was studied with X-ray


diffraction techniques, using a Philips PW.1730 diffractometer
(Eindhoven, the Netherlands). The main crystalline compounds
found in the discards were quartz (Q), muscovite (Mu), microcline (M), and hematite (H) (Fig. 1). The discards showed an
amorphous material content of 38%. Although in principle a
high percentage of crystalline material is detrimental to pozzolanic activity, certain theories sustain that crystalline particles
may act as nucleation kernels and some crystalline phases have
been shown to enhance slag reactivity.13 Svatovskaya et al.14
reported that the feldspar and mica in ceramic materials may
activate C3S hydration.
(B) Cement: The cement used was CEM II/A-V 42.5R,
according to European Standard EN 197-1:2000 Standard,15
with an average content of 80%94% clinker, 6%20% siliceous y ash, and additional components up to 5%, their physical and chemical properties specied are shown in Table II. This
cement was used in keeping with present procedures at the concrete tile works where the trials were conducted.
(C) Sand: The sand used was a natural and siliceous
sand or sand mix whose particle size distribution was kept within the range dened at each plant. The amount of water added
was corrected for sand humidity rate, but in any event water/
cement ratios were kept to about 34% to maintain a dry consistency.

(2) Industrial Trials


(A) Procedure: The starting point for the industrial trials
conducted in a concrete roof tile factory consisted of replacing
part of the cement with the ground waste.
Concrete tiles are usually made by extruding, pressing, or
vibrating mortar having an appropriate particle size distribution
and mineral grain, 0/4-mm sand, cement, pigment, water, and
possibly admixtures as the main constituents.
The concrete is compacted and shaped on to molds under
high pressure in a machine known as an extruder and then cut
into individual tiles, which are then treated with a surface nish
as appropriate, consisting of one or several coats of pigmented
cementitious slurries.
Table II. Characteristics of Standard Cement CEM II/A-V
42,5R
Properties

Compressive strength 2 days


Compressive strength 28 days
Setting time (beginning)
Expansion
SO3
Cl-

Values








Cement replacement (%)

T-0 (control)
T-1
T-2
T-3
T-4
T-5
T-6
T-7

Mu

Vol. 90, No. 11

20 MPa
42.5 and r62.5 MPa
60 min
10 mm
4.0%
0.10%

Clay discard neness

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.

III. Results and Discussion


The two distinctive areas of the concrete tiles made with waste
red clay materialvalleys and rollswere sampled for testing
to take account of possible differences resulting from the manufacturing process (extrusion and pressing).

(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

Total porosity (%)


Roll 15.54 14.28 15.23 16.40 13.92 13.78 13.61 14.63
Valley 14.14 14.63 15.35 16.60 14.19 13.70 13.78 14.34
Apparent density (g/ml)
Roll
2.52 2.57 2.53 2.55 2.53 2.51 2.52 2.55
Valley 2.52 2.52 2.53 2.54 2.52 2.54 2.51 2.54
Median pore diameter (mm)
Roll
0.16 0.14 0.17 0.17 0.15 0.13 0.14 0.15
Valley 0.14 0.14 0.18 0.18 0.14 0.13 0.13 0.15

November 2007

0.01
T-0

T-1

T-2

Incremental volumen (mL/g)

Incremental volumen (mL/g)

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

Pore diameter (um)

10

0.1

0.01

0.001

0.01

0.001

Pore diameter (um)


0.01

T-0

T-4

T-5

T-6

Incremental volumen (mL/g)

0.01
Incremental volumen (mL/g)

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Concrete Tiles Containing Waste Fired Clay Materials

T-7

0.005

0
1000

100

10

0.1

0.01

0.001

Pore diameter (um)

T-3 R

T-3 V

0.005

0
1000

100

10

0.1

Pore diameter (um)

Fig. 2. Differential pore distribution in tile rolls.

Fig. 4. Differential pore distribution in tile rolls and valleys.

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.

Incremental volumen (mL/g)

0.01
T-0

T-1

T-2

(2) Backscattered Electron Images (BSE) Study


Sample morphology was studied with BSE analysis conducted
on tiles obtained from the demolding machine. In this study,
specimens for backscatter examination were prepared by epoxy
impregnation, followed by precision sawing and careful polish-

T-3

0.005

0
1000

100

10

0.1

0.01

0.001

Pore diameter (um)


Incremental volumen (mL/g)

0.01
T-0

T-4

T-5

T-6

T-7

0.005

0
1000

100

10

0.1

0.01

0.001

Pore diameter (um)

Fig. 3. Differential pore distribution in tile valleys.

Fig. 5. Backscattered electron images of T-0 roll: anhydrous products


and unreacted cenospheres.

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Journal of the American Ceramic SocietySanchez de Rojas et al.

Vol. 90, No. 11

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

Fig. 7. Backscattered electron images of T-2 roll: anhydrous products


and unreacted cenospheres.

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).

(3) Mechanical Resistance


The mechanical resistance of the tiles upon removal from the
molds (9 h), after 7 and 28 days, determined as the average
transverse exural strength as per European Standard EN 491,22
is given in Fig. 10. The standard deviation does not increase with
respect to the control specimens (batch T-0).
After 9 h, the transverse exural strength values for the tiles
with and without (control T-0) discarded materials were similar.
After 28 days, all the tiles manufactured with the waste red clay
product had higher strength values than the control, with the
exception of trials T-2 and T-3. The highest strength value was
14%, reached in trial T-1 (Fig. 11). This behavior is an outcome
of the pozzolanic reaction, which takes place in the medium- or
long-term depending on the reaction rate of the material. It
may therefore be sustained that because the waste red clay
material act as pozzolans and contribute to the development of

November 2007

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Concrete Tiles Containing Waste Fired Clay Materials

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. 10. Mechanical resistance: Transverse strength (test method


EN 491).

Average Transverse Strength (%)

Average Transverse Strength (N)

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

Fig. 11. Mechanical resistance related to T-0. Age: 28 days.

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)

Average transverse strength - 9 hours

T-7
Porosity

4200

17

3900

14

3600

11

3300

Porosity (%)

Strength (N)

2400

Porosity (%)

Journal of the American Ceramic SocietySanchez de Rojas et al.

3564

3000
T-0

T-1

T-2

T-3

T-4

T-5

Average transverse strength - 28 days

T-6

T-7
Porosity

Fig. 12. Mechanical resistance and total porosity.

mechanical strength, lower cement content is required to attain


the desired strength values.
Figure 12 shows the exural strength at different ages and the
roll porosity of the tiles obtained in the different industrial trials,
from which it may be concluded that the higher the porosity, the
lower the exural strength and vice versa.

(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

Table V. EN 490 Specications for the Concrete Tiles


Tests

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

Vol. 90, No. 11

waste red clay material has no impact on the manufacturing


process, the use of this by-product is industrially feasible.
The inclusion of such discards does not increase the total
porosity of concrete roof tiles. A slight rise in porosity was
observed in only one of the products, tile T-3.
Pore size did not vary in either rolls or valleys when cement
was partially replaced by waste red clay, and pore size distribution in the respective samples was the same as in the T-0
control. The only difference found was a slight decline in the
proportion of larger diameter pores (over 0.1 micron), which are
the ones that might have an adverse effect on permeability.
Waste red clay material prompts pozzolanic reactions, enhancing mechanical strength; the percentage decline in strength
in the early hours was smaller than the proportion of cement
replaced by the discard material. After 28 days, transverse exural strength may increase by up to 14%; this effect may be
explained by the increasing pore renement and it is believed to
be caused by the additional CSH gel produced from the
pozzolanic reaction between waste red clay material and portlandite from the hydrating cement. This lends support to the
existence of a relationship between increased porosity and lower
mechanical strength.
Therefore, although variations in the porosity and mechanical resistance were observed among the different samples, these
differences were not appreciated in the microstructure, as the
tests carried out by means of BSE analysis do not put off relief
signicant differences with the waste red clay material replacement with the different percentages and neness. Concrete
roong tile microstructure is not altered by the inclusion of
waste red clay product; anhydrous products were found in all
the samples taken, due to the low W/C ratio, accelerated curing,
and the early testing age, immediately upon demolding.
The replacement of cement by waste red clay material
affords both technical and economic advantages. Concrete
roof tiles manufactured with waste red clay material meet the
requirements laid down in the existing legislation.
In light of the above ndings, the use of waste red clay
product in the manufacture of concrete roof tiles is presently
under study. This line of research is therefore being pursued and
further tests are being conducted to determine possible longterm variations in performance.

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&