Journal of Chemical Technology and Biotechnology

J Chem Technol Biotechnol 77:331335 (online: 2002) DOI: 10.1002/jctb.583

Advantages in the use of y ashes in cements containing pozzolanic combustion residues: silica fume, sewage sludge ash, spent uidized bed catalyst and rice husk ash
,* J Monzo , MV Borrachero, F Amahjour, I Girbe s, J Paya zquez n S Vela and LM Ordo ez
n en Qu n, GIQUIMA, Departamento de Ingenier n mica de los Materiales de Construccio a de la Construccio Grupo de Investigacio cnica de Valencia, Camino de Vera s/n, E-46071 Valencia, Spain Universidad Polite

Abstract: The enhancement in the workability of Portland cement concrete when coal y ashes are added to the mix is well-known. This behaviour has been attributed to the spherical shape and the smooth surface of the y ash particles. On the other hand, when other combustion residues with pozzolanic properties are added to concrete mix formulations, a loss in workability is observed, and an increase in water content may be necessary for obtaining a satisfactory plastic consistency of the concrete, or alternatively chemical additives may be used (plasticizers and superplasticizers). The effect of the combination of y ash with other mineral admixtures in respect of the effect on the workability of mortars has been studied. The pozzolanic combustion residues examined were: silica fume, sewage sludge ash, spent uid catalytic cracking catalyst and rice husk ash. Additionally, and due to the pozzolanic properties of coal y ash and these residues, the strength developments of Portland cement mortars containing y ash and the selected admixtures have also been measured. # 2002 Society of Chemical Industry

Keywords: combustion residues; pozzolans; concrete admixtures; silica fume; sewage sludge ash; spent uid catalytic cracking catalyst; rice husk ash
INTRODUCTION

Fly ashes from thermoelectric power plants generally present a typical spherical or spheroidal shape particle morphology, which together with their granulometric particle size distribution and the surface texture of the particles provide an enhancement to the properties of fresh concrete (eg workability and bleeding).1 Usually, these improved physical properties are not found for other industrial, agricultural and combustion wastes, and normally difculties related to increased water adsorption are found when these materials are used in concrete production. It is considered that these problems could be minimized by combining these wastes with y ashes (FA), resulting in a positive correction of the plasticity of the waste-containing concrete. Additionally, most of wastes used as cementreplacing materials possess pozzolanic activity, and their use in concrete enhances some properties of the nal cured product, especially strength and durability. The possibility of combining wastes and FA as pozzolanic ingredients in the mix could have some advantages such as a higher degree of cement

replacement, an extension of hydrated lime xation and synergic effects on the hydration of Portland cement and the pozzolanic reaction. We present here the results of the effect of the combination of FA and four types of pozzolanic wastes on the workability and strength of mortars: (a) sewage sludge ash, SSA, obtained from the incineration of municipal sewage sludge;2 (b) rice husk ash, RHA, obtained from the controlled autocombustion of rice husks;3 (c) silica fume, SF, from industrial synthesis of silicon alloys;4 and (d) spent uidized bed catalyst, FC3R, from a petrol renery.5

EXPERIMENTAL

The chemical composition and particle mean diameter (dm) for the pozzolans used are given in Table 1. Mortars were prepared with a 3:1 sand/binder weight ratio, the binder being the sum of cement and pozzolans (if used). Dosages for fresh mortar measurements and hardened mortar measurements are listed in Tables 2 and 3 respectively. The Workability of

, Grupo de Investigacio n en Qu n, GIQUIMA, Departamento de Ingenier mica de los Materiales de Construccio a * Correspondence to: J Paya n Universidad Polite cnica de Valencia, Camino de Vera s/n, E-46071 Valencia, Spain de la Construccio E-mail: jjpaya@cst.upv.es Paper presented at the PROGRES Workshop: Novel Products from Combustion Residues, 68 June 2001, Morella, Spain n General de Investigacio n Cient gica, Spain; contract/grant number: AMB 1998-0337 ca y Tecnolo Contract/grant sponsor: Direccio (Received 4 July 2001; revised version received 14 November 2001; accepted 20 November 2001)

# 2002 Society of Chemical Industry. J Chem Technol Biotechnol 02682575/2002/$30.00

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 et al J Paya
Table 1. Characteristics of pozzolans

Parameter LOI SiO2 AI2O3 Fe2O3 CaO MgO Na2O K2O SO3 dm (mm)

FA 2.44 40.94 24.65 13.59 9.83 1.59 0.34 1.40 1.60 21.94

SSA

RHA

SF

FC3R

5.10 17.05 6.69 1.50 20.80 78.33 91.05 48.2 14.90 nd 0.21 46.0 7.40 nd 0.14 0.95 31.30 0.35 0.48 nd 2.60 nd 0.19 nd nd 0.83 nd 0.50 nd 1.45 0.50 nd 12.40 0.25 0.14 0.04 30.70 19.73 44.41 19.95

nd: not determined.

mortars was evaluated by the measurement of the ow table spread (FTS).6 Compressive and exural strength were determined according to EN 196-1.

RESULTS AND DISCUSSION SEM characterization

The shape and surface texture of the pozzolanic residues were examined by SEM. The FA showed the typical spherical shape and characteristic surface smoothness, as expected (Fig 1(a and b)). The other four pozzolanic materials showed their own particular morphological characteristics. SSA (Fig 1(c)) was present as highly irregular-shaped particles with very rough surfaces. RHA (Fig 1(d)) partially maintained the organic structure of the original husk, presenting high porosity. SF (Fig 1(e)) consists of agglomerates of small particles in a densed structure, also with an high porosity. And nally, FC3R (Fig 1(f)) particles showed irregular shapes (due to grinding of the sample) and a high degree of roughness.
Workability studies

mean of the maximum and the minimum diameters of the spread cone and was given as FTS in mm. The FTS values found for pozzolanOPC mortars were compared with those found for control mortars (only OPC as binder material) by calculating the DFTS. This was obtained by measuring the difference between the FTS for pozzolanOPC mortar and the FTS for control mortar, both with the same water/ binder ratio. Thus, positive values for DFTS indicated an enhancement in owable properties of particular mortar mixes, whereas negative values suggest a negative effect of the pozzolan in the workability of a specic mortar due to the replacement of part of the OPC by the pozzolan or by a mix of two pozzolans (one of them FA). Figure 2 shows the DFTS values for pozzolanOPC mortars. It can be noticed that mortars containing FA showed higher workability than found for control mortars (positive DFTS values), conrming the plastizicing contribution of FA particles due to the ball-bearing effect. On the other hand, loss in the workability of mortars containing the other four pozzolans was observed (negative DFTS values) when OPC was replaced by the pozzolan at a value of 10% by mass, indicating the high water demand of these pozzolan particles in respect to the OPC particles. This workability loss is clearly compensated when FA is used as a second replacing material. Thus, for 10% P/20% FA mortars, positive DFTS values were obtained again, suggesting the strongly positive effect of FA particles in these mixtures. This effect was particularly important for RHA and SF mortars, where DFTS values were greater than 5 mm for RHA mortars and greater than 10 mm for SF mortars. For all cases, replacing with 20% FA amply compensates in workability the negative effect of mixes containing 10% of the other pozzolan (SSA, RHA, SF or FC3R) without FA.
Strength development studies

The workability of the experimental mortars was measured by determining the spreading of the mortar cone on a ow table. The value was expressed as a

The formation of hydraulic products from the pozzolanic reaction between FA and lime (calcium

Pozzolan (P) SSA RHA SF FC3R

OPC type I-42.5R I-52.5R I-42.5R I-52.5R

w/b ratio 0.5 0.5 0.5 0.45

Prepared mortars: replacement percentages (%P/%FA) 0%/0%; 0%/0%; 0%/0%; 0%/0%; 10% 10% 10% 10% 0%; 0%; 0%; 0%; 0%/20%; 0%/20%; 0%/20%; 0%/20%; 10%/20% 10%/20% 10%/20% 10%/20%

Table 2. Mortar dosage and components for workability studies

Pozzolan (P) OPC type w/b ratio Sp a (%) SSA RHA SF FC3R
a

Prepared mortars: replacement percentages (%P/%FA) 0%/0%; 0%/20%; 20%/20% 0%/0%; 10% 0%; 0%/20%; 10%/20% 0%/0%; 10% 0%; 10%/20% 0%/0%; 10% 0%; 0%/20%; 10%/20%

Table 3. Mortar dosage and components for strength studies

I-42.5R I-52.5R I-42.5R I-52.5R

0.44 0.45 0.4 0.35

1% 0% 1% 5%

Sp: superplasticizer.

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J Chem Technol Biotechnol 77:331335 (online: 2002)

Advantages of using y ashes in cements

Figure 1. SEM microphotographs of pozzolans: (a) and (b) FA; (c) SSA; (d) RHA; (e) SF; (f) FC3R.

hydroxide) takes place mainly during medium or long curing times for FAOPC pastes, because FA is considered to be a medium-reactive pozzolan. Consequently, the development of strength due to the pozzolanic reaction for FA is evident for curing times of 1490 days at room temperature. The compressive strengths (Rc) for control mortars and FAOPC

mortars reveal this point (see Table 4): Rc data for a 7-days curing period in 20% -FA-replacing mortars are much lower than those found for control mortars, whereas for a 28-days curing period they also were much lower except for samples prepared with a very low water/binder ratio (0.35 in FC3R system), where both Rc values were similar. However, longer curing

Figure 2. Workability results (DFTS) for pozzolanOPC cements: (a) SSA mortars; (b) RHA mortars; (c) SF mortars; (d) FC3R mortars.

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 et al J Paya Compressive strength (MPa) 7 days 41.24 31.51 21.92 45.1 40.8 47.3 39.4 41.98 43.67 41.83 56.76 44.89 66.48 55.05 28 days 50.2 43.79 36.3 51.2 44.5 53.5 52.1 49.92 56.53 52.62 59.11 59.05 75.9 65.95 90 days 49.06 49.36a 48.51a 58.2 56.8 62.5 59.7 56.66 62.3 62.04 72.63 67.68 83.67 70.08
a

Pozzolan (P) SSA

Mortars (%P/%FA) Control 0%/20% 20%/20% Control 0%/20% 10%/0% 10%/20% Control 10%/0% 10%/20% Control 0%/20% 10%/0% 10%/20%

Flexural strength (MPa) 7 days 7.06 6.14 7.72 8 6.8 7.7 6.5 6.39 7.28 5.83 7.65 6.86 9.6 7.61 28 days 7.43 6.79 6.43 8.7 8.1 8.8 8 7.42 8.44 8.47 9.33 6.52 10.08 8.27 90 days 6.01a 8.4a 8.39a 9.5 9.1 8.5 7.9 7.86 9.2 9.47 9.67 9 11.44 9.14

RHA

SF

FC3R

Table 4. Compressive strength (Rc) and exural strength values (Rf) for prepared mortars

Data for 28-days curing time at 40 C.

times (90 days, or 28 days at 40 C) yielded similar Rc values for FAOPC and control mortars. When a medium-activity pozzolanic material was used (SSA), similar Rc data to the control mortar were obtained with a 20% SSA plus 20% FA replacement (that is 40% of total replacement) for a 28-days curing time at 40 C, and this value was also similar to 20% FAOPC mortar at the same age and curing temperature, showing that this mixture (20% SSA/20% FA) of both pozzolans is very favourable for strength development. The results for RHA and SF were similar in respect to their strength development (they show pozzolanic reactivity at early ages), and RHAOPC and SFOPC mortars yielded higher Rc values than those found for control mortars with curing times of 7, 28 on 90 days, as expected. Of considerable interest were the Rc values for the corresponding RHAFAOPC and SFFAOPC mortars, which were similar to their respective controls at 7 days and 28 days. However, for a 90-days curing time they were also found to be similar or slightly higher than those for control mortars, suggesting that the pozzolanic reaction was also maintained over this longer curing time, despite the lime xation taking place earlier. Apparently, at an early age the presence of FA particles favoured the development of both OPChydraulic products and pozzolanhydraulic products from the second pozzolan, whereas for longer curing times FA played an important role in the lime xation process. For the highest reactive pozzolan tested (FC3R), certain peculiarities were found. Due to its high reactivity, FC3R-containing mortars yielded greater Rc values than those for the control mortars, except for FC3RFAOPC mortar at 90 days, where it was slightly lower than control mortar. Apparently, the presence of this highly reactive pozzolan produces a crucial lime xation level, diminishing the possibility
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of FA reacting with any remaining lime over the longer period. Finally, exural strength (Rf) values for prepared mortars are also listed in Table 4. The positive effect on Rf values due to the presence of FA in the mortar composition, specially for SSA- and SF-containing mortars, is noticeable. However, for the highly reactive pozzolan FC3R, the contribution of FA to the value of Rf was much less important than found for the FC3R alone.

CONCLUSIONS

It can be concluded that the use of FA as a second replacement material in mortars containing waterdemanding pozzolans is an appropriate procedure for enhancing the workability of the mixtures. The contribution to strength development due to the presence of FA in association with other pozzolanic such as SSA, RHA, SF or FC3R in OPC mortars becomes important, especially for long curing times (2890 days).

ACKNOWLEDGEMENTS

n General This work was supported by Direccio n Cient ca y Tecnolo gica, Spain de Investigacio (DGICYT, Proyecto AMB1998-0337). Thanks are ntica, Consell Metropolita given to BP Spain, Ferroatla de I'Horta and Manuel Planes (SEM-UPV Service).

REFERENCES
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J Chem Technol Biotechnol 77:331335 (online: 2002)

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Mellado A, Cenizas de cascara de arroz (CCA) obtenidas en n no controladas: posibilidades de uso condiciones de combustio en hormigones, in Proc III Congreso Nacional de Materiales Compuestos, Ed by Corz A and Pintado JM, pp 501508 (1999). 4 Fidjestol P and Lewis R, Microsilica as an addition, in Lea's Chemistry of Cement and Concrete, 4th edn, Ed by Hewlett PC, pp 675708 (1998). J, Monzo J and Borrachero MV, Fluid catalytic cracking 5 Paya catalyst residue (FC3R), an excellent mineral by-product for improving early strength development of cement mixtures. Cem Concr Res 29:17731779 (1999). J and Monzo J, Inuence of different sized 6 Peris-Mora E, Paya fractions of a y ash on workability of mortars. Cem Concr Res 23:917924 (1993).

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