A Brief Overview of Fly Ash Brick Production

Hakan Cengizler Celal Bayar University, Manisa, Turkey. Tayfun iek, Mehmet Tanrverdi Dokuz Eyll University, zmir, Turkey. ABSTRACT: Fly ash is a waste material of coal firing thermal plants and its accumulation near power plants causes severe pollution problems. Therefore, its utilization as a raw material for brick making will be a very beneficial solution in terms of economical and environmental aspects. In this paper, the brick industry of Turkey was briefly presented in general terms. The methods of FA brick production and the leaching behaviours of heavy metals were discussed. The methods of producing non-fired fly ash bricks seems to be an advantageous way to confront the challenges for environment and ecologically sustainable development. Additional economical benefits will also contribute to the Turkish economy while increasing demand for greener building products will be met locally and also globally. INTRODUCTION Fly ash (FA) arising from the combustion of coal is being accumulated as waste material in large quantities near thermal power plants. FA which has pozzolanic properties creates serious environmental pollution problems and poses serious operational constraint and environmental hazard as a recognized environmental pollutant. In Turkey, the disposal of FA is also a significant problem and 15 million tons of FA was generated by power plants in 2000 (Ttnl and Atalay, 2001). This output is expected to reach 50 million tons by the year of 2020 (Ttnl and Atalay, 2001). However, only about 3 % (weight per cent) FA, mainly for cement production, is being utilized for production of building materials which is a rather low utilization ratio compared with those in the countries such as Germany, Holland, Belgium, UK, USA, and China (Ttnl and Atalay, 2001; Arunta, 2006; Lingbawan, 2009). Therefore, large volume utilization of FA as a main raw material to produce building elements will be a good solution to handle such a hugely polluting material raising environmental and economical concerns. For instance, its utilization in the manufacture of FA bricks (FAB) will not only create ample opportunities for its proper and useful disposal but also help in environmental pollution control to a greater extent in the surrounding areas of power plants. In this paper, the brick industry of Turkey is briefly presented in general terms and the technologies used to manufacture bricks are shortly described. Methods to manufacture FAB as an alternative to conventional fired brick are briefly overviewed. Leaching behaviors of heavy metals are also discussed (Cengizler, 2009; Tanrverdi, 2006). TURKISH BRICK INDUSTRY Raw material: The raw material of traditional brick industry is clay which is one of the most abundant natural mineral materials on earth. Clay for the production of brick must, however, possess some specific properties and characteristics. To satisfy production requirements, clays must have plasticity, which permits them to be shaped or molded when mixed with water; and they must have sufficient wet and airdried tensile strength to maintain their shape after forming. Also, when subjected to rising temperatures, the clay particles must fuse together. Clays occur in three principal forms such as surface clays, shales and fire clays, all of which have similar chemical compositions but different physical characteristics. Surface clays may be the upthrusts of older deposits or of more recent, sedimentary formation. As the name implies, they are found near the surface of the earth. Shales are clays that have been subjected to high pressures until they have hardened

almost to the form of slate. Fire clays are usually mined at deeper levels than other clays and have refractory qualities. Clays are complex materials; surface clays and fire clays differ from shales more in physical structure than in chemical composition. Chemically, all three are compounds of silica and alumina with varying amounts of metallic oxides and other impurities. Although technically metallic oxides are impurities, they act as fluxes, promoting fusion at lower temperatures. Metallic oxides (particularly those of iron, magnesium and calcium) influence the color of the finished fired product. The manufacturer minimizes variations in chemical composition and physical properties by mixing clays from different locations in the pit and from different sources. However, because clay products have a relatively low selling price, it is not economically feasible to refine clays to produce uniform raw materials. Since variations in properties of raw materials must be compensated for by varying manufacturing processes, properties of finished products from different manufacturers will also vary somewhat. Definition of the sector and its limitations: Brick and roof tile sector which is a subdivision of fired clay and cement products industry has been manufacturing construction products. The production scope of the sector comprises various building bricks and roof tiles. The main products are load-bearing floor bricks, non-load-bearing bricks, solid bricks (clinker brick), horizontally perforated bricks, vertically perforated bricks, horizontally and vertically perforated bricks, roof tiles (laced), hollow blocks, chimney bricks, decorative bricks, paving bricks, and facing bricks (TUKDER, 2008). Production process, technology and standards: The definition of brick technology is classified according to the drying method (natural or artificial drying), manufacturing process (labor or technology intensive), automation (automatic or semi-automatic), raw material processing and shaping (vacuumed or non-vacuumed) and firing method (Hoffman and tunnel furnace usage). In Turkey, the designation of the existing technology is mostly done according to the firing method. When considered in this respect, the most common method is Hoffman system. Brick plants working with tunnel furnaces are limited. In the course of time, these systems are somehow merged together to bring about mixed technologies such as Hoffman furnaces with artificial drying, tunnel furnaces with natural drying or the mix of tunnel and Hoffman furnaces to introduce arch tunnel furnaces (TUKDER, 2008). The former Turkish standards TS 704, TS 705, TS 4563 and TS 4377 were abolished in order to comply with the European standards and the new standard for bricks, TS EN 771-1, was put into effect. Most of the producers have completed their compliance period to CE standards (TUKDER, 2008). Size of brick industry: There are 417 plants disseminated all over Turkey but in small concentrations in the regions where the raw materials are easily supplied. Of 417 plants, 48 plants produce roof tiles, 8 plants produce roof tiles and bricks and the rest produce only bricks. The total brick production capacity is 5 327 000 000 units/year which corresponds to 15 981 100 tons/year (one unit is 3 kg). On the other hand, the total roof tile production capacity is 609 000 000 units/year which corresponds to 1 522 500 tons/year (one unit is 2.5 kg). The total exports and imports between January and July 2008 were reported to be 20 727 582 $US and 3 535 962 $US, respectively (TUKDER, 2008). METHODS OF FAB PRODUCTION For more than two decades, researchers have been investigating the viability of using FA for brick making. Prior to discussing them shortly, a simple classification of the methods of manufacturing FAB must be done. Generally, two fundamentally different approaches exist to make brick and other building products from FA. One is the traditional way of brick making by firing the brick material except that the FA substitutes a portion of clay or entire amount of clay in brick making. The other is based on the self cementing property of Class C FA that contain a large amount of calcium. In this case, firing or heating in kilns is not needed to obtain the final product. Instead, the bricks produced can be cured in the same way concrete is cured. Therefore, hereafter, the bricks made from FA with different clay replacing ratios fired at high temperatures such as 950-1200 oC will be referred to as fired FA bricks (FFAB) and the ones

produced by making use of other means at ambient temperatures rather than sintering will be referred to as non-fired FA bricks (NFFAB). Methods of FFAB production: In this method, FA was used as a raw material to replace brick clay partially with different replacement ratios or with 100 % FA ratio. The mixture of FA and clay were shaped and fired over 1100 oC to obtain FFAB. There were number of studies all reporting positive results meeting or overtaking required standards for traditional clay bricks (Ttnl and Atalay, 2001; Chou et al., 2006; Chou et al., 2001; Kute and Deodhar, 2003; Lingling et al., 2005; Pimraksa et al., 2001; Kayali, 2005; Cengizler, 2008). On the other hand, 100 % FA bricks manufactured by Kayalis process using technology similar to conventional clay bricks were named Flyash Bricks (Kayali, 2005). A 100% class F FA mixture was moulded into a brick (Flash Brick) and fired in a conventional kiln. The finished brick was 28% lighter and 24% stronger than comparable clay bricks. It is reported that the Flash Brick competed on all technical levels with clay bricks. The use of FFAB was authorized in number of countries such as Germany, the United Kingdom and India (Lingbawan, 2009). Methods of NFFAB production: The production of non-fired FA-sand-lime bricks: The method is based on mainly CaOSiO2H2O (CSH) formation (Ball and Carroll, 1999; Baoju et al., 2001; Ma and Brown, 1997; Peng et al., 1999) due to the reaction taking place between lime and silica in the presence of water. Calciumsilicatehydrate is formed by the reaction of Ca(OH)2, SiO2 and H2O under pressurized steam at 125200 oC. In the beginning of this reaction, a lime-rich Tobermorite gel is formed. The composition of this gel is probably C7S4Hn. This phase reacts with residual SiO2 to form C5S4Hn and finally the low-lime C2S3H2 phase (Al-Wakeel et al., 1999). The steam autoclaved FAB based partly on the formation of this CSH phase CaOAl2O3SiO2H2O (CASH), Hydrogarnet is also found to be formed in the presence of Al2O3 (Goni et al., 2003; Klimesch and Ray, 1998). Thus, mainly CSH and CASH phases contribute to the hardening of FA/lime materials since FA contains considerable amounts of Al2O3 and SiO2. In a recent research work (iek and Tanrverdi, 2007; Tanrverdi ve iek, 2007; iek ve Tanrverdi, 2004), FA-sand-lime bricks were produced using an F Class Turkish FA and firstly optimum FAsandlime mixing ratio, brick forming pressure, steam pressure and autoclaving time were determined. The specimens were pre-cured for about 24 h prior to autoclaving. The specimens were steam autoclaved with maximum operating pressure of 4 MPa. Autoclaved specimens were tested for their volume weight, compressive strength and water absorption according to Turkish Standards TS 705 that was valid at the time the study was conducted. The FAsandlime bricks produced seemed to be suitable for use as a construction material and their properties under optimum conditions are summarized and compared with the properties of solid clay bricks in Table 1. Table 1. Properties of fly ashlime bricks produced under optimum conditions (iek and Tanriverdi, 2007). Solid clay bricks TS 705 88 Fly ash (%) (%) Brick type: 1.8/100 12 Hydrated lime (%) 14 Water (%) 35 Forming pressure (MPa) 1.5 Autoclave pressure (MPa) 6 Curing time (hour) 3 1.12 1.8 Volume weight (g/cm ) 1 1 0.36 0.7 Thermal conductivity Wm K 12.0 min. 7.8 Compressive strength (MPa) 38.3 max. 18 Water absorption (%)

The production of non-fired 100 % FA bricks(NF100%FAB): H. Liu developed a technique (Figure 1) compressing wet FA and curing the moulds for 24 hours in a steam bath (Liu et al., 2009; Liu et al., 2005; Liu et al., 2007; Liu, 2005; Liu, 2007). This method, which relies on self-cementing property of Class C FA, or FA that contain a large amount of calcium, do not need to fire or heat the products in kilns. Instead the products can be cured in the same way concrete is cured by keeping the products in wet environment for more than 24 hours until the material sets and hardens due to the chemical reaction with the water or moisture contained in the products. The reaction mentioned is the hydration reaction that also occurs in Portland cement as explained above in the section of the production of non-fired FA-sand-lime bricks. There are a number of patents on the use of FAlime mixtures for making unfired bricks (Lingbawan, 2009; Liu, 2007). Recent researches on the advantages of both pure FA and FA-based granules used for the production of unfired brick (Pimraksa et al., 2006; Chindaprasirt and Pimraksa, 2008) and on masonry blocks produced using lime stone powder waste and C class FA (Turgut, 2010) also reported positive results. The production of non-fired alkali activated 100 % FA geopolymer bricks (NFAA100%FAGPB): The method makes use of the alkali activation of FA. Alkali activation is a chemical process in which a powdery aluminosilicate such as a FA is mixed with an alkaline activator and cured at a mild temperature to promote polymerization to produce a paste capable of setting and hardening within a reasonably short period of time to generate compact solids (Palomo and Fernandez-Jimenez, 2011). Very broadly, the activation process can be viewed as a series of destructioncondensation reactions in which initially unstable structural units

Figure 1. NF100%FAB compacted in laboratory by H. Liu and his co-workers (Liu et al., 2005; Liu, 2005) using a high-grade Class C FA. subsequently form coagulated structures able to condense into the hydrated products (alkaline aluminosilicate hydrate, NASH gel) (Criado et al., 2005). From the chemical standpoint alkali activation of FA is a process that differs widely from Portland cement hydration, but is very similar to the chemistry involved in the synthesis of a large groups of zeolites (Al Bakri et al., 2011). There are two models of alkali activation. Activation of a material containing primarily silicate and calcium by a low to mild alkali will produce calcium silicate hydrate gel (C-S-H) which is similar to that formed in Portland cement but with a lower Ca/Si ratio (Adam, 2009). The second mechanism involves the activation of material containing primarily silicate and aluminates using a highly alkaline solution. This reaction will form an inorganic binder through a polymerization process (Adam, 2009). The term Geopolymer is used to characterize this type of reaction from the previous one, and accordingly, the name geopolymer has been adopted for this type of binder. Therefore bricks produced, using alkali activation process, were named as geopolymer bricks or shortly geobricks. The geopolymeric reaction differentiates geopolymer

from other types of alkali activated materials (such as; alkali activated slag) since the product is a polymer rather than C-S-H gel(Adam, 2009). In a recent study (Arz et al., 2008a; Arz et al., 2008b), geopolymer bricks were produced by using F type FA, C type FA, sodium hydroxide solution, sodium silicate solution by means of pressure forming. Then, the geobricks were heat treated at the temperature of 75 C for olymerization process. Afterwards, the compressive strength values of the geopolymer bricks were determined. A compressive strength of 47.6 MPa was achieved by geobrick produced by F type FA cured in air and then treated in oven for 15 hours. The test results showed that the compressive strength of geobricks increased with increase in solution to FA ratio. The test results revealed that the heat treatment duration considerably affected the compressive strength of geobricks. The compressive strength increased as the heat treatment duration increased. DISCUSSION Of the two main methods mentioned above, the route of making fired FFAB is very similar to conventional clay brick production. Therefore, FA can be easily incorporated in conventional brick manufacturing without making any major change in the production line. These methods mentioned above (Ttnl and Atalay, 2001; Chou et al., 2006; Chou et al., 2001; Kute and Deodhar, 2003; Lingling et al., 2005; Pimraksa et al., 2001; Kayali, 2005; Cengizler, 2008) are easily adaptable by existing clay brick factories. But, during firing process, sulfur dioxide is normally released from burning process. Besides, making fired FFAB consumes expensive heat energy which is very important from economical view point. Therefore, the second route of making NFFAB seems to be the trend to follow in terms of environmental concerns. The method to produce non-fired FA-sand-lime bricks is an alternative in order to use FA as a replacement of sand. As explained above, hydration reactions similar to that in Portland cement take place to form mainly CSH and CASH phases contributing to strength. But, in order to achieve that and to accelerate the reaction kinetics, curing process must be conducted under pressurized steam at 125200 oC in an autoclave which translates itself into additional costs. At this point, the balance between cost and demand should be well established. The production of NF100%FAB developed in USA (Liu et al., 2009; Liu et al., 2005; Liu et al., 2007; Liu, 2005; Liu, 2007) is another alternative in this respect. Especially, no need for extra energy to fire or cure the bricks renders this method a favorable route. But, because it relies on self cementing property of C Class FA or FA that contains a large amount of calcium, the consistency in FA composition is crucial. In literature, more than 24 hours curing time is mentioned until the material sets and hardens during the hydration reactions taking place. This means the need for time and space for FAB at production site can be a drawback. However, the continuation of strength gain even during storing and transportation can also be mentioned as practical benefits of the method. As to geopolymer brick production, CO2 emission for their manufacture is much less than that for conventional brick production (Palomo, 2011) as is the case for NF100%FAB (Liu et al., 2009). Besides, their mechanical and chemical properties are favorable (Palomo and Fernandez-Jimenez, 2011). However, because of using alkali solutions to activate FA brings about extra expenses. Furthermore, the mild temperatures attained for curing are also an added cost for production. Especially the use of sodium silicate solution of which its production leads to heavy effects (Habert et al., 2011) should be taken into account and its use as an activator should be reduced as much as possible. Although geopolymers are presented by many authors as a solution for green concrete, few studies have quantified the environmental impact of geopolymers (Habert et al., 2011). Therefore, a detailed environmental impact assessment of standard geopolymer brick production is necessary and should be compared with other brick production methods. Recently, studies were conducted towards the leaching behaviour of heavy metals from fired (Cengizler, 2009) and non-fired (Tanrverdi, 2006) autoclaved FA-lime bricks. The former was composed

of 40 % Seyitmer FA and 60 % brick clay while the latter was containing 88% Seyitmer FA and 12% hydrated lime. In both studies, two different toxicity tests were conducted on the whole FA brick pieces and ground brick material to determine the solubility values of the elements in their matrix. The leach test procedures performed on the bricks were TCLP (EPRI, 1987) (toxicity characteristic leaching procedure) [Improved Method 1311] and ASTM (U.S. EPA, 1987) (American society of testing and materials) Method A extraction procedure. TCLP method, simulating the solubility of the elements contained in the FA brick samples under a weak acid rain water environment, is used to check the leaching hazards of the solid wastes (it is especially suitable for the acidic wastes). The method predicts the leaching behaviour of the trace elements in the disposed waste during weathering. ASTM method, similar to water leaching and simulating long-term leaching behaviour of the elements in natural circumstances, is performed to predict the leaching behaviour of the trace elements for long-term weathering conditions. The determination of the leaching behaviour of the trace elements in long term stored wastes can be done using this method which is based on extended extraction with distilled water. In terms of simulating long-term leaching behaviour of the elements in natural circumstances, TCLP is considered to be too aggressive; whereas, water extraction, as in the case of the Method A extraction procedure seems to be more adequate (U.S. EPA, 1987). The results for autoclaved FA-lime bricks showed that the whole brick pieces of the non-fired autoclaved FA lime bricks were environmentally sound in terms of the solubility of toxic elements. Therefore, the bricks can be safely used in buildings exposed to weathering conditions. However, Fe, Pb, Zn, Cu, Ni, Co and Mn were detected in the leachates of the test runs performed with ground brick samples. This indicated that the leachability of some toxic elements was promoted if the contact surface area of the bricks with water was increased by grinding of the brick samples. However, only Fe, Pb, Ni, Co and Mn concentrations in the test leachates were higher than the concentrations allowed in the drinking water standards of WHO (WHO, 2004) and TSE (TSE, 2005)0 aada. The results for fired FFAB (Table 2) indicated that, although Fe, Zn and Mn were detected in the leachate obtained from the test run with the whole brick pieces using TCLP method, their solubility levels were in compliance with the drinking water standards (WHO, 2004; TSE, 2005) except the Mn concentration which is not in conformity only with TSE. Furthermore, no detectable level of any element was found in the leachates obtained from the test runs performed with the whole brick pieces and ground brick using ASTM method. Therefore, it can be concluded that the fired FFAB can be safely used in buildings exposed to weathering conditions. The solubility concentrations of the elements such as Fe, Zn, Cu, Cr, Ni and Mn from the leachate obtained from the ground brick using TCLP method were higher than those of the leachate obtained from the whole brick pieces using TCLP method. This result again reflects the effect of grinding which promotes the leaching of these elements due to the increased contact surface area with the leach solution. Therefore, if the large surface areas of the bricks are somehow exposed to weathering conditions acidic in nature, the leaching of above mentioned elements might be expected. However, only Fe, Ni and Mn concentrations were determined to be higher than those allowed in the drinking water standards of WHO and TSE (WHO, 2004; TSE, 2005).

Table 2. Concentration of the elements leached from the light weight FAB samples (Cengizler, 2009). Elements TCLP improved method ASTM method A extraction procedure (mg/L) Drinking 1311 (mg/L) water standards (mg/L) Ground Brick piece Ground Brick piece WHO TSE brick brick 0.20 ND ND 0.330 0.200 Fe 15.00 ND ND ND ND 0.003 0.005 Cd ND ND ND ND 0.010 0.050 Pb 0.75 0.05 ND ND 3.000 5.000 Zn 0.03 ND ND ND 2.000 3.000 Cu 0.05 ND ND ND 0.050 0.050 Cr ND ND ND 0.020 0.050 Ni 0.10 ND ND ND ND 0.010 ** Co ND ND ND ND ** 0.010 Sb ND ND 0.4(C) 0.050 Mn 0.55 0.10 TCLP = Toxicity characteristic leaching procedure; ASTM = American society of testing and materials; ND = Not detectable; **Not available in TSE266; C: Concentrations of the substance at or below the health based guideline value may affect the appearance, taste or odour of the water, leading to consumer complaints. CONCLUSION Several studies conducted on the viability of manufacturing fired brick partially or 100 % made of FA led to rather promising results (Chou et al., 2006; Chou et al., 2001; Kute and Deodhar, 2003; Lingling et al., 2005; Pimraksa et al., 2001; Kayali, 2005; Cengizler, 2008; iek and Tanrverdi, 2007 Tanrverdi ve iek, 2007b; iek ve Tanrverdi, 2004; Pimraksa et al., 2006; Chindaprasirt and Pimraksa, 2008). The use of such bricks is authorized in many countries such as Germany, the United Kingdom and India (Lingbawan, 2009). There are also a number of patents on the use of FAlime mixtures for making unfired bricks (Lingbawan, 2009). Environmental concerns raised in some parts of the world, such as in India, even resulted in legislation that obliged the brick industry to incorporate at least 25 % FA in the brick making mixture if the industry was within 100 km from a coal power generation plant (Lingbawan, 2009). Using FA partially as a supplement for clay to manufacture common burnt building bricks or totally to produce 100 % FA bricks will help to conserve natural resources and improve environmental quality while turning this waste material gainfully into an asset. On the other hand, either manufacturing conventional clay bricks or FFAB requires kilns fired to high temperatures that wastes energy, pollutes air and generates greenhouse gases that contribute to global warming. In contrast, by making use of some of the methods discussed above, NFFAB with high FA volume ratio or even NF100%FAB are manufactured at room temperature (Liu et al., 2009; Liu et al., 2005) and these innovative bricks using the residual FA are considered high quality building materials by the manufacturers. They conserve energy, cost less to manufacture, and don't contribute to air pollution or global warming (Liu et al., 2009). Furthermore, with increasing focus on sustainable development, there is little doubt that FAB having comparable characteristics to conventional clay bricks will have a potential competitive edge over current products.

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