CHARATERISTIC OF MASONY BLOCK MANUFACTURED WITH RICE STRAW ASH

ABSTRACT
To prevent the burning rice straw in the field which affects the purity of air and causes the formation of black clouds in Egypt. So that the aims of the present work was to study the characterization of rice straw ash by using chemical analysis, mineralogical composition as well as the effect of heat on ash in the temperature from 400 up to 1000C. Also, the application of the rice straw and its ashes in clay bricks at different clays were also investigated. The results indicated that the silica of rice straw is as amorphous at firing temperature 400 up to 600 C beside traces of calcite mineral. At 700C gave complete dissociation of calcite. By increasing firing temperature from 800 to 900C, the crystallinity increased as well as cristobalite and tridymite were identified. The cristobalite was increased by increasing firing temperature up to 1000C. By applying rice straw and its ash in clay bricks manufacture at different clays with the same firing temperature at 900C for 2 hours soaking time. The results revealed that, the crushing strength, bulk density and linear firing shrinkage were decreased by increasing addition of straw and ash to clay bricks. At the same time, apparent porosity, water absorption as well as loss in weight are increased. Also, the physico-mechanical properties of clay to ash mixture were higher than clay with straw due to loss in weight of ash was lower than straw and the reactivity of silica in the ash, which increases the reactivity during firing process.

INTRODUCTIO|N
Over one million acres of rice crops were grown in Egypt. One of acre of rice produces two tones of straw, meaning that over two million tons of straw waste was left behind after the harvest in October and November. Field burning of waste straw emits CO and particulates, by products found to a significant effect on the quality of air and people's health. Rice burning has been linked to the formation of similar black clouds around the world. Many attempts have been carried out to utilize the rice husk for the production of building units. This method is concerned with the use of the husk, in their natural state, as aggregate mixed with ordinary Portland cement to produce various constructional units [1]. However, such products are a very limited use. In the second method, the ash residue of the husk is mixed with Portland cement and lime and pressed bricks which are then treated with special materials develop strength.

The constituents of rice husks are both organic and inorganic compounds Analysis reported in the literature showed that, the organic matter present in the husks are generally, lygnin and cutin, carbohydrates and nitrogen compounds are also reported such as lipids, organic acids and traces of vitamins. The inorganic constituents have generally been determined in the ash which comprise about 13-29% of the husk [2]. The predominant compound of ash is silica. Other elements are also present such as Na, K, Ca, Mg, Fe, Al, Mn, P and Cu. The silica values present about 94-96% by weight of the ash. In general, the ash may well be considered as impure silica. The nature of white rice husk as silica is still under investigation ]3]. The results showed that nuclei disordered cristabalite is present and its growth is governed by two factors, namely nucleation and temperature. The nucleation process manifests itself in the low temperature range 800-900C, while growth is more pronounced in the temperature range 1000-1100C. Due to light silica content and the porous texture of the ash produced by the incineration of rice husk, it is recommended, the silica in rice husk ash is present in an amorphous state, which increases its reactivity during the firing process. Light weight clay bricks and blocks can be produced by adding any of the following combustible material, which are the by product or waste products of different industries: foamed polystyrene, perlite, saw dust shavings, paper making sludge, coal dust and chopped straw [4-5]. The use of these combustible materials as pore forming agents in the production of light weight, thermally insulating bricks has two additional advantages: firstly, energy consumption in the early part of the firing process is reduced, due to the large amount of energy generated by the combustion of the pore forming, resulting in considerable savings in fuel. At the same time large quantities of waste products can be consumed usefully instead of having to dispose of them as landfill. The objective of the present work is to study the nature of rice straw ash formed at different firing temperature from 400 up to 1000C. Also the effect of rice straw and its ash on physico-mechanical properties of clay brick samples at different clays.

Experimental Work 10 kg of rice straw was cut by scissor to obtain small pieces and ground in a ball mill then sieved through 1mm. The thermal behavior as well as the ash content of the rice straw was studied by diffraction thermal analyses and thermal gravimetry. Chemical analysis of the rice straw ash is as follows: Si02 = 77.80%, A1203 = 9.79%, Fe203 = 0.76%, Ti02 = 0.65%, CaO = 6.58%, MgO = 1.86%, K20 = 0.64, Na2O = 1.18, P205 = 0.65. Rice straw was heated in a muffle furnace in an atmosphere of air at a constant rate of 20C/min up to required temperature. Heating was initiated at 400, 500, 600, 700, 800, 900 up to 1000 C for 2 hrs, then cooled slowly in the furnace. The nature of the silica in the rice straw ash was studied by X-ray diffraction analysis. The rice straw was divided into two parts. One part was grinded to pass particles of a diameter less than 1 mm. The second parts was fired at 400C firing temperature for 2 hrs soaking time and screen by sieving 1 mm to obtain ash which contains carbon content 17%. Each mixture was prepared from clay [Wadi El-Hai or Aswan] and reducing agent such as rice straw and its ash. The prepared batches were then mixed together with different ratio for one hour in ball mill to obtain batches of complete homogeneity as shown in Table (1).

Table 1 Mix composition of the prepared mixes, wt.

Mix o. 1 2 3 4 5 6 7 8 9 1 0 1 1 1 2 1 3 1 4 1 5 1 6

Aswan Clay 1 0 0 9 9 9 8 9 7 9 6 9 5 9 9 9 8 9 7 9 6 9 5

Wadi El-Hai Clay 1 0 0 9 9 9 8 9 7 9 6 9

Rice Straw 1 2 3 4 1 2 3 4 5 -

A sh 1 2 3 4 5 1 2 3 4 5

Ash* from firing rice straw at 400C, for 2 hrs soaking time.

Oxides Si02 A1203 Fe203 Ti02 CaO MgO Na20 K0

Table (2) Chemical analysis of the raw materials, Wadi ElAswan Clay Rice Straw Hai Cl 54. 59. 10. 69 0. 00 0. 00 0. 00 0. 00 0. 00 0.

Rice Straw Ash at 4000C 65. 57 7. 10 0. 51 0. 85 4. 70 2. 42 1.

95 52 23. 12. 17 30 7. 7. 76 27 1. 1. 85 55 2 0. 3. MnO P20 33 06 5 0. 2. L.O.I 84 29 T.I.O 0. Total Impurity 1. Oxides. L.O.I.- loss of ignition, T.I.O.-

The mineralogical composition of the Aswan and Wadi El-Hai clays were studied by x-ray diffactometer and DTA, TG techniques, finally grain size distribution are seen in Table 3.

Table 3. Grain size distribution of Aswan and Wadi El-Hai Clays Particle size pm 1000-500 500-250 250-125 125-63 63-20 20-8 8-2 <2 Aswan, % Wadi EI-Hai,

pressure of 50 kg/cm2 using about 5% water as binder. The batches were coulded into one inch cylinder samples. The physico-mechanical properties of the dried and fired briquettes were measured as well as phase composition of the fired briquettes were determined.

0. 70 8. 3 00 1 11. 0 30 8 14. 24 00 .2 14. pressing and a 12 from the dry mix by semi-dry The briquette samples were prepared

Results and Discussion

The Nature of Rice Straw Ash The nature of rice straw ash silica, obtained from burning rice straw, is still a matter of study. The ash is slightly impure silica. The silicon occurs in the straw as a hydrated amorphous form of silica, whether this is opaline or a silica gel is a question still not completely answered, although the evidence for opaline form is rather strong [6]. There is fairly general agreement that the silica is predominantly in inorganic linkages. The formation of tridymite at the expense of cristobalite in high temperature fired ash is dependent on the intensity and duration of combustion [7]. To show the effect of firing temperature on the crystallinity of rice straw ash silica, samples were fired from 400 C to 1000C for 2hrs soaking time and then cooled slowly in the muffel furnace. Figure (1) illustrates the diffraction patterns of rice straw ash fired at 400, 500, 600, 700, 800, 900, and 1000 C for 2 hrs. It is seen that the silica of rice straw ash is amorphous at lower temperature beside trace of calcite mineral at firing temperature 400, 500 and 600C, whereas at 700C firing temperature gave complete dissociation of calcite. At 800C silica gave small crystalline state, on increasing the firing temperature to 900C, the crystallinity increased and the crystalline phase was identified as cristobalite with tridymite. Moreover the cristobalite increased with increasing firing temperature up to 1000C. The stability range of the three predominant crystalline modifications of silica are considered by Fenner [8] to be as follows Quartz 870C Tridymite 14700 C Cristobalite

According to the view suggested by Florke [9] and supported by other authors [1013] the conversion from quartz to cristobalite does not proceed through the intermediate form tridymite. The presence of impurities favours the formation of tridymite. In an earlier work [14], the appearance of cristobalite was reported to occur at

higher temperature (900C) than in the present study. This result may be attributed to the firing condition and the presence of lime (6.58%) can catalyse the conversion of quartz to cristobalite, whilst iron (0.76%) favour the formation of tridymite [15]. The rate of conversion of one form to another is also increased by increasing the fineness of the ash. Organosilicon compounds are assimilated into the rice plant and form part of the plant tissure. Silicon atoms are first transformed by the combustion process into amorphous silica. Silicon atoms are first transformed by the combustion process into amorphous silica. Silicon atoms in amorphous silica are bonded to oxygen atoms in two ways; either to two oxygen atoms, thereby forming a siloane group (Si-O) or to a hydroxyl group, thereby forming a silanol group (Si-O-H). Both groups exist at temperature up to 700C but in varying properties depending on the firing temperature. The siloane groups unit by the corners to produce low form cristobalite. Any impurities that are present enter the crystal lattice, thereby forming a kind of solid solution. Figure (2) shows the DTA and TG curves of rice straw, initial endothermic peak at about 100C followed small endothermic at 166C corresponding to the loss of mechanical held water. This is accompanied by loss in weight represented by the TG curve of about 9.25% of the initial weight sample. The thermal decomposition of the rice straw is characterized by an exothermic peak at 283C. This peak is probably characteristics of cellulose and hemicellulose which are the main major constituents of organic part of the rice straw. Corresponding to these reactions, an abrupt loss in weight of about 53.78%. At 564

630 C a small endothermic peak may be due to the low high quartz transformation. At 930 C the presence of an exothermic peak indicates complete decomposition of Si02 in the rice straw 16.97% is the weight loss of the remaining part of the rice straw was gradual increased and completed at about 1000C. Characterization of Clays in Investigated Work The grain size distribution of the clay affects the linear shrinkage, the drying behaviour, apparent porosity, bulk density and also crushing strength of the fired bricks [16]. Winkler [17-18] has described the possibility of producing different types of bricks based on the grain size distribution of the investigated clays. The percentages of the fractions <2 m 2 to 20 m and > 20 m were determined and plotted on a triangle diagramme Figure (3). It contains fo ur areas ea ch one is suitable for one type of bricks 1-solid bricks; 2- perforated bodies; 3- roof tiles and hollow bricks and 4thin-walled, large ceiling and hollow bricks. From the results of grain size distribution, it was evident that clay Wadi El-Hai was suitable for perforated bodies while Aswan clay can be used for thin walled, large celling and hollow bricks. Figure (4) show the x-ray diffraction pattern of Wadi El-Hai clay sample which contains quartz and feldspare as major mineral, in addition to montmorillonite, goethite, halite as minor mineral and traces of calcite as well as gypsum. On other hand Aswan clay contains kaolinite clay mineral is the predominant one, in addition to quartz, magnetite and feldspar. Figures (5) show DTA and TG analyses pattern of Wadi El Hai, and Aswan clays. Ramachanch [19] indicated the characterstic endothermic and exothermic effects of different clay minerals. The thermograms of Wadi El-Hai Clay show a large endothermic peak existing at temperature 118C and 150C. This large low temperature endothermic

effect is characteristics to the three layer clay minerals namely montmerillonite. It is mainly due

to the loss of sorbed water, largely that existing in the inter layer spaces of montmorillonite structure. The size shape and temperature of such peak depend on the type of exchangeable cation held with water in the interlayer species [20,21]. The dehydration of interlayer water of montmorillonite is accompanied with a total loss in weight of about 4.95% up to 160C. A weak endothermic is observed at about 277C, which is probably due to the dehydroxylation of small amount of goethite and or gibbsite [22]. The dehydration is accompanied with a loss in weight of about 0.7%. At 507-574 C there is large and broad enothermic peak doublet due to the dehydroxylation of montmorillonite clay mineral which is accompanied with about 4.1% loss in weight. This eak includes part l y t he end ot herm i c effect occuring at 574 due t o t he low high quartz transformation. By rising the temperature up to 890C end ot h erm i c p e ak i s o bse rv ed, and it is meanly due to the dissociation of calcium carbonate mineral. The loss in weight at this temperature is about 1.3%. Finally an endothermic/ exothermic (S) shaped reaction at 890-930C due to a structural reorganization and formation of new crystalline phases e.g. silica rich, - A12O3 having the spinel structure [20,21]. The DTA and TG of Aswan clay are shown in figure (5). As it is shown a broad endothermic at 106C which is meanly due to the dehydration of the adsorped and interlayer water of the Kaolinite that accompanied with about 0.9% loss in weight. At 338C there is exothermic peak due to the presence of magnetite mineral, with about 1.13% loss in weight by dehydration. Followed by a large endothermic peak at 541C due to the dehydroxylation of kaolinite mineral which is accompanied with about 6.2% loss in weight. Also, exothermic peak is detected at about 952C due to recrystallization of -A12O3 in the spinel structure, with 1.15% loss of weight. Effect of straw and its ash on Clay Bricks The strength of material is due to the cohesion of particles of which it is composed and the resistance to pressure of the individual grains. The crushing strength of material is expressed in terms of its resistance to compression. It has a great importance for the utilization of most ceramic materials, especially those used for constructional purposes. As the ceramic material acquires a high crushing strength, it must comprise a good binding agent, the grains must interlock sufficiently and the individual grains must be of considerable density, or lower porosity. The crushing strength is therefore closely related to the texture of material. Tables (4) and (5) show the physico-mechanical properties of briquettes such as dry and fired crushing strength, water absorption, apparent porosity, bulk density as well as loss in weight and linear shrinkage made from wadi E1-Hai and Aswan clays with variable amounts of rice straw as well as its ash fired at 900 C for 2 hours soaking time. From the results, it was revealed that the dried strength increases with the increases of rice straw and decreases with ashes in bricks Wadi El-Hai and Aswan clays as the fibrous structure of rice straw has a favourable influence on the stability of green bodies during drying and counteracts cracking. At the same time the compressibility of rice straw is low; so that a relatively high shaping pressure can be applied which increases the stability of the green body [23]. But ash, as a silica, (non plastic material) decreases the binding clay so that the green crushing strength was decreased. The crushing strength of fired Wadi El Hai clay brick samples is lower than that of Aswan brick samples. This is due to the large proportion of fluxes in Wadi El-Hai that equals

to 17% which affects the strength. The bond produced by the fluxes will be soft and mobile therefore, unable to import the necessary rigidity of the fired bricks. Another explanation is the difference in composition and mineralogical constitution that occur when clays are fired, accompanied by corresponding changes in physical properties. From the results of the above tables, it is found that the bulk density and linear firing shrinkage were decreased by increasing addition of straw and ash to clay briquettes at the same time apparent porosity and water absorption as well as loss on weight are increased. This is due to the great loss of rice straw and ash. It gives about 80% loss on ignition of rice straw and 17% in the case of ash. Therefore, the loss in clay weight relate to the loss in weight rice straw or rice ash increases with the increase of rice straw or ash content. In another words, the loss in weight upon firing is proportional to the amount of the clay refacture also the amount rice straw or ash. Briquettes with high amounts of rice straw or as give high percentage of apparent porosity, water absorption due to their contents of components which volatilise, evaporate or decompose with gas liberation at particular temperature. The rice straw or ash decomposes with the evolution of gases leaving nearly 17-80% of its volume as voids which increases the apparent porosity and water absorption. The water absorption and apparent porosity are inversely proportional to the crushing strength and bulk density. The results illustrated that physical properties of clay: Ash mixture were higher than clay straw mixtures due to loss in weight content of ash was lower than straw and the activity of amorphous silica in the ash which increases the reactivity during firing process. The ash plays two roles as a pore forming agent and activation role but straw gives another roles as a pore of forming material as well as retarding effect. This result is agreed with the x-ray diffraction pattern of (Wadi ElHai and Aswan Clays) clays with straw and/or Ash bricks. The mix composition contains (10095) % clay and (0-5)% straw or Ash fired at 900C for 2 hours soaking time as seen in Figure (6). Albite, hematite and quartz are main minerals of fired pure Wadi el-Hai clay. The same minerals were appeared by mixture composition contains 95% clay and 5% Ash but different in intensity of peaks albite and quartz due to amorphous silica in ash which increase the reactivity indicated by intensity of the above minerals. In the case of contains 95% clay with 5% Straw, beside main minerals, calcite was appeared at the same condition, in spite of the calcite disappeared at 750C fired clay so that, straw as retarding effect. Also, the clay was indicated by hematite the same direction when firing clay at 900C Figure (7). Aswan The main minerals were albite, and quartz. The mixture contains 95% Aswan with 5% straw was indicated the presence of Kaolinite mineral which approved that straw has retarding effect in clay bricks during firing process.

CONCLUSIONS
From the above results obtained it was concluded that: I . Rice straw and its ash can be used as a pore forming agent in clay bricks at different clays. 2. Rice straw has higher poring effect and usage in insulating products than rice ash.

3. Straw can be used in clay bricks to prevent burning in the fields which effects on the quality of air. 4. Straw as retarder but Ash as accelerator during firing.

REFERECES
1. Chittenden, A.E. and Flams, I.J. "The use of rice hulls as aggregate in lightweight concrete" Trop. Prod. Inst., Minstry of Overseas Development, London, (1960).

2. Gobel, R.L. and Burke, J.O. "Progress in Ceramic Science" VIII, Pergamon Press (1963). 3. Ibrahim, D.M. and Helmy, M. "Crystalline growth of rice husk ash silica "Thermochim. Acta, 45, P. 79 (1981). 4. Hauck, D. and Jung, E. "Improvement of the Coefficient of thermal conductivity of Light Weight Clay Bricks and Blocks" In: ZI Annual for the Brick and Tile, Structural Ceramic and Clay Pipe Industries (Ed. C. Kokot), Wiesbaden, P. 108 (1991). 5. Junge, K. and Spitzer, M. "Foamed clay Bricks insulation Material" In: ZI Annual for the Brick and Tile, Structural Ceramic and Clay Pipe Industries (Ed. C. Kokot), Wiesbaden, P.96 (1997). 6. Lanning, F.C., J. Agric. Food Chem., 11, P. 435 (1963). 7. Houston, D.F. "Rice Chemistry and Technology" American Association of Cereal Chemists, (1972). 8. Fenner C.N., Am. J. Sci., V. 4, P. 331 (1913). 9. Florke, O.W. Ber, Dtsch. Keram. Ges., V. 32, P. 359 (1955). 10. Coquerelle, M. Silic. Ind., V. 26, P. 505 (1961). 11. Dekeyser, W. and Cypres, R. Silic. Ind., V. 26, P. 237 (1961). 12. Wahl, F.M., Grim, R.E. and Graf, R.B. Am. Mineral., V. 46, P.196, (1961). 13. Eitel, W. Am. Ceram. Soc. Bull., V. 36, P. 142, (1957). 14. Ibrahim, D.M.; El-Helmaly, S.A. and Abdel-Kerim, F.M., Thermochim. Acta, V. 37, P. 307 (1980). 15. Ryan, W. "Properties of Ceramic raw Materials" 2nd Edition (1978).

16. Balint, P., Und Mattyasovsky, T. "Anwendung des Winkler Schen Dreieck Diagramms Zur Qualitatsbeurteilung Von Tonen Und Massen. Tonind-Ztg. V. 102, P. 588, (1978).17. Winkler, H.G.F., Ber. Dt. Keram. Ges. V. 11, P. 337, (1954).

18. Winkler, H.G.F., Ziegel-Ind. V. 6, P. 281, (1953). 19. Ramachandran, V.L. " Application of differential thermal Analysis in Cement Chemistry" Chemical Publishing Co. Inc., New York (1969). 20. Grim, R.E. and Bradley, W.F. "Investigation of Effect of Heat on Clay Mineral, Illite and Mentmorillonite" J.Am. Ceram. Soc., V. 23, P. 242, (1940). 21. Todor, D.N. "Thermal Analysis of Minerals" Abacus Press. Abacus House, England, (1976). 22. Basta, E.Z., Philip, G. and Halaka, S.G. "Mineralogical Studies on the Clay Fraction of Some Soil Sediments from El-Beheira Governorate, North and South Nubariya Canal". Egypt. J. Soil. Sci., V. 22, 111, (1982). 23. Junge, K. "Porous Light Weight Clay Bricks and Blocks" A step Towards a better Environment, ZI-Brick and Tile Industry International, V. 1, P.35 (1994).

Figure 1. X-ray diffraction pattern of rice straw ash fired at 400, 500. 600, 700, 800, 900 and 1000C for 2 hours soaking time.

Figure 2: DTA and TG of rice straw

1818

Figure 5: DTA and TG of Wadi El-Hai and Aswan Clays.

Figure 6: X-ray diffraction pattern of Wadi EI-Hai Clay bricks without and/with straw or ash fired at 900C for 2 hours soaking time.

Figure 7: X-ray diffraction pattern of Aswan clay bricks without and/ With straw or ash fired at 900C for 2 hours soaking time.