Applied Clay Science 53 (2011) 669675

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Applied Clay Science

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c l a y

Research Paper

Custom formulation of red ceramics with clay, sewage sludge and forest waste
M. Devant , J.A. Cusid, C. Soriano
Departament de Fsica i Enginyeria Nuclear, Universitat Politcnica de Catalunya, Pere Serra, 1-15, 08193 Sant Cugat del Valls, Barcelona, Spain

a r t i c l e

i n f o

a b s t r a c t
The large quantities of sewage sludge that are currently generated require new alternatives for its recycling and nal destination, beyond already known methods in the agriculture and cement industry. The use of this sludge as raw material for the production of structural ceramics, such as clay bricks, may become an interesting alternative, both from an industrial and environmental point of view. Several investigations have addressed this issue by formulating binary mixtures of sludge with clay. However, the incorporation of forest waste into the binary mixture described in this paper allows a high amount of sewage sludge to be assimilated into an extrudable mix and represents a better choice for the valorization of this hazardous waste. In this study the physicochemical properties of several formulations of ternary mixtures were analyzed. A ternary pseudo diagram was obtained relating the physicochemical properties of the ceramic product to the fraction of the raw materials. The optimal ternary mixture of 10% sludge, 10% forest waste and 80% clay, yielded a ceramic material with compression strength of 96 kp/cm 2. It also met the technological limit of 8 bar to give and extrudable material. The mixture would be suitable for building ceramics, with low thermal conductivity (0.31 W/mK) and high porosity (59.4%). The environmental aspects of the production of these ceramics were investigated by leaching and outgassing tests. 2011 Elsevier B.V. All rights reserved.

Article history: Received 7 December 2010 Received in revised form 8 June 2011 Accepted 9 June 2011 Available online 13 July 2011 Keywords: Urban sewage sludge Forest wastes Inertization Ceramics Customized bricks Waste

1. Introduction The incorporation of waste into ceramic matrices has been studied extensively over the past twenty years (Anderson, 2002; Berman, 1982). The large amount of sludge produced in waste water treatment plants (WWTPs) and the high demand of structural ceramics for construction suggest that the conuence of both productions may be a good solution for the nal waste destination. This could be a successful alternative to other more common uses of sludge as the agriculture and cement industry. Underlying this issue is the fact that sewage sludge cannot be disposed of in a controlled landll due to its high organic matter content (Council Directive, 1999). Since the early work of Alleman and Berman (1983) and Tay (1987), there has been a considerable amount of literature on the production of clay bricks using binary mixtures (Jordn et al., 2005; Liew et al., 2004a, 2004b; Monteiro et al., 2008; Weng et al., 2003; Wiesbusch et al., 1998) and ternary mixtures (Chiang et al., 2009; Montero et al., 2009). In most of these studies, the sludge used for the production of clay bricks came from WWTPs. In some cases, however, dehydrated sewage sludge or incinerated sewage sludge ash were used (Lin and Weng, 2001). Other studies used industrial wastewater sludge from the paper

industry (Demir et al., 2005), the galvanic industry (Magalhaes et al., 2004) or the olive oil industry (Monteiro and Vieira, 2005). More recently, pelletized dehydrated WWTP sludge was used to produce bricks (Qi et al., 2010). Finally, as an alternative to the production of structural ceramics from sludge waste, some efforts were directed toward its use in the manufacturing of concrete blocks (Kaosol, 2010). As for ternary mixtures, several materials may be added to the clay and WWTP sludge: rice husks, agricultural wastes, forest weeding wastes, chips and sawdust from old furniture, by-products of the marble and stone industry, and grogs (chamottes) from the ceramic industry. Considering all of the above facts, the main advantages of ternary mixtures of clay, sewage sludge and forest waste can be summarized as: i) Adding forest waste to sludge provides higher granulometry to the mixture. Crushed forest residues are impregnated with the sludge which alone is a occulated paste, and the mixture adopts the grain size of the forest waste. ii) The extrusion limit of the ceramic green body is highly dependent on the composition of the mixture. The use of ternary mixtures allows a high content of sewage sludge of the extrudable mix. For example, a formulation with 0% forest waste allowed the addition of a maximum of 6% sludge; a ternary mixture with 10% forest waste allowed the addition of 10% sludge.

Corresponding author. Tel.: + 34 93 4017900; fax: + 34 93 4017901. E-mail address: marti.v.f.devant@upc.edu (M. Devant). 0169-1317/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.clay.2011.06.002

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M. Devant et al. / Applied Clay Science 53 (2011) 669675 Table 1 Qualitative mineral analysis of amounts of clays from X-ray diffractometry (from *, minor amounts, to ****, major presence). Mineral group Mineral Clay CP1 Quartz Carbonates Feldspars Clays Quartz Calcite Dolomite Feldspars Muscovite Chlorite Montmorillonite Hematite Goethite **** ** * * ** ** ** * CP2 **** ** * * ** ** ** * CA1 **** **** * * ** ** *

iii) If the mixture of sewage sludge with forest waste is carried out in WWTP facilities, which is strongly encouraged, it becomes easy to handle and helps to reduce and almost eliminate leaching during storage and transport. The emission of odors is also minimized. iv) Sewage sludge and forest wastes from old furniture or vegetable waste with harmful compounds are simultaneously leading to valorized products. v) The higher heating value (HHV) of the ternary mixture implies an important energy saving, improving the ceramic process from an energetic point of view. In view of the facts and the advantages described above, the objective of this study is to investigate the optimal formulation in ternary ceramic mixtures, to measure the physical properties, and to analyze its environmental characteristics. The nal purpose is to illustrate the possibility of designing tailor-made ceramics that fulll custom-physical properties, which are appropriate for particular construction uses. 2. Materials and methods For quality assurance and reproducibility, all the tests and measurements were performed with at least three replicas. The results were expressed as average values. This study was carried out under the hypothesis of worst case scenario meaning that the material used in the tests represented the worst possible choice with respect to physicochemical properties and potential environmental risk. 2.1. Selection of raw materials Three sludges were obtained from the biological treatment of three WWTPs: Gav (SG), Martorell (SM) and Tarragona (ST). All of them are medium-size cities with a strong industrial base, located at a short distance from Barcelona, Spain. The forest wastes were sawdust for domestic uses (FW1) and sawdust from shredding of old furniture (FW2). Clay was supplied from two quarries at El Papiol (CP1, CP2) and one at Alcoletge (CA), both in Catalonia.

Hematite Goethite

The moisture content of the clays varied between 3% and 9%. The moisture of the forest wastes varied between 7% and 10%. The water content of the sewage sludge varied between 72% and 85%. Due to the large variation of the water contents, the formulations were retained to the dried mater (d.m.). The granulometry analysis of the clays revealed a Gaussian distribution, which made them suitable for the ceramization process. The approximate composition was 33% sand, 41% silt and 26% clay minerals. The mineralogical analysis (Philips X-ray diffractometer PW 1710) is shown in Table 1. The selection of the sludge for the tests was based on their capacity for the retention of heavy metals during incineration. Heavy metal content and arsenic and selenium concentration were analyzed after calcination at 450 C (Table 2). The experimental analysis was done by total extraction of the samples with acid, as described in EN 12457-1 (EN, 12457-1, 2002). The three types of sludge used in this work arrived to the laboratory with high water content. The standard analytical method to measure the concentration of heavy metals and other elements required both the elimination of water and organic matter from the samples. For this reason they had to be calcinated at 450 C. This fact explains the low concentrations of volatile metals (Hg, As, Cd) found in the calcinated samples, in comparison with the concentration of the rest of the elements in Table 2. Mineral content of the sludge calcinated at 450 C (Table 3, Fig. 1) was similar to that of the clays CP1, CP2 and CA (Table 1). Pure illite

Fig. 1. X-ray diffractogram of sludge ST incinerated at 450 C. Numbers identify main compounds found: 1-Quartz, 2-Calcite, 3-Dolomite, 4-Microcline, 5-Montmorillonite, 6-Clinochlore, 7-Muscovite and 8-Sepiolite.

M. Devant et al. / Applied Clay Science 53 (2011) 669675 Table 2 Concentration of heavy metals (plus As and Se) in the sludge. (d.m) dried material, (c.m) material calcined. Element Sludge SG Hg (ppm) As (ppm) Se (ppm) Zn (ppm) Pb (ppm) Ni (ppm) Cu (ppm) Cr (ppm) Mn (ppm) Cd (ppm) Total (% d.m.) Total (% c.m.) 2.3 0.1 11 2 b 3.2 1200 10 290 25 260 20 8005 40 420 10 130 10 2.5 0.2 0.31 0.74 SM 32 6.9 0.2 b 4.2 975 5 62.5 0.6 30.0 0.2 1084 4 46.9 0.1 145 2 4.7 0.1 0.24 0.56 ST 3.0 0.3 71 b3.2 1100 100 103 6 30 1 285 25 87 6 199 3 2.8 0.1 0.18 0.55

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minerals start melting at 1050 C, but the presence of chlorite decreases the melting point to 900 C, whereas the presence of carbonates (calcite) increases it (Brownell, 1976). These values are important to consider when choosing the appropriate sintering temperature. The sludge nally chosen to prepare the samples was that of Tarragona (ST). Because this particular sludge did not contain chlorite, its capability for adsorption of heavy metal ions was low, especially for Pb and Cr ions. Among the clays, CP1, with the lowest concentration of chlorite, was chosen because chlorite increases the amount of the vitreous phase at low temperatures. Regarding the forest waste, the choice was the sawdust produced from shredding of old furniture (FW2) due to its higher pollution as compared to wood sawdust (FW1). Therefore, all the selections were in agreement with the worst case scenario hypothesis.

2.2. Sample preparation and sintering

Table 3 Qualitative mineral analysis obtained by X-ray diffractometry of the sludge after calcination at 450 C. Mineral Sludge SG Quartz Calcite Dolomite Albite Microcline Muscovite Chlorite Montmorillonite Sepiolite Baryte Anhydrite *** **** *** * * * * * SM *** **** * ** * * * * * ST *** **** *** *** * * *

A number of 30 ceramic pieces were made from a mixture of 10 kg. By comparison, industrial tests would require the use of a minimum of 10,000 kg of material to prepare 30 samples. A set of 31 mixtures were prepared according to Table 4. The clay content in the mixtures was between 79% and 83%. Clay contents below 79% were not considered because the resulting material had insufcient mechanical strength. The mixtures were extruded and cut into test pieces 5 to 12 cm long for the compression tests. Cylindrical pieces of 5 cm diameter and 1.5 cm height were used for thermal conductivity tests. Other ceramic properties, such as retraction, water absorption, density, and porosity were studied with rectangular pieces of 12 cm. The pieces were red in a propane oven (Formagas, model HG-150) at a heating rate of 160 C h 1, from room temperature to 980 C. They

Table 4 Ternary mixtures samples prepared (under the worst case scenario) to produce the ternary pseudo diagram, and their corresponding values of green body moisture (h,%), extrusion pressure (p, expressed in bars), porosity (por,%), mechanical strength (, kp/cm2) and thermal conductivity (, W/m C). Sample Composition (fraction of unity) c (clay) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 1 1 1 1 1 0.79 0.79 0.79 0.79 0.79 0.79 0.79 0.79 0.79 0.833 0.833 0.831 0.83 0.83 0.829 0.829 0.828 0.828 0.827 0.827 0.818 0.818 0.80 0.75 0.718 0.677 x (sludge) 0 0 0 0 0 0.08 0.09 0.10 0.10 0.10 0.11 0.12 0.14 0.21 0 0 0.033 0.043 0.043 0.054 0.054 0.065 0.065 0.076 0.076 0.182 0.182 0.15 0.126 0.18 0.238 fw (forest waste) 0 0 0 0 0 0.13 0.12 0.11 0.11 0.11 0.10 0.09 0.07 0 0.167 0.167 0.136 0.127 0.127 0.117 0.117 0.107 0.107 0.097 0.097 0 0 0.05 0.124 0.102 0.085 h (moisture,%) 14.0 0.1 14.8 0.2 15.0 0.5 16.4 0.2 18.0 0.4 29.3 0.1 29.5 0.1 24 2 28.4 0.1 29.6 0.1 29.9 0.1 30 0.3 33.2 0.1 28.1 0.2 25.3 0.3 23.9 0.2 30.8 0.1 21.6 0.1 28.4 0.1 24.2 0.2 28.9 0.1 25.8 0.2 26.1 0.5 26.2 0.2 26.3 0.3 27 5 29.6 0.2 28.5 0.1 34.4 0.1 39.9 0.2 46 0.1 p (extr. pres., bar) 16 0.5 8.5 0.5 20.5 0.5 10 0.5 6.5 0.5 9.5 0.5 9 0.5 13.5 0.5 11.5 0.5 9.5 0.5 9 0.5 7 0.5 5 0.5 11 0.5 9 0.5 11 0.5 3.5 0.5 11 0.5 6 0.5 10 0.5 4.5 0.5 7.5 0.5 12 0.5 9.5 0.5 8.5 0.5 0 0.5 5 0.5 7.5 0.5 4.5 0.5 0 0.5 0 0.5 por (porosity,%) (kp/cm2) (W/m C)

32 3 64 1 61 2 59 1 62 1 62 1 59 1

419 45 391 85 420 45 77 14 81 11 64 8 76 9 90 10 88 16 80 22 99 5 88 8 122 12 90 7 118 19 131 24 146 21 122 12 105 32 64 12 51 9 50 3

0.69 0.01 0.29 0.26 0.30 0.30

56 1 58 2 61 2 58 2 58 1 58 2 56 2

0.19 0.36 0.01 0.26 0.03 0.30 0.01 0.30 0.01 032 0.02 0.28 0.02 0.36 0.01

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M. Devant et al. / Applied Clay Science 53 (2011) 669675 Table 5 Extraction scheme according to NEN 7345. Extraction 1st 2nd 3rd 4th 5th 6th 7th 8th Extraction time (days 10%) 0.25 1 2.25 4 9 16 36 64

were maintained at this maximum temperature for 3 h, after which they were removed from the oven and cooled down during 12 h to reach room temperature. The temperature curve was chosen similar to that for industrial structural ceramic materials, such as clay bricks. After sintering, and in agreement with Jordn et al. (2005), the mineral phases were gehlenite, anorthite, wollastonite, diopside and spinel. The composition was very similar to that identied in a standard clay brick (Brownell, 1976). The thermal decomposition of sewage sludge and solid wastes, in general, is the main problem regarding its use as a raw material in the production of bricks (Lee and Bae, 2009). The presence of sewage sludge and forest waste leads to emission gases during ring (Cusid et al., 2003). These gaseous emissions cause the high porosity of the ceramics (Fig. 2). Increasing sintering temperatures increased the pore diameter of the material (Chiang et al., 2009). The microscopic porosity in the nal product was similar to that of 100% clay bricks. The porosity due to the decomposition of the organic material and volatile compound was about 3% of the total porosity of the product. The inorganic compounds of the sludge were incorporated in the amorphous or vitreous phase of the product. 2.3. Characterization and environmental analysis of the ceramic pieces 2.3.1. Physical properties The moisture content of the ceramic pieces was measured using the method of constant mass at 105 C (APHA, 1992). The extrusion pressure was measured with an analogical manometer. The mechanical resistance was measured with an Instron LC8800 system according to norm UNE-67-026-94. The porosity was calculated using the expression (Harlbut and Klein, 1992) : por = 1001r = a 1

where r is the density measured by pycnometry and a is the bulk density, measured as the mass-to-volume ratio of the parallelepiped pieces where the total volume includes particle volume, interparticle void volume and internal pore volume. The thermal conductivity of the pieces was measured using a Holometrix ED 200 LT-A guarded heat-ow meter. A thermal ow was applied at a constant rate through a cylindrical sample, and thermocouples were placed at both sides of the sample for measurements.

2.3.2. Leaching tests The leaching tests were performed according to norm NEN 7345 of the Netherlands Tank Leaching Test (NEN 7345, 1993), a regulation specically dedicated to building materials and widely used in the EU. The EU standard EN 12457-2 Characterization of Waste Leaching Compliance Test for Leaching of Granular Waste Materials and Sludges (EN, 12457-1, 2002) was not applicable in this case because it is designated to characterize sludge per-se. Leaching tests were performed with 8 cm long samples and consisted of the introduction of a sample into acidic water, followed by a measure of concentration of inorganic components during different time intervals. For each sample, eight extractions were performed. The sample was left in the solution for a certain number of days, depending on the number of extraction (Table 5). Extractions were done without stirring the solution, and the extractant agent was replaced after every extraction. Leaching tests were conducted on samples corresponding to different compositions of the ternary mixtures, including sample blanks (Table 6, for sample #28). Refractory metals (such as Va, Cr) do not react with aluminum-silicates and therefore were not incorporated into their vitreous matrix (Kingery et al., 1976). Instead, they remain encapsulated (Eddings et al., 1994), and its weak xation on the material makes them easy to leach. Other heavy metals are rst volatilized from the surface during cooking, and later they start to react with aluminum silicates, becoming incorporated into the vitreous matrix making leaching more difcult. The tests revealed leaching concentration far below the limit dened in NEN 7345 for a material to be classied for building uses. In most of the cases, the concentrations were below the detection level of the technique used. Detectable concentration levels were only found for V, Cr, Sb, Ba and F. The presence of these elements in the leachate was directly related to the properties of CP2, the main component of the ternary mixture. Adding sludge into the mixture did not vary the concentration of these elements in the leachate. 2.3.3. Off-gassing and out-gassing tests Off-gassing and out-gassing tests were performed according to ESA PSS-01-702 (1994) and ESA PSS-01-729 (1991) of the European Space Agency (Cusid and Soriano, 2011). The values obtained (Table 7, for sample #28 and sample blank #2) were well below the maximum levels allowed and were almost identical to the blanks (100% clay): thus the use of the ceramic material as building material is not limited.

1 mm

3. Results and discussion 3.1. The pseudo diagram Statistical analyses were used to evaluate the relationships between the different compositions and the physical properties (Table 4). The technical uses of the ternary mixture require two parameters: the wet consistency of the pieces shaped by the extrusion of the green

Fig. 2. Optical microscopy photograph at 10 showing the microstructure of a ceramic piece of ternary mixture (sample #25, 83% clay, 7% sludge, 10% forest waste). Sintering temperature was 980 C. The open porosity can reach diameters on the order of 1 mm. The presence of the pores provided lightness and improved the thermal and acoustic insulation properties of the material.

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Table 6 Leaching tests NEN 7345 of sample #28 (80% clay, 15% sludge and 5% forest waste). Concentrations and standard deviation of 3 parallel samples expressed in mg/m2 except for (1) (in g/m2) or (2) (in g/m2). (n.d.) under the detection limit of the instrument. Element Leaching Extraction (Leaching concentration expressed in mg/m2 except in 1st As Ba Cd Co Cr Mo Ni Pb Sb(1) Se Sn V Zn Br Cr F 2(2) SO4 n.d. n.d. n.d. n.d. 1.6 0.3 n.d n.d. n.d. 30 1(1) n.d. n.d. 15 3 n.d. n.d. n.d. n.d. 3.8 0.l(2) 2nd n.d. n.d. n.d. n.d. 2.5 0.4 n.d n.d. n.d. 23 0.1(1) n.d. n.d. 11 1 n.d. n.d. n.d. n.d. 2.9 0.1(2) 3rd n.d. n.d. n.d. n.d. 4.2 0.4 n.d. n.d. n.d. 10 10(1) n.d. n.d. 51 n.d. n.d. n.d. n.d. 3.4 0.2(2) 4th n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 21 2(1) n.d. n.d. 12 1 n.d. n.d. n.d. n.d. 3.4 0.4(2)
(1) (2)

and

) 6th n.d. 0.54 0.5 n.d. n.d. n.d. n.d n.d. n.d. 46 5(1) n.d. n.d. 85 n.d. n.d. n.d. n.d. 1.3 0.8(2) 7th n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. 100 30(1) n.d. n.d. 71 n.d. n.d. n.d. 30 30 1.7 0.1(2) 8th n.d. 1.2 0.1 n.d. n.d. 1.8 0.6 n.d. n.d. n.d. 320 + 90(1) n.d. n.d. 11 3 n.d. n.d. n.d. 65 60 0.02 0.01(2)

Cumulative leaching

Limit (NEN-7345)

5th n.d. 0.74 0.1 n.d. n.d. n.d. n.d. n.d. n.d. 50 10(1) n.d. n.d. 95 n.d. n.d. n.d. n.d. 3.1 0.7(2)

n.d. 2.5 0.6 n.d. n.d. 10 1 n.d. n.d. n.d. 3500(1) n.d. n.d. 79 3 n.d. n.d. n.d. 95 92 20 l(2)

40 600 1 25 150 15 50 100 3500(1) 1.5 25 250 200 25 20,000 1500 25 (2)

body; and the compression strength after ring. A minimum pressure of 8 bar was necessary to extrude a wet piece of the ternary mixture (Alleman and Berman, 1983). This limit could also be determined by the Atterberg limits for ceramic green bodies (Vieira et al., 2008). The simplest model to parameterize extrusion pressure is to perform a multiple linear regression with cross terms of the following variables: h (green body extrusion moisture, in%); c (fraction of clay); and x (fraction of sludge). In order to choose the linear model that best tted the data, stepwise regression methods were used (Minitab, 1995), in which the choice of the statistically signicant predictive variables was carried out by an automatic procedure to maximize a statistical function, F. The linear regression performed to adjust extrusion pressure, p (expressed in bar), as a function of the green body extrusion moisture, h, provided the following expression (2), with a coefcient of determination R 2 = 71.1%. p = 38:2 + 1:19 h2:79 ch 2

where is the compression strength (kp/cm 2), and por is the porosity of the ceramic piece expressed in %. The porosity (por) and mechanical strength () data were adjusted by the following expression with R2 = 88.8%: = 2465 exp 5:47 por = 100: 4

The thermal conductivity (W/m 2K) can also be described as a function of porosity according to expression (Ryskewitsch, 1953): = 0 100por = 100 + por: 5

The thermal conductivity () and porosity (por) data could be tted by the expression: = 1:23100por = 100 + por: 6

This shows that the content of moisture in the mixture was the dominant for the extrusion pressure. In the ternary pseudo diagram, the 8-bar isobar, represented as a black continue line, was drawn using Eq. (2) by substituting p = 8 bar and h equal to the mean of moisture content of clay, sludge and forest waste. The obtained isobar tended to be parallel to the x-axis (content of sludge), meaning that the other two variables (c, fw) play a minor role for the nal extrusion pressure, due to the high water content of the sludge. The compression strength is a limiting technological parameter for mixtures because it denes the compositions that are suitable for an industrial process. It is exponentially dependent on the porosity of the cooked ceramic pieces, following expression (3) (Kingery et al., 1976): = 0 expnpor = 100 3

Using the experimental data collected in Table 4, a step-regression linear adjustment was carried out to express porosity (por) as a function of the ternary composition of the mixture (variables x, c). The resulting equation had R 2 = 96.7%. por = 19552:2 x163 c: 7

Thus, the inuence that the clay fraction c has on the porosity of the mixture was approximately three times higher than that of the sludge fraction, x. Contour lines of porosity were almost parallel to contour lines of the clay fraction (Fig. 3). Contour lines for the mechanical strength and thermal conductivity were added to the ternary pseudo diagram after using the expressions described above (Fig. 3). 3.2. Use of the pseudo diagram Simultaneous representation in a ternary pseudo diagram of contour lines of the compression strength, thermal conductivity and extrusion limit pressure (p = 8 bar) allow the formulation of ternary mixtures according to the desired properties of the nal material. To illustrate the use of the pseudo diagram, let us suppose that the mechanical strength should be 50 kp/cm 2. Assuming that the 40% of the volume are voids (Fig. 4) the mechanical strength should be above 83 kp/cm2. According to the pseudo diagram (black triangle in Fig. 3), the ternary mixture should contain 10% sludge, 10% forest waste and 80% clay (or in wet condition 31% sludge, 8% forest waste and 61% clay). The compression strength (Eq. (4)) would be 96 kp/cm2. According to

Table 7 Degasing and toxicity tests for sample #2 (100% clay) and sample # 28 (80% clay, 15% sludge and 5% forest waste). % Sludge Outgassing test TLM (%) 0 15 Limit value of the test 0.054 0.055 1 VCM (%) b0.001 b0.001 0.1 Offgassing test CO (g/g) b0.1 b0.1 b 25 TOC (g/g) b 0.1 b 0.1 b100

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Fig. 3. Ternary pseudo diagram obtained for this work. In the graph, c corresponds to the fraction of clay participating in the mixture, x is the fraction of sludge and fw is the fraction of forest waste. All fractions are expressed as percentages in dried matter. The dashed line in the diagram represents the 8-bar extrusion pressure isobar. Mixtures positioned to the right of this line could not be properly extruded. Continuous lines represent contours of constant mechanical strength to compression, thermal conductivity and porosity. The black triangle () indicates the optimal formulation of 10% sludge, 10% forest waste and 80% clay (31% sludge, 8% forest waste and 61% clay in wet). A material with such composition would have a mechanical strength to compression of 96 kp/cm2, a thermal conductivity of 0.31 W/mK and 59.4% porosity.

Eqs. (6) and (7), the material would have a thermal conductivity of 0.31 W/mK (much lower than that of 100% clay) and 59.4% porosity. A slight increase in the sewage sludge content would move the mixture to the right of the technological limit, making it unsuitable for extrusion. The construction of a pseudo diagram is also useful to perform sensitivity studies for ternary formulations. For instance, without forest waste (fw = 0), the extrusion limit would allow a maximum content of sludge (x), in a binary mixture with clay, of 6%. Adding 10% forest waste (moving along the line representing the extrusion limit boundary), the ternary mixtures could contain up to 10% sludge. This

result justies the addition of the forest waste in the production of bricks. The pseudo diagram is also helpful in analyzing the properties of ceramic products following the lines for the content of the individual components. It must be noted that the presented pseudo diagram is only valid for the raw materials specically studied. However, the main characteristics of other types of mixtures would not be very different from the one presented here because the raw materials would not be that different. 4. Conclusions Sewage sludge and forest waste, such as sawdust from shredding of old furniture, for the production of red clay ceramics had three main advantages: valorization of hazardous wastes that are generated in large quantities; immobilization of heavy metals, and reduction of costs of raw materials including clay and water. The addition of forest waste in the formulation of ternary mixtures to produce building materials increased the t extrusion limit. The use of ternary mixtures produced ceramic pieces with increased porosity which reduced the thermal conductivity to less than half the value of conventional red clays. The ternary mixtures also decreased the compression strength to values suitable for industrial production (96 kp/cm 2 in bulk), with 0.31 W/mK and 59.4% porosity, for the optimal mixture of 80% clay, 10% sludge and 10% forest waste in dried conditions. The construction of a ternary pseudo diagram, although developed for a specic set of raw materials, was proven to be a useful tool for the formulation of clay bricks with custom physical properties. The pseudo diagram was also helpful to study the sensitivity of the physical properties to changes in the composition of the ternary mixture, a useful tool during the early stages of experimental design.

Fig. 4. Photograph showing the industrial production (cutting stage) of the proposed ceramic material made of ternary mixtures of clay, sewage sludge and forest waste. Note the roughness of the borders of the pieces due to the presence of sludge and forest waste.

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Additionally, this study demonstrated the possibility to design tailormade ceramics, with custom physical properties for the use in construction. Finally, from an environmental point of view, leaching and toxicity (degassing) tests performed on the new material have demonstrated the absence of environmental risks for end users. References
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