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Alkaline activation of ceramic waste materials
L. Reig
1
, M.M. Tashima
2
, L. Soriano
2
, M.V. Borrachero
2
, J. Monzó
2
, J. Payá
2
1
EMC, Universitat Jaume I, Av. Sos Baynat s/n 12071 Castelló de la Plana, Spain
2
Instituto de Ciencia y Tecnología del Hormigón (ICITECH), Universitat Politècnica de València, Camino de
Vera s/n 46022 Valencia, Spain.
Corresponding author: L. Reig; lreig@uji.es
Tel.: +34 96 472 9163
Fax: +34 96 472 81 06
E-mail addresses: lreig@uji.es; maumitta@hotmail.com; lousomar@ gmail.com; vborrachero@cst.upv.es;
jmmonzo@cst.upv.es; jjpaya@cst.upv.es
Abstract
Ceramic materials represent around 45% of construction and demolition waste, and originate not only from the
building process, but also as rejected bricks and tiles from industry. Despite the fact that these wastes are mostly
used as road sub-base or construction backfill materials, they can also be employed as supplementary
cementitious materials, or even as raw material for alkali-activated binders. This research aimed to investigate
the properties and microstructure of alkali-activated cement pastes and mortars produced from ceramic waste
materials of various origins. Sodium hydroxide and sodium silicate were used to prepare the activating solution.
The compressive strength of the developed mortars ranged between 22 and 41 MPa after 7 days of curing at
65ºC, depending on the sodium concentration in the solution and the water/binder ratio. These results
demonstrate the possibility of using alkali-activated ceramic materials in building applications.
Keywords: Ceramic waste, Waste management, Alkaline activation, Compressive strength.
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1 Introduction
The Portland cement clinker is the dominant binder used in concrete. However, its production requires
approximately 850 kcal and involves the emission of nearly 0.8-1.0 kg of CO
2
per kg of cement produced [1].
The cement industry, together with the scientific community, is actively seeking alternatives to reduce the
energy involved in cement production, to produce low-CO
2
binders and to reuse waste materials from other
industries.
Ceramic wastes in Spain abound and they are generated by not only the industry, but also by the construction
sector. According to [2], approximately 950 kg per person/year derived from the construction field in 2007 in
Spain, although this amount lowered in subsequent years due to the economic crisis (520 kg per person and per
year in 2009). Approximately 45% of construction and demolition wastes are ceramic in nature. Different
ceramic materials production categories can be distinguished in accordance with the source of raw materials:
structural ceramic products (i.e., bricks, roofing tiles, vaults, etc.), ceramic tiles and sanitary ware. As reported
by HYSPALIT (the Spanish Association of Manufacturers of Bricks and Clay Roofing Tiles), the manufacture
of structural ceramics increased progressively from 1994 to 2006 when almost 30 million tonnes were
manufactured. The production rate dramatically decreased since then, and only 7.7 million tonnes were
generated in 2010. Moreover, the Ceramic World Review survey [3] reported a world tile production of 9515
million square meters in 2010, of which 96.0% (9170 Mill m
2
) implied the 30 major manufacturing countries.
Although the Spanish industry recorded a reduction in production of almost 40% from 2006 to 2010 (608 to 366
million m
2
, respectively), it still ranked seventh in the list of manufacturers in 2010 with 3.8% of total world
production. Since consumption in the Spanish market has diminished by 54.0% since 2006, two thirds of
manufactured tiles were exported.
Despite the vast majority of the ceramic wastes being used in landfills with a low added value, prior research has
proved its suitability in concrete and as cementitious materials. In the studies by Medina et al. [4], up to 25.0%
of natural coarse aggregates were replaced with ceramic sanitaryware wastes to obtain concrete for structural
purposes. Similarly, Pacheco-Torgal and Jalali [5] observed not only a slight increase in water absorption and
permeability when replacing traditional coarse aggregates with ceramic wastes, but also superior durability when
traditional sand was replaced. Furthermore, several studies have confirmed the potential of ceramic wastes to
produce pozzolanic cements [6-9]. Among them, Puertas et al. [7] not only successfully used up to 35.0% of
certain types of ceramic wastes as pozzolan admixtures, but also proved their suitability as raw materials for
Portland cement clinker production.
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Although ceramic materials can be used as cement admixtures and concrete aggregates, in these applications
only a portion of cement is replaced (usually 10-35%) so, it is interesting to develop binders that are made
entirely, or almost entirely, from waste materials [10]. This can be achieved by the alkali activation process. A
conceptual model of the reaction processes involved was proposed by van Deventer et al. [11] for the metakaolin
system. An aluminosilicate-based material is dissolved by a highly concentrated alkali hydroxide and silicate
solution, giving rise to sodium or potassium silicate and aluminate monomers. These precipitate and form an
alkali-aluminosilicate gel (amorphous) and sites for the nucleation of zeolitic type phases (nanocrystalline),
brought about by the transformation of the gel. As Deventer et al. pointed out [11], the reaction mechanism is
modified depending on the chemistry of the raw material.
The success of converting waste materials into useful products following this process has been extensively
proved in materials such as silicoaluminous fly ash, metakaolin or blast furnace slag [12-14], and its suitability
has also been confirmed for other waste materials, such as hydrated-carbonated cement [15], glass [16] or
ceramic materials [17-19]. In the study by Puertas et al. [17], six different ceramic wastes were mixed with
NaOH and sodium silicate solution to give a maximum compressive strength of 13 MPa for pastes cured for 8
days at 40ºC. Mortars with similar compressive strengths (14 MPa) were obtained by Reig et al. [18,19] by
mixing red hollow bricks with a NaOH solution and by curing samples for 7 days at 65ºC. However, further
research must be done in order to understand the influence of the alkali activator on the alkali activation process
of ceramic materials of different natures. For this purpose, two different ceramic products, with very different
sintering temperatures and chemical compositions, were selected: red clay bricks and porcelain stoneware. While
the former are sintered at temperatures ranging from 800ºC to 1000ºC [9], porcelain tiles are usually sintered
between 1190ºC and 1220ºC [20]. According to Baronio and Binda [21], powder from bricks is expected to
present pozzolanic activity as the crystalline network is destroyed when the structural hydroxyl groups of clay
minerals (phyllosilicates or sheet silicates) are lost (600°C -900°C). According to the study by Zanelli et al. [22],
which analyzed 93 porcelain stoneware samples, porcelain tiles are also presumed to react. Their mineralogy is
composed of some crystalline phases, such as quartz, mullite or feldspars, which are dispersed throughout a main
vitreous phase whose proportion varies from 40% to 80% depending on the sample.
This research aimed to develop binders by the alkali activation of two different ceramic waste materials (porous
red clay brick and porcelain stoneware) and to analyze the influence of the alkali activator concentration on the
mechanical strength and microstructure of the binders formed.
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2 Experimental
2.1. Materials
Two different ceramic waste materials were used for the alkaline activation process: red clay brick (B) and
porcelain stoneware (P). The materials were crushed in a jaw crusher to obtain a particle diameter of less than 4
mm. This granulated material was then ground in a laboratory-type ball mill (alumina medium, 40 min). Particle
size distribution was measured using a laser analyzer (Mastersizer 2000, Malvern Instruments). Figure 1 presents
both cumulative curves. As shown, both powders presented a similar particle distribution, with particles ranging
from 0.2 to 100 µm, 90% in volume under 50 µm, and almost 7% had a diameter under 1 µm. Despite both
ceramic materials having a mean particle diameter close to 20 microns, a slightly larger amount of thinner
particles (under 10 micron) was observed in the red clay brick powder.
In Figure 2, both ground materials were examined by scanning electron microscopy (JEOL JSM-6300). The
irregular shape of the milled particles is observed and particles show no significant porosity.
The chemical composition of the milled samples was determined by an X-ray fluorescence analysis (XRF). As
shown in Table 1, the amount of SiO
2
was larger in the porcelain waste (71% versus 51%), while the presence of
other compounds (CaO, K
2
O, MgO and Fe
2
O
3
) was barely noticeable. In fact, 94% of porcelain stoneware was
composed of SiO
2
, Al
2
O
3
and Na
2
O. For red clay brick waste, the sum of silica, alumina and sodium amounted
to less than 70%. In both cases, loss on ignition (LOI) was below 2%.
The mineralogical composition of raw materials was determined by XRD in a Philips diffractometer PW1710
with Cu Kα radiation under the routine conditions of 40 kV and 20 mA, from 5-55º (2θ). As shown in Figure 3,
the major crystalline phase was quartz (SiO
2
, PDFcard 331161), which was found in both waste materials. Other
previously reported compounds in the mineralogy of ceramic materials [5,17], such as mullite (Al
6
Si
2
O
13
,
PDFcard 150776), anortite (CaAl
2
Si
2
O
8
, PDFcard 100489), wollastonite (CaSiO
3
, PDFcard 350755), gehlenite
(Ca
2
Al
2
SiO
7
, PDFcard 350755) or celite (Ca
3
Al
2
O
6
, PDFcard 320148), were found in minor quantities. Mullite,
an important constituent in porcelain material [23], was observed in the porcelain stoneware powder.
5"
2.2. Preparation of paste and mortar samples
To develop the alkali-activated binders, ceramic waste materials were mixed with an alkaline solution. The
activating solution was prepared by dissolving sodium hydroxide pellets (Panreac, 98% purity) with water and a
sodium silicate solution (Merck, Waterglass SiO
2
=28%, Na
2
O=8%, H
2
O=64%).
Paste samples were obtained by mixing ground ceramic with the required alkaline solution for 4 min, and they
were cast in plastic containers. Mortar samples were prepared by mixing the ceramic material with the activating
solution for 2 min. Siliceous sand (4.36 modulus fineness and maximum particle diameter of 2 mm) was then
added and the mixing process was continued for a further 3.5-min period. The formed mortar samples were
placed into a mould and were vibrated for 4 min. Both pastes and mortars were stored in a thermostatically
controlled bath at 65ºC for 7 days at 100% relative humidity.
Table 2 summarises the mix proportions used in this study. Mixes are coded as ‘x/ω/m/r-c’, where x is the type
of ceramic waste (binder: B=brick and P=porcelain), ω is the amount of water per 100g of binder, m is the
molality (mol/kg) of Na
+
in the activating solution, r is the SiO
2
/Na
2
O molar ratio in the activating solution and –
c is the percentage of Ca(OH)
2
(93% purity) used to replace ceramic waste.
A water/binder (w/b) ratio of 0.45 was used for the samples made with brick, which was lowered in samples
‘B/40/8.0/1.60’ and ‘B/35/9.0/1.60’ to analyze the influence of this parameter (w/b). Due to the reduced water
absorption of the porcelain stoneware (less than 0.5%) [24], the w/b ratio was lowered to 0.35 for all the
porcelain waste mixes. A binder/sand (b/s) ratio of 1:3 was employed for all the mortars tested in this paper (see
Table 2).
2.3. Sample testing
Compressive strength was determined on the alkali-activated mortars following the UNE EN 196-1 standard.
The microstructure was examined on paste samples using SEM-EDX (JEOL JSM-6300) and mineralogical
phases were identified by X-ray diffraction XRD. Thermogravimetry (TG, TGA-850 Mettler-Toledo
thermobalance) was done to determine the mass loss of samples in an N
2
atmosphere using sealed pinholed
aluminium crucibles at a heating rate of 10ºC min
-1
. Tests were run from 35ºC to 600ºC to assess the mass loss
related to bonded water molecules or hydroxyl groups in the pastes. Samples were taken on day 7 of curing at
65ºC and with a relative humidity of 95-100%.