Applied Clay Science 53 (2011) 669–675

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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. Cusidó, C. Soriano
Departament de Física i Enginyeria Nuclear, Universitat Politècnica de Catalunya, Pere Serra, 1-15, 08193 Sant Cugat del Vallès, 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 final 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/m·K) 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 confluence of both productions may be a good solution for the final 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 landfill 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 (Jordán 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 flocculated 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

The moisture of the forest wastes varied between 7% and 10%. 4-Microcline. it becomes easy to handle and helps to reduce and almost eliminate leaching during storage and transport. 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. The approximate composition was 33% sand. 5-Montmorillonite. In view of the facts and the advantages described above. 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. Selection of raw materials Three sludges were obtained from the biological treatment of three WWTPs: Gavà (SG). Fig. . the objective of this study is to investigate the optimal formulation in ternary ceramic mixtures. / Applied Clay Science 53 (2011) 669–675 Table 1 Qualitative mineral analysis of amounts of clays from X-ray diffractometry (from *.1. The mineralogical analysis (Philips X-ray diffractometer PW 1710) is shown in Table 1. which are appropriate for particular construction uses. in comparison with the concentration of the rest of the elements in Table 2. major presence). both in Catalonia. Heavy metal content and arsenic and selenium concentration were analyzed after calcination at 450 °C (Table 2). The forest wastes were sawdust for domestic uses (FW1) and sawdust from shredding of old furniture (FW2). to ****. CP2) and one at Alcoletge (CA). located at a short distance from Barcelona. The results were expressed as average values. Devant et al. 2-Calcite. The selection of the sludge for the tests was based on their capacity for the retention of heavy metals during incineration. Mineral content of the sludge calcinated at 450 °C (Table 3. The experimental analysis was done by total extraction of the samples with acid. which made them suitable for the ceramization process. The emission of odors is also minimized. 1) was similar to that of the clays CP1. Spain. Numbers identify main compounds found: 1-Quartz.670 M. Clay was supplied from two quarries at El Papiol (CP1. iv) Sewage sludge and forest wastes from old furniture or vegetable waste with harmful compounds are simultaneously leading to valorized products. 3-Dolomite. v) The higher heating value (HHV) of the ternary mixture implies an important energy saving. X-ray diffractogram of sludge ST incinerated at 450 °C. 2.m. 12457-1. 41% silt and 26% clay minerals. Hematite Goethite The moisture content of the clays varied between 3% and 9%. The final purpose is to illustrate the possibility of designing tailor-made ceramics that fulfill custom-physical properties. 7-Muscovite and 8-Sepiolite. As. all the tests and measurements were performed with at least three replicas. and to analyze its environmental characteristics. improving the ceramic process from an energetic point of view. to measure the physical properties. 1. 6-Clinochlore. The granulometry analysis of the clays revealed a Gaussian distribution. CP2 and CA (Table 1). Due to the large variation of the water contents. Pure illite Fig. The water content of the sewage sludge varied between 72% and 85%. the formulations were retained to the dried mater (d. Materials and methods For quality assurance and reproducibility. 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. Cd) found in the calcinated samples. Martorell (SM) and Tarragona (ST). All of them are medium-size cities with a strong industrial base. which is strongly encouraged. 2002). minor amounts. This fact explains the low concentrations of volatile metals (Hg. For this reason they had to be calcinated at 450 °C. as described in EN 12457-1 (EN. The three types of sludge used in this work arrived to the laboratory with high water content. 2.).

01 0.829 0.01 0.8 ± 0.10 0.10 0.2 26.2 26..1 34.5 7. density.2 28.5 ± 0.828 0.24 0.000 kg of material to prepare 30 samples.18 0.5 4.5 20.5 9 ± 0. kp/cm2) and thermal conductivity (λ.m.2 1100 ± 100 103 ± 6 30 ± 1 285 ± 25 87 ± 6 199 ± 3 2.1 24 ± 2 28.2 ± 0.2.8 ± 0.831 0.1 29.2 30.15 0. Regarding the forest waste.5 ± 0.818 0.26 0.2 28.79 0.9 ± 0.79 0.74 SM 3±2 6.5 ± 0.4 ± 0. They Table 4 Ternary mixtures samples prepared (under the worst case scenario) to produce the ternary pseudo diagram.09 0.12 0.14 0.m) material calcined.79 0.01 .097 0.107 0.126 0.4 ± 0.30 56 ± 1 58 ± 2 61 ± 2 58 ± 2 58 ± 1 58 ± 2 56 ± 2 0.10 0.1 29.5 7 ± 0.07 0 0.127 0.5 ± 0.827 0.5 0 ± 0.%) σ (kp/cm2) λ (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 0.83 0.1 24.7 ± 0. The mixtures were extruded and cut into test pieces 5 to 12 cm long for the compression tests.5 8.3 33.2 1084 ± 4 46.5 ± 0.1 28.9 ± 0.5 4. with the lowest concentration of chlorite.6 ± 0.1 ± 0.076 0.065 0.5 9.167 0.043 0.1 28.30 0. industrial tests would require the use of a minimum of 10.02 0.9 ± 0.4 ± 0.79 0. Other ceramic properties.5 10 ± 0. but the presence of chlorite decreases the melting point to 900 °C.5 9.09 0.30 ± 0.83 0. model HG-150) at a heating rate of 160 °C h −1.5 9.5 7.11 0.102 0.9 ± 0.80 0. water absorption. 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. all the selections were in agreement with the worst case scenario hypothesis. / Applied Clay Science 53 (2011) 669–675 Table 2 Concentration of heavy metals (plus As and Se) in the sludge.9 ± 0.%).30 ± 0.3 27 ± 5 29.79 0. especially for Pb and Cr ions.6 30.1 30 ± 0.5 16.124 0.718 0. The sludge finally chosen to prepare the samples was that of Tarragona (ST).065 0.5 11 ± 0. (c.10 0.12 0.69 ± 0.79 0.3 ± 0.5 12 ± 0.076 0.5 10 ± 0.5 cm height were used for thermal conductivity tests.5 ± 0.2 46 ± 0.18 0.03 0.127 0.M.5 6 ± 0.2 15.829 0. whereas the presence of carbonates (calcite) increases it (Brownell.043 0. its capability for adsorption of heavy metal ions was low.m.107 0.2 0.097 0 0 0.3 ± 0.2 ± 0.5 11 ± 0. Therefore. The clay content in the mixtures was between 79% and 83%.2 975 ± 5 62.1 0. from room temperature to 980 °C.5 ± 0.19 0.31 0.5 5 ± 0.033 0. expressed in bars).167 0.5 11.833 0.29 0.182 0.5 6.1 0. was chosen because chlorite increases the amount of the vitreous phase at low temperatures.1 29.5 9 ± 0.75 0.4 ± 0.02 0.01 0.5 por (porosity.3 ± 0.677 x (sludge) 0 0 0 0 0 0.5 26.1 25.36 ± 0. extrusion pressure (p.1 39.0 ± 0.01 032 ± 0.5 ± 0.08 0.5 ± 0.79 0. CP1.2 25.%) 14.m) dried material.5 ± 0.5 11 ± 0. W/m °C).5 ± 0.5 ± 0. These values are important to consider when choosing the appropriate sintering temperature.0 ± 0.36 ± 0. bar) 16 ± 0.8 ± 0.5 0 ± 0.5 ± 0. Cylindrical pieces of 5 cm diameter and 1.117 0.5 ± 0.827 0.0 ± 0.13 0.3 ± 0.26 ± 0.%).11 0.5 ± 0.117 0.5 ± 0. 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 0.2 18.11 0.5 13.182 0.05 0. Clay contents below 79% were not considered because the resulting material had insufficient mechanical strength.55 671 minerals start melting at 1050 °C.21 0 0 0.5 3.2 b 4.1 14.5 ± 0.28 ± 0.79 0.136 0. pres.2 ± 0. mechanical strength (σ. and their corresponding values of green body moisture (h.) Total (% c.56 ST 3.5 8.1 11 ± 2 b 3.1 21. Devant et al.6 ± 0. porosity (por. 2.2 1200 ± 10 290 ± 25 260 ± 20 8005 ± 40 420 ± 10 130 ± 10 2.8 ± 0.3 23. Sample preparation and sintering Table 3 Qualitative mineral analysis obtained by X-ray diffractometry of the sludge after calcination at 450 °C. 1976).833 0.054 0. the choice was the sawdust produced from shredding of old furniture (FW2) due to its higher pollution as compared to wood sawdust (FW1). By comparison.3 7±1 b3.5 9 ± 0. 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.0 ± 0.5 5 ± 0.5 0 ± 0.828 0.1 p (extr. such as retraction. Among the clays.085 h (moisture. and porosity were studied with rectangular pieces of 12 cm.0 ± 0.6 ± 0.1 ± 0. Because this particular sludge did not contain chlorite.238 fw (forest waste) 0 0 0 0 0 0.79 0.1 145 ± 2 4. (d.818 0.11 0.5 ± 0.054 0. The pieces were fired in a propane oven (Formagas.9 ± 0.4 29.) 2. A set of 31 mixtures were prepared according to Table 4.

672 M. The presence of these elements in the leachate was directly related to the properties of CP2. 10% forest waste). The technical uses of the ternary mixture require two parameters: the wet consistency of the pieces shaped by the extrusion of the green Fig. anorthite. The temperature curve was chosen similar to that for industrial structural ceramic materials. 7% sludge.3. the concentrations were below the detection level of the technique used. followed by a measure of concentration of inorganic components during different time intervals. and thermocouples were placed at both sides of the sample for measurements. diopside and spinel. Results and discussion 3. 2003). and in agreement with Jordán et al. 1994). depending on the number of extraction (Table 5). The open porosity can reach diameters on the order of 1 mm. Optical microscopy photograph at 10× showing the microstructure of a ceramic piece of ternary mixture (sample #25. .3. The pseudo diagram Statistical analyses were used to evaluate the relationships between the different compositions and the physical properties (Table 4). the mineral phases were gehlenite. and the extractant agent was replaced after every extraction. 1976). including sample blanks (Table 6. 2009). Adding sludge into the mixture did not vary the concentration of these elements in the leachate. / Applied Clay Science 53 (2011) 669–675 Table 5 Extraction scheme according to NEN 7345. 2.3.. Refractory metals (such as Va. Sintering temperature was 980 °C. after which they were removed from the oven and cooled down during 12 h to reach room temperature. Other heavy metals are first volatilized from the surface during cooking. and its weak fixation on the material makes them easy to leach. Cr) do not react with aluminum-silicates and therefore were not incorporated into their vitreous matrix (Kingery et al. 1976). Instead. in general. Extraction 1st 2nd 3rd 4th 5th 6th 7th 8th Extraction time (days ± 10%) 0. Increasing sintering temperatures increased the pore diameter of the material (Chiang et al. Sb.. becoming incorporated into the vitreous matrix making leaching more difficult. 2. 1 mm 3.3. 2. they remain encapsulated (Eddings et al. The microscopic porosity in the final product was similar to that of 100% clay bricks. Ba and F. Leaching tests The leaching tests were performed according to norm NEN 7345 of the Netherlands Tank Leaching Test (NEN 7345. interparticle void volume and internal pore volume.25 1 2. The tests revealed leaching concentration far below the limit defined in NEN 7345 for a material to be classified for building uses. (2005). Devant et al. These gaseous emissions cause the high porosity of the ceramics (Fig. 83% clay. The porosity was calculated using the expression (Harlbut and Klein. Cr.3. 1993). After sintering. 1992) : por = 100ð1−ρr = ρa Þ ð1Þ where ρr is the density measured by pycnometry and ρa is the bulk density. eight extractions were performed.2. The mechanical resistance was measured with an Instron LC8800 system according to norm UNE-67-026-94. The sample was left in the solution for a certain number of days. Detectable concentration levels were only found for V. measured as the mass-to-volume ratio of the parallelepiped pieces where the total volume includes particle volume. The presence of sewage sludge and forest waste leads to emission gases during firing (Cusidó et al. The presence of the pores provided lightness and improved the thermal and acoustic insulation properties of the material. 2). Extractions were done without stirring the solution. The thermal decomposition of sewage sludge and solid wastes. the main component of the ternary mixture.1.. Leaching tests were conducted on samples corresponding to different compositions of the ternary mixtures. The EU standard EN 12457-2 – Characterization of Waste Leaching Compliance Test for Leaching of Granular Waste Materials and Sludges – (EN. such as clay bricks. 2011). wollastonite.. for sample #28). 2002) was not applicable in this case because it is designated to characterize sludge per-se. The inorganic compounds of the sludge were incorporated in the amorphous or vitreous phase of the product. 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. In most of the cases. 2009). Characterization and environmental analysis of the ceramic pieces 2. 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 (Cusidó and Soriano. 1992). The extrusion pressure was measured with an analogical manometer. and later they start to react with aluminum silicates.25 4 9 16 36 64 were maintained at this maximum temperature for 3 h. For each sample.1. The values obtained (Table 7. Leaching tests were performed with 8 cm long samples and consisted of the introduction of a sample into acidic water. The porosity due to the decomposition of the organic material and volatile compound was about 3% of the total porosity of the product. 2. A thermal flow was applied at a constant rate through a cylindrical sample. The composition was very similar to that identified in a standard clay brick (Brownell. a regulation specifically dedicated to building materials and widely used in the EU. is the main problem regarding its use as a raw material in the production of bricks (Lee and Bae. Physical properties The moisture content of the ceramic pieces was measured using the method of constant mass at 105 °C (APHA. The thermal conductivity of the pieces was measured using a Holometrix ED 200 LT-A guarded heat-flow meter. 12457-1.

d. 2.001 0. A minimum pressure of 8 bar was necessary to extrude a wet piece of the ternary mixture (Alleman and Berman.d.d.54 ± 0.d. The linear regression performed to adjust extrusion pressure.5 ± 0. n.8 ± 0.055 1 VCM (%) b0. (4)) would be 96 kp/cm2. n.d. 320 + 90(1) n. The compression strength (Eq. Contour lines for the mechanical strength and thermal conductivity were added to the ternary pseudo diagram after using the expressions described above (Fig.d. n.d.d. n.d.2 ± 0. To illustrate the use of the pseudo diagram.d. n. the ternary mixture should contain 10% sludge. the 8-bar isobar.d.1%. 15 ± 3 n.d. the influence that the clay fraction c has on the porosity of the mixture was approximately three times higher than that of the sludge fraction.d.d.d.d. n.d.d. n. / Applied Clay Science 53 (2011) 669–675 673 Table 6 Leaching tests NEN 7345 of sample #28 (80% clay. 1.d. n.2 ± 0. 2.d.d.. 4. Use of the pseudo diagram Simultaneous representation in a ternary pseudo diagram of contour lines of the compression strength. n. following expression (3) (Kingery et al. n. n.d. n. n.d.d.d.d.d.d. n.d.054 0. n.d.1 n. 1995).d. 95 ± 92 20 ± l(2) 40 600 1 25 150 15 50 100 3500(1) 1.d. This limit could also be determined by the Atterberg limits for ceramic green bodies (Vieira et al. n.d. 3). n. n. The obtained isobar tended to be parallel to the x-axis (content of sludge).d.3 ± 0.d.d. c).d.2. n.4 ± 0.d. thermal conductivity and extrusion limit pressure (p = 8 bar) allow the formulation of ternary mixtures according to the desired properties of the final material.d.d.d.d. 10 ± 1 n.d.d. 1983). n.2(2) 4th n.d.3 n.9 ± 0. 12 ± 1 n.4 n. The resulting equation had R 2 = 96.d.1 b100 .d.d. 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. n. sludge and forest waste. stepwise regression methods were used (Minitab. n. n. n.d. 100 ± 30(1) n. por = 195−52:2 x−163 c: ð7Þ Thus.1 b 25 TOC (μg/g) b 0. n. n. p = 38:2 + 1:19 h−2:79 c⁎h ð2Þ where σ is the compression strength (kp/cm 2). 9±5 n.d.d. in%). fw) play a minor role for the final extrusion pressure. 0.1 n.d.d. 3500(1) n.d. n.d.d.d. meaning that the other two variables (c. 65 ± 60 0.7 ± 0.02 ± 0.d. n.7(2) n. n.d.4 n. 46 ± 5(1) n. n. n.d. n. 3.d. According to Table 7 Degasing and toxicity tests for sample #2 (100% clay) and sample # 28 (80% clay.d.4 ± 0. n. 30 ± 30 1. n.d.d.. h. n. 21 ± 2(1) n. x. n. n.d. n.d.8(2) 7th n. n.1 ± 0. 1953): λ = λ0 ½ð100−porÞ = ð100 + porފ: ð5Þ The thermal conductivity (λ) and porosity (por) data could be fitted by the expression: λ = 1:23½ð100−porÞ = ð100 + porފ: ð6Þ This shows that the content of moisture in the mixture was the dominant for the extrusion pressure.M.d. 2008). represented as a black continue line. and x (fraction of sludge). was drawn using Eq. and por is the porosity of the ceramic piece expressed in %.d. let us suppose that the mechanical strength should be 50 kp/cm 2.d.8 ± 0.d. due to the high water content of the sludge.4(2) (1) (2) and ) 6th n. n.5 25 250 200 25 20.d n. with a coefficient of determination R 2 = 71. n. According to the pseudo diagram (black triangle in Fig.d. n. % Sludge Outgassing test TLM (%) 0 15 Limit value of the test 0.d.01(2) Cumulative leaching Limit (NEN-7345) 5th n. n. n. 23 ± 0. Assuming that the 40% of the volume are voids (Fig.) under the detection limit of the instrument. n. 7±1 n. 10% forest waste and 80% clay (or in wet condition 31% sludge. n. Concentrations and standard deviation of 3 parallel samples expressed in mg/m2 except for (1) (in μg/m2) or (2) (in g/m2). n.d.d. 11 ± 1 n.l(2) 2nd n.000 1500 25 (2) body.d.6 ± 0.d. 8±5 n. a step-regression linear adjustment was carried out to express porosity (por) as a function of the ternary composition of the mixture (variables x. 3. 50 ± 10(1) n. 15% sludge and 5% forest waste). n.d.d. 1. 8% forest waste and 61% clay).d. n. n. n. 1. F.d. 15% sludge and 5% forest waste).d. n.d. 3).8%: σ = 2465 exp ð−5:47 por = 100Þ: ð4Þ The thermal conductivity λ (W/m 2K) can also be described as a function of porosity according to expression (Ryskewitsch. 1976): σ = σ0 expð−npor = 100Þ ð3Þ Using the experimental data collected in Table 4. 3. n. The compression strength is a limiting technological parameter for mixtures because it defines the compositions that are suitable for an industrial process.d.1 b0. n. n. 1. n.d.d.d. n.7%.1 Offgassing test CO (μg/g) b0.d.001 b0. (n. n.d.d. and the compression strength after firing. 79 ± 3 n. n. 0.d. n.d.d. n.d.d. n.d.d. 2.d n.d. in which the choice of the statistically significant predictive variables was carried out by an automatic procedure to maximize a statistical function.6 n.1(2) 3rd n.6 n.d.d. 3.5 n. 11 ± 3 n.d.d. The porosity (por) and mechanical strength (σ) data were adjusted by the following expression with R2 = 88. In order to choose the linear model that best fitted the data. n.d. In the ternary pseudo diagram.1 b 0. as a function of the green body extrusion moisture. (2) by substituting p = 8 bar and h equal to the mean of moisture content of clay. 10 ± 10(1) n. p (expressed in bar). 3. n. n. n. 30 ± 1(1) n. provided the following expression (2).1(1) n. n.1(2) 8th n.d.d. Contour lines of porosity were almost parallel to contour lines of the clay fraction (Fig. n.d.d. n.d. n.d.74 ± 0. n. 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.d. 3). Devant et al. It is exponentially dependent on the porosity of the cooked ceramic pieces.d n. n. n. 4) the mechanical strength should be above 83 kp/cm2.5 ± 0. 5±1 n.d.d. n. n. c (fraction of clay).

4% porosity. Fig. 4. although developed for a specific set of raw materials. In the graph. Photograph showing the industrial production (cutting stage) of the proposed ceramic material made of ternary mixtures of clay. 4. with 0. such as sawdust from shredding of old furniture. Conclusions Sewage sludge and forest waste. The ternary mixtures also decreased the compression strength to values suitable for industrial production (96 kp/cm 2 in bulk). a useful tool during the early stages of experimental design. (6) and (7). The construction of a ternary pseudo diagram. The dashed line in the diagram represents the 8-bar extrusion pressure isobar.31 W/m·K (much lower than that of 100% clay) and 59.4% porosity. However. the ternary mixtures could contain up to 10% sludge. the material would have a thermal conductivity of 0. The construction of a pseudo diagram is also useful to perform sensitivity studies for ternary formulations. 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. c corresponds to the fraction of clay participating in the mixture. making it unsuitable for extrusion. Ternary pseudo diagram obtained for this work. This result justifies the addition of the forest waste in the production of bricks. thermal conductivity and porosity. for the optimal mixture of 80% clay. 3. The black triangle (▲) indicates the optimal formulation of 10% sludge. was proven to be a useful tool for the formulation of clay bricks with custom physical properties. 10% sludge and 10% forest waste in dried conditions. The addition of forest waste in the formulation of ternary mixtures to produce building materials increased the t extrusion limit. It must be noted that the presented pseudo diagram is only valid for the raw materials specifically studied. All fractions are expressed as percentages in dried matter. Note the roughness of the borders of the pieces due to the presence of sludge and forest waste.674 M. . The pseudo diagram was also helpful to study the sensitivity of the physical properties to changes in the composition of the ternary mixture.31 W/m·K and 59. a thermal conductivity of 0. 8% forest waste and 61% clay in wet). in a binary mixture with clay. 10% forest waste and 80% clay (31% sludge. Eqs. Devant et al. The pseudo diagram is also helpful in analyzing the properties of ceramic products following the lines for the content of the individual components. the extrusion limit would allow a maximum content of sludge (x).4% porosity. A slight increase in the sewage sludge content would move the mixture to the right of the technological limit. Mixtures positioned to the right of this line could not be properly extruded. for the production of red clay ceramics had three main advantages: valorization of hazardous wastes that are generated in large quantities. of 6%. Continuous lines represent contours of constant mechanical strength to compression. immobilization of heavy metals. without forest waste (fw = 0). / Applied Clay Science 53 (2011) 669–675 Fig. A material with such composition would have a mechanical strength to compression of 96 kp/cm2.31 W/m·K and 59. For instance. and reduction of costs of raw materials including clay and water. Adding 10% forest waste (moving along the line representing the extrusion limit boundary). 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. x is the fraction of sludge and fw is the fraction of forest waste. sewage sludge and forest waste.

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