Chapter 1

INTRODUCTION
1.1 General : Concrete is a widely used construction material around the world, and its properties have been undergoing changes through technological advancement. Numerous types of concrete have been developed to enhance the different properties of concrete. So far, this development can be divided into four stages. The earliest is the traditional normal strength concrete which is composed of only four constituent materials, which are cement, water, fine and coarse aggregates. With a fast population growth and a higher demand for housing and infrastructure, accompanied by recent developments in civil engineering, such as high-rise buildings and long-span bridges, higher compressive strength concrete was the need of time. At the beginning, reducing the water-cement ratio was the easiest way to achieve the high compressive strength. Thereafter, the fifth ingredient, a water reducing agent or super plasticizer, was indispensable. However, sometimes the compressive strength was not as important as some other properties, such as low permeability, durability and workability. Thus, high performance concrete was proposed and widely studied at the end of the last century. Currently, high-performance concrete is used in massive volumes due to its technical and economic advantages. Such materials are characterized by improved mechanical and durability properties resulting from the use of chemical and mineral admixtures as well as specialized production processes. HPC is used in massive volumes due to its technical and economical advantages. Such materials, so called the 21st century concrete, are distinguished by enhanced mechanical and durability properties due to use of chemical and mineral admixtures as well as specialized production processes. In the literature, different types of mineral admixtures in forms of binary, ternary or quaternary blended mortars have been used. Pozzolanic additives are the materials or admixtures that can improve concrete properties such as concrete strength, durability and impermeability. They are used either as partial substitutes of Portland cement or as an addition . The main component of pozzolanic additives is usually active SiO2 in the amorphous phase. Pozzolanic reaction is a simple acid-based reaction between calcium hydroxide (Ca(OH)2) and silicium acid (H4SiO4) . Mechanism of pozzolanic reaction between microsilica and calcium hydroxide in water solution has been investigated particulary by Grutzeck. According to his study, during the first hour of getting in contact with water, gel is formed on the surface of microsilica particles that is rich in silicium and poor in calcium. In presence of water microsilica particles form agglomerates. After a while, the gel on the surface of microsilica particles dissolved and microsilica agglomerates started reacting with calcium hydroxide thus forming calcium hydrosilicates. In the presence of cement the above mentioned mechanism becomes more complicated. In this case, microsilica absorbs lime containing water, forms silicium-rich gel and consumes most of the available water. Gel particles clump together and fill the voids between the cement particles and agglomerates in bigger masses. Within the first 15 minutes up to one hour, calcium hydrosilicate particles that do not contain water are enclosed by microsilica gel. In case of ordinary concrete, approximately 3 hours later discrete calcium hydroxide crystals are formed in pores, however when pozzolanic admixtures are used such weak crystals are not formed because excess lime reacts with the surface of silicium-rich gel thus forming calcium hydrosilicates, which is a stronger binder phase than calcium hydroxide. The reactivity of pozzolans is closely linked to the silicate and alumosilicate content in the amorphous phase as well as to the fineness of the

material (surface area available for reaction). The influence of superplasticizer on the performance of concrete is reviewed in this paper as well. Previously, the influence of superplasticizer was studied by many authors . At present, superplasticizers play an important role in concrete mix composition (especially in case of high and ultra-high strength concrete), where reduction of water amount is necessary to obtain higher compressive strength. When dry particles are mixed with small amount of water, the electric charges upon the solid particles tend to cause their aggregation and prevent free distribution of the water between solid particles, thus preventing ultimately an optimal repartition of the hydrates formed between the particles. Originally the term pozzolan was associated with naturally formed volcanic ashes and calcined earths, which react with lime at ambient temperatures in the presence of water. The admixtures in the form of siliceous aluminous materials which, in finely divided form and in the presence of water, will react chemically with calcium hydroxide Ca(OH)2 to form compounds that possess cementitious properties. This generalized definition covers waste products such as fly ash (FA), rice husk ash and silica fume (SF). Portland cement, if fully hydrated, produces calcium hydrate (CH) which does not make a significant contribution to strength and can be harmful to concrete durability. The complete elimination (or) partial reduction of (CH) with the reaction of pozzolan results in stronger and durable concrete. Because of these technical advantages over the last few decades, there has been increasing and widespread utilization of FA, SF and natural zeolite in concrete. The volume of industrial by products with pozzolanic properties, produced world wide exceeds their current utilization and it is widely believed that their utilization will increase with increasing realization of the environmental benefits associated with such use. This will immensely help in the protection of environment and leads to sustainable construction. There are therefore competing reasons, in the long term, to extend the practice of partially replacing cement with waste by products and processed materials possessing pozzolanic properties. Natural pozzolans in the form of calcined earths blended with lime have been used to produce cementitious materials for thousands of years. The utilization of calcined clay in the form of Metakaolin (MK) as a pozzolanic addition for mortar and concrete has received considerable interest in recent years. Much of this interest has been focused on removal of the CH, which is produced by the hydration of cement and which is associated with poor durability. Reduction of CH makes the concrete and mortars more resistive to sulphate attack and reduces the effect of alkali - silica reaction. This provides enhanced strength which is derived from the additional cementitious phases generated by the reaction of CH with MK. MK is processed from high - purity kaolin clay by calcination at moderate temperature (6500C-8000C). The silica and alumina in the MK reacts effectively with the CH. The principal reasons for the use of clay-based pozzolans in mortar and concrete have been due to availability of materials and durability enhancement. In addition, it depends on the calcining temperature and clay type. It is also possible to obtain enhancement in strength, particularly during the strength of curing. The very early strength enhancement is due to a combination of the filler effect and acceleration of cement hydration. Consequently, these effects are improved by the pozzolanic reaction between MK and the CH produced during the hydration of cement. Therefore MK is a very effective pozzolan and results in enhanced early strength with no detriment to the long-term strength. MK modifies the pore structure in cement paste, mortar and concrete and makes the mixes more resistive to the diffusion of harmful ions and penetration of water which lead to degradation of the matrix. Presently Metakaolin is more expensive than Portland cement, as is Silica Fume, even though moderately low temperatures are required for its processing and its overall production cost is significantly less than that of Portland cement.

Metakaolin differs from other supplementary cementitious materials (SCMs), like fly ash, silica fume, and slag, in that it is not a by-product of an industrial process; it is manufactured for a specific purpose under carefully controlled conditions. 1.2 Objective of study
This study is conducted to accomplish some predefined objectives. The objectives are: 1.To study the performance of concrete containing different percentages of metakaolin and to identify the optimum replacement percentage. 2.To compare the performance of metakaolin blended concrete by micro-silica powder with other cement replacement materials (CRMs).

1.3 Significance of the Study : Concrete has been used in the construction industry for centuries. Many modifications and developments have been made to improve the performance of concrete, especially in terms of strength and durability. The introduction of pozzolans as cement replacement materials in recent years seems to be successful. The use of pozzolan has proven to be an effective solution in enhancing the properties of concrete in terms of strength and durability. The current pozzolans in use are such as fly ash, silica fume and slag. Development and investigation of other sources of pozzolan such as kaolin will be able to provide more alternatives for the engineer to select the most suitable cement replacement material for different environments. Unlike other pozzolans, metakaolin is not a by-product which means its engineering values are well-controlled. Therefore, using metakaolin should promise some advantages compared to other cement replacement materials. In this case, it is needed to study the performance of concrete using metakaolin, silica fume and its blend. The performance of metakaolin-silica fume concrete will be compared to the cost of production of metakaolin and silica fume to determine whether it is worthy to be developed as a new cement replacement material. 1.4 Scope of Study : This study focuses on the strength performance of concrete with metakaolin, silica fume and its blend. Strength is the most important property of concrete since the first consideration in structural design is that the structural elements must be capable of carrying the imposed loads. Strength characteristic is also important because it is related to several other important properties which are more difficult to measure directly. With regard to this matter, the development of compression strength of metakaolin, silica fume and its blend concrete is studied. Cement replacements by 5%, 10%, 15%, 20% with metakaolin, silica fume and its blend are studied. Concrete tests are conducted on the concrete samples at the specific ages. All the strength tests are limited to the ages of 28 days. For the performance comparison study, the cement replacement materials used are silica fume and metakaolin. These two cement replacement materials are chosen as they are the most common replacement materials nowadays and will be good comparisons to metakaolin. The comparison is made on the compressive strength performance of metakaolin, silica fume concrete.

Chapter 2
LITERATURE REVIEW
2.1. General : Concrete is known to be a simple material in appearance but with a very complex internal nature. In contrast to its internal complexity, versatility, durability, and economy of concrete have made it the most frequently used construction material in the world. Concrete is a mixture of cement, water, and aggregates, with or without admixtures. The cement and water will form a paste that hardens as a result of a chemical reaction between the cement and water. The paste acts as glue, binding the aggregates (sand and gravel or crushed stone) into a solid rock-like mass. The quality of the paste and the aggregates dictate the engineering properties of this construction material. During hydration and hardening, concrete will develop certain physical and chemical properties, among others, mechanical strength, low permeability and chemical and volume stability. Concrete has relatively high compressive strength, but significantly lower tensile strength (about 10% of the compressive strength).Concrete is used to make pavements, building structures, foundations, roads, overpasses, parking structures, brick/block walls and bases for gates, fences and poles. Over six billion tons of concrete are made each year, amounting to the equivalent of one ton for every person on Earth 2.2. Review of literature of concrete containing pozzolanic materials such as silica fume and metakaolin : Many Researchers have studied the effect of replacement of Portland cement by Metakaolin and also on fibre addition on the mechanical and durability properties of ordinary Portland cement concrete. The literature being reviewed is given under three sections : Review of literature of concrete containing pozzolanic materials such as Metakaolin. Review of literature of OPCC, MKC & SFRC on exposure to elevated temperatures. Review of literature of OPCC on compressive strength, split tensile strength, flexural strength and modulus of elasticity when exposed to different thermal cycles. Yogendran et al. (1987) made an attempt to modify the properties of concrete with respect to its strength and other properties by using silica fume and chemical admixtures. They concluded that optimum replacement of cement by silica fume for high strength is found to be 15% for a water cementatious ratio of 0.34 at all age. Alhozaimy, A.M., et al (1995) carried out experimental investigations on the effects of adding low volume fractions (<0.3%) of calculated fibrillated polypropylene fibres in concrete on compressive flexural and impact strength with different binder compositions. They observed that polypropylene fibres have no significant effect on compressive (or) flexural strength, while flexural toughness and impact resistance showed increased values. They also observed that positive interactions were also detected between fibres and pozzolans. F.Curcio, B.A. De Angelis, and S.Pagaliolico (1998) in their investigation, super-plasticized mortars containing Metakaolin (MK) as 15% replacement of cement and with a water/binder ratio of 0.33 have been characterized with four commercially available MK samples have

been studied and compared to silica fume. Three out of four Metakaolin samples showed improvement in compressive strength at early ages, when compared to SF, but at 90 days and later the difference is reduced. The difference in the compressive strength between the specimens with micro fillers and the control decreases after 28 days, because of a smaller slow down of the hydration rate in the control. This can be related to the fineness of the micro-filler in the specimens with Metakaolin. At 90 and 180 days Metakaolin and silica fume specimens gave similar strengths. F.Curcio and B.A. De Angelis (1998) in their investigation, cement pastes containing Metakaolin have been studied with a co-axial cylinder rotational viscometer. They show a dilatent behavior that is strongly dependent on the water /binder ratio, on the level of cement replacement by Metakaolin and on the fineness of the latter. Dilatency is caused by angular and plate like shape of MK particles. They concluded that dilatency is governed by water to binder ratio , amount of metakaolin and its fineness. Finally, the dilatant properties can be explained by considering the plate like and angular shape of MK particles in comparison with SF. Handong yan, Wei Sun, Husiu chen (1999) in their investigation, the impact and fatigue performance of high-strength concrete (HSC), silica fume high-strength concrete (SIFUHSC), steel fibre high strength concrete (SFR HSC), and steel fibre silica fume highstrength concrete (SSF HSC) under the action of repeated dynamic loading were studied. The mechanisms by which silica fume and steel fibres, reduce the damage were investigated.The results indicate that, steel fibre effectively restrained the invitation and propagation of cracks during the failure. The presence of steel fibres in high strength concrete was effective in restoring the structure under fatigue and impact by delaying the damage process. Silica fume effectively improved the structure of the inter-face, eliminated the weakness of the interfacial zone, reduced the number and size of cracks, and enhanced the ability of steel fibres to resist cracking and restrain damage. As a result, the incorporation of steel fibres and silica fume can together increase greatly one performance of HSC subjected to impact and fatigues. The filler effect of silica fume can reduce the number and size of the original cracks in the interfacial zone and in the bulk of concrete and enhanced the interfacial effect. Steel fibres mainly strengthen, toughen and resist cracking in HSC. J.M. Kinuthia et al. (1999) An experimental investigation is made by the authors in studying the workability of concrete incorporating combinations of pulverized fuel ash (PFA) and Metakaolin (MK) as partial replacements for Portland cement (PC). The aim of the research work is to explore the potential of using PFA and MK as blends with PC in terms of the flow properties of the resulting concrete. Mixtures containing 0, 10, 20, 30 and 40% total replacement of cement with combinations of Metakaolin (0-15%) and PFA (0-40% for concretes with water-to-binders ratios of 0.4, 0.5 and 0.6 were prepared. Workability of the concrete was measured by the slump, compacting factor and vee-bee time tests. The following conclusions are made by the authors. i). The workability of PC-MK concrete is substantially reduced with an increase in MK content. The workability reduction caused by MK is attributed to its high chemical activity and high specific surface, resulting in increased intake and hence greater water requirement. The influence of MK on compaction and flow is reduced to the thixotropic nature of clay suspension and to a reduction of void space due to the improved dispersal of the MK particles.

ii). The workability of PC-PFA concrete without super plasticizer increases significantly with increase in PFA content. For PFA contents above 10% PFA workability falls. The reduction in workability is attributed to flocculation/coagulation at low PFA concentration and the increase in workability at high concentration is attributed to neutralization of positive charges on cement particles and their resultant dispersal. When super plasticizer is used as a dispersing agent, no fall in workability is observed. iii). Loss of workability due to the present of MK can be compensated for by the incorporation of PFA. The degree of restoration of workability, provided by PFA, is influenced significantly by the cement replacement level, the MK/PFA ratio and the W/b ratio-dispersed mixture is a critical MK/PFA ratio at which the loss in workability imparted by the MK is exactly compensated for by the gain in workability imparted by the PFA. Kinuthia J.M. et al (2000) The contribution by the authors in this paper forms a part of an ongoing investigation examining the potential of using Metakaolin, pulverized fuel ash (MKPFA) blended for cements in concrete. The investigation involves the examination of the effect of the blends on the strength development and factors affecting durability including chloride penetration, carbonation and water transport properties. The following conclusions were made by the authors: i) Although the early compressive strength of concrete is reduced by the incorporation of PFA as a partial replacement for cement, pozzolanic action develops in the medium term and up to 30% PFA may be used without detriment to the strength at 90 days. PFA is particularly effective in this respect at the moderately low water-to-binder ratios of 0.4 and 0.5. ii) ii) Up to 15% partial cement replacement by Metakaolin results in considerable enhancement in strength in both the short and the medium term. The strength enhancement is obtained for all the water to binder ratios used (0.4-0.6). iii) The contrasting roles played by PFA and Metakaolin in the strength development, particularly at the early stages, can be compared to produce effective blends for cement. At short curing times, only mixtures with low PC replacement levels and high MK/PFA ratios achieve strength in excess of the control. However, after 90 days curing, mixtures with high PC replacement levels and low MK/PFA ratios also achieve strengths in excess of the control. iv) The incorporation of small quantities of PFA, as partial cement replacement, results in an acceleration of PC hydration, which in turn gives rise to increased strength. M.Frias, M.I.Sanchez derojas, J.Cabrera (2000) In their experimental work, the influence of the pozzolanic activity of the Metakaolin(MK) on the hydration heat has been studied in comparison to the behaviors of other traditional pozzolanic materials such as flyash and silica fume. The results revealed that MK mortars produce a slight heating increase when compared to a 100% Portland cement mortar, due to the high pozzolanic activity of MK. With respect to the hydration heat, MK-blended mortar showed closer behaviors to silica fume than to fly ash. Moises Frais, Joseph Cabrera. (2000) the authors shows the results of an investigation focusing on the effect of Metakaolin (MK) on the micro-structure of MK-blended pastes. Pastes containing 0%, 10%, 15%, 20% and 25% of MK were prepared at a constant water/binder ratio of 0.55 and cured at 200c for hydration periods from 1 to 360 days. They investigated total capillary and gel porosity evolution with the curing period and also estimated the degree of hydration in the ordinary Portland cement and Metakaolin blended pastes. The values of the degree of hydration are calculated from the amount of Ca(OH)2

present in the paste and from the data of differential thermal analysis (DTA) thermogravimetry (TG). A good association between porosity and degree of hydration has been established. The total porosity decreases up to 28-56 days of curing time. They observed that, up to 28 to 56 days of curing the porosity is same for all the mixes. Beyond 56 days the porosity of all the Metakaolin mixes increasing when compared with OPC mix. Similar phenomenon is observed for capillary porosity. The best evidence of the influence of MK on the refineness of the pore structure was detected in pores with radius smaller than 100 0A. Between 7-90 days, the gel porosity of MK mixes increase, while the OPC mix remains practically constant. The results show the necessity of obtaining important improvement in the porosity reducing the average pore diameter and gel porosity. Measured lime contents show the total consumption of MK (10% to 15%) at 90 days of hydration time. A good statistical relationship has been found between the degree of hydration and the porosity. Brooks et.al. (2000) after studying the effect of silica fume, Metakaolin, fly ash and ground granulated blast furnace slag on setting times of high strength concrete, they concluded that there was increase in the retarding effect up to 10% replacement of cement by Metakaolin and as the percentage replacement is increased, the retarding effect is reduced. Shannag (2000) designed and studied very high compressive strength of 69 to 110 MPa along with incorporation of locally available natural pozzolana and silica fume. He concluded that 15% replacement of cement with silica fume along with 15% natural pozzolan gave relatively higher strength than without natural pozzolan. A.Shvarzman, K.Kovler, G.S.Grader G.E.Shter (2001) The effect of heat treatment parameters on the dehydroxylation/amorphization process of the kaolinite based materials such as natural and artificial kaolin clays with different amounts of amorphous phase (Metakaolin) was investigated by the above authors. The process of dehydroxylation/amorphization of kaolinite were characterized by DTA/TGA with massspectrometry and x-ray power diffraction. The influence of the heat treatment, temperature and content of the amorphization phase on pozzolanic activity was studied. The results obtained are important for an optimization of the process of the Metakaolin large scale production and its use as a pozzolanic admixture. At the calcination temperature below 4500C kaolin clays show relatively low level of the dehydroxylation degree, less than 0.18. In the range from 4500C to 5700C, the degree of dehydroxylation sharply increased to 0.95, and finally at the temperature range between 570 and 700OC the kaolinite was fully dehydroxylated since the only moderate change of degree of dehydroxylation was observed in this range (from 0.95 to 1.0). It was found that the dehydroxylation is accompanied with the kaolinite amorphization which affects the activity of additives. A method of qualitative evaluation of amorphous phase content (APC) in treated materials was developed and applied for characterization of the investigated samples. Therefore, even with the partial dehydroxylation of kaolinite accompanied with approximately 55% ammorphization, the material may be considered as very active pozzolanic admixture (according to ASTM 618). This finding seems to be extremely important for reduced energy demand during the production of Metakaolin. K.A.Gruber, Terry Ramlochan, AndreaBoddy, R.D.Hooton, M.D.A.Thomas (2001) The investigations carried out by the above authors revealed that the temperature rise in MK-PC mortars (above 5% MK and up to at least 15% MK) is greater than that in equivalent PC mortar (other than at very low MK levels). The increase in heat evolution during initial hours

of hydration was resulted from the combined effect of accelerated Portland cement hydration and pozzolanic reaction. The temperature rise in PFA-PC mortars is less than that in equivalent PC mortars, this is attributed to the dilution of the PC by the PFA coupled with the latters negligible pozzolanic activity during the reaction, both the rate of heat evolution and the total heat evolved. Xia Oquian and Zongjinli (2001) studied the stressstrain relationships of concrete containing 0% to 15% of Metakaolin at an incremental rate of 5%. They concluded that incorporation of Metakaolin up to 15% has increased the tensile and compressive strength and also peak strain is increased at increasing rate of Metakaolin up to 15%. Incorporation of Metakaolin has slightly increased the compressive elasticity modulus. Poon et al (2001) investigated the rate of pozzolanic reaction of Meta kaolin in high performance cement mortars. They studied the hydration progress of Metakaolin in terms of its compressive strength, porosity and pore size distribution. They concluded that the higher pozzolanic reactivity results in a higher rate on strength development and its pore structure refinement for the cement pastes at earlier ages. W.Aquino, D.A.Lange, J.Olek (2001) Attempt is made by the authors to study the influence of SF (Silica Fume) and HRM (High Reactivity Metakaolin) on the chemistry of ASR (Alkali Silica reaction) products. They observed that silica fume and high reactivity Metakaolin reduce expansion due to ASR. Also they observed that the calcium content of ASR products is increasing with time in all the samples without mineral admixtures and a lower level of calcium was detected in samples containing mineral admixtures. In addition, X-26 ray microanalysis showed that calcium content increases with time in ASR products. It was found that as ASR reaction proceeds, the calcium to silica reaction of the reaction products increases following a linear trend. From the results it is suggested that calcium in gel products may be responsible for expansion. D.M.Roy, P.Arjunan, M.R.Silsbee (2001) In their investigation, effects of aggressive chemical environments were evaluated on the mortars prepared with low-calcium fly ash/Metakaolin (MK)/silica fume (SF)/ordinary Portland cement (OPC) and at various replacement levels. The natural adverse chemical environmental conditions were simulated using sulphuric acid, hydrochloric acid, nitric acid, acetic acid, phosphoric acid and a mixture of sodium and magnesium sulphates. They proposed resistance of the above mortars against the chemical environment was in concurrence with compressive strength measurements. The results show some interesting trends with respect to acid resistance. Substitution of SF, MK, or FA under certain conditions has been shown to increase the chemical resistance of such mortars over those with plain Portland cement. The mortar made from all three series showed poor resistance to higher acid concentrations of 5% sulphuric acid, 5% acetic acid, and 5% phosphoric acid environments. Chemical resistance increased in the order of SF to MK to FA series and decreased as the replacement level is increased from 0-10% weight replacement level to 15-30% weight level. They observed that compressive strength is increasing in the order of fly ash to Silica fume to Metakaolin. Megat Johari M.A. et al. (2001) In their investigation, the effect of Metakaolin (MK) on the creep and shrinkage of concrete mixes containing 0%, 5%, 10% and 15% MK has been studied. The outcomes showed that autogenous shrinkage measured from the time of initial set at the early age of the concrete was decreased with the inclusion of MK, but the long term autogenous shrinkage measured for the age of 24 hrs was increased at 5% replacement

level, the effect of Metakaolin has increased the total autogenous shrinkage considering from the time of initial set. While at replacement levels of 10% and 15% it reduced the total autogenous shrinkage. The total shrinkage (autogenous plus drying shrinkage) measured from 24 hrs was reduced by the use of MK, while drying shrinkage was significantly less for the MK concrete than for the control concrete. At higher Metakaolin replacement levels, the total creep, basic creep as well as drying creep was significantly reduced. On overall, compared with the control concrete, the greater part of the total shrinkage of the MK concrete is constituted by autogenous shrinkage, the smaller part being drying shrinkage. Particularly at higher Metakaolin replacement levels, drying creep, basic creep and total creep were greatly reduced. Jamal M.Khatib, Roger M.Clay (2003)74 in their investigation, the water absorption (WA) by total immersion and by capillary rise of concrete containing Metakaolin (MK) is studied. Cement was partially replaced with up to 20% MK. The results show that the presence of Metakaolin is greatly beneficial in reducing the water absorption by capillary action. There is a systematic reduction in water absorption by capillary action with the increase in Metakaolin content in concrete. Between 14 and 28 days curing, there is slight increase in absorption by total immersion and by capillary rise for all MK concretes. The partial replacement of cement with MK reduces the water penetration in to concrete by capillary action. The water absorption of concrete by total immersion, however is slightly increased in concrete containing Metakaolin. WA decreases with duration of curing for all MK concretes up to 14 days. Between 14 and 28 days of curing, there is a slight increase in water absorption. After 28 days of curing there is little change in WA. An increase in the total pore volume leads to an increase in water absorption. Sabir, B.B. et al (2002) The authors reports the influence of the composition of Portland cement, pulverized fuel ash and Metakaolin (PC-PFA-MK) binders on sorptivity and strength development of Portland Cement Pulverised Fuel Ash - Metakaolin concrete cured both in water and in air and on carbonation depth, and relates this to measured changes in absorptivity of the concrete. Concrete mixtures covering four different total cement replacement levels (10%, 20%, 30% and 40%) for PC-PFA-MK concrete with various MK/PFA proportions, water and air cured for upto 18 months were investigated. The change in compressive strength and absorptivity with age at all cement replacement levels under both water and air curing are compared with those of the control Portland cement concrete. The results presented in this paper from part of an investigation in to the optimization of a ternary blended cementitious system based on ordinary Portland cement, Pulverised Fuel Ash and Metakaolin for the development of HPC. Increasing replacement of PC with PFA in PC-PFA air (CO2 enriched) cured concrete increases carbonation depth where as systematically replacing the PFA with MK in PC-PFA-MK concrete reduces carbonation depth. Jain-Tong Ding and Zongjinli (2002) investigated the properties of concrete by incorporating 0% to 15% cement replacement by Metakaolin (or) silica fume. They concluded that by incorporation of Metakaolin and silica fume, they can reduce the free drying shrinkage and restrained shrinkage cracking width. Also they can reduce the chloride diffusion rate significantly. Luccourard et al. (2003) studied the durability of mortars containing Metakaolin. The studies on transport and chemical behaviors by means of chloride diffusion tests and sulfate immersion were carried out. They concluded that 10% to 15% replacement of cement by Metakaolin lead to low decrease of workability and best mechanical performance and inhibition effect on chloride diffusion and sulfate attack for 20% Metakaolin.

T.Ramlochan, et al. (2003) the expansive behaviors of heat cured mortars containing pozzolans and slag was investigated by the authors. In almost all the mortars, the addition of any amount of pozzolans and slag to the mixture usually reduced the onset of expansion, the rate of expansion, and long-term expansion. However, the efficiency of a particular pozzolan (or) slag in controlling expansion may depend on its Al2O3 content. Metakaolin, which contains a higher amount of reactive Al2O3, was the most effective at controlling expansion at relatively low cement replacement levels. Slag and fly ash which are also sources of Al 2O3 were also effective at suppressing expansion at higher replacement levels. Silica fume was less effective at controlling expansion at conventional replacement levels, and even at higher replacement levels expansion may be delayed. Zongjin Li, Zhu Ding (2003) in their investigation, the physical and mechanical properties of Portland cement (PC) containing Metakaolin (MK) or combination of MK and slag and the compatibility between such materials and super-plasticizers were studied. The following conclusions are made by the authors: MK is a new active mineral admixture used in cement concrete products. It has a positive effect on the mechanical properties of cement. However, MK blended cement has a poorer fluidity compared to Portland cement under the condition which used the same amount of super plasticizer. By the addition of ultra fine slag this can be improved. By incorporating 10% MK and 20% (or) 30% ultra-fine slag jointly into PC, not only the fluidity of blended cements was improved, but above the 28-day compressive strength of the cements was enhanced. Metakaolin is a high active pozzolanic mineral admixture. The formula can prompt the hydration of PC, shorten the setting time of cement, increase the water requirement and increase the fluidity losing of the fresh paste. However, slag can delay the reaction of cement hydration and prolong the setting time of cement paste. Both MK and slag can react with CH released by cement clinker hydration to produce secondary C-S-H gel inside the cement paste matrix. Therefore the macroscopic property of cement was improved. XRD analysis indicates that more Calcium Hydroxide was consumed after adding both mineral admixtures. Jamal Khatib and Roger (2003) investigated the water absorption by total immersion and by capillary rise of concrete containing Metakaolin up to 20% replacement level. They concluded that water absorption of curing for all Metakaolin concretes up to 14 days and between 14 and 28 days of curing there is a small variation in absorption. E.Badogiannis, V.G.Papadakis, E.Chaniotakis, S.Tsivilis (2004) in their investigation, the effect of Metakaolin on concrete, kaolin was thermally treated at defined conditions, and the produced Metakaolin was superfine ground. For comparison, a commercial MK of high purity was used and the strength development of Metakaolin concrete was evaluated using the K - value (efficiency factor). The produced Metakaolin as well as the commercial one imparted similar behaviour with respect to the concrete strength. Both conventional and commercial Metakaolins demonstrate very high K-values (close to 3.0 at 28 days) and are depicted as HR pozzolanic materials that may lead towards concrete production with an exceptional performance. Juenger et al. (2004) studied the alkali-silica reactivity of large silica fume derived particles. They reported that under accelerated testing agglomerated silica fume decrease expansion when used as a 5% replacement of reactive sand.

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Fabien Lagier, Kimberly E.Kurtis (2007) in their investigation, the research on two Metakaolins which vary principally in their surface area, and Portland cements of varying composition were examined via isothermal calorimetry for pastes at water cementitious materials ratio of 0.50 containing 8% cement replacement by weight of Metakaolin. The following preliminary conclusions are made by the authors: i). The Metakaolins examined appear to have a catalyzing effect on cement hydration, leading to acceleration in the reaction rates, an increased in cumulative heat evolved during early hydration and for some cements apparently an increased intensity in heat evolved during certain periods of each hydration. The surface area of the Metakaolin also seems to influence these early hydration behaviors, with the higher surface area material producing a greater rate of heat evolution, greater cumulative heat, and greater intensity during early hydration. It is proposed that the Metakaolin may act to enhance dissolution of cementitious phases and or by providing nucleation, in addition to increasing the solubilized aluminium in the system at early ages. ii). Strongly exothermic reactions appear to occur between the cements and Metakaolin examined, particulars in the first 24 hours, and these reactions seem to be most closely allied with the Third Peak experiential in calorimetry related to the reaction of calcium aluminate phases. iii). The reaction of MK appears to be quite sensitive to variation in total alkali content in the cement. When the alkali content increases the beginning of MK appears to result in amplification of the third peak viewed during calorimetry. It is proposed that an increasing rate of Metakaolin dissolution with increasing cement alkali-content may accelerate (or) intensify the reaction of C3A phase. David G. Snelson et al. (2008) investigated the effect of using Metakaolin and flyash as partial replacements with cement on the rate of heat evolution during hydration. It was observed that adding flyash to Portland cement enhanced the Portland cement hydration in the very early stages of hydration, but at extended periods an increase in flyash replacement causes a systematic reduction in heat output. When combining Metakaolin and flyash in ternary blending, the Metakaolin has a dominant influence on the heat output versus time 2.3 Effect of silica fume on strength High compressive is normally the first property associated with silica fume concrete.The relationship between tensile, flexural and compressive strengths in silica fume concrete is the same as those for ordinary strength concrete. Increase in compressive strength by using silica fume also results an increase in the tensile and flexural strength. This plays an important role when silica fume concrete is used in bridging, flooring, and roadway projects. Increased tensile strength causes a possible reduction in slab thickness while maintaining high compressive strengths. Hence, it reduces the overall slab weight and cost . The stronger concrete is more brittle and silica fume concrete is no exception to this rule. Modulus of elasticity does not follow the pattern of tensile strength, but only displays slight increase compared to the compressive strength. Thus, high and ultra-high strength concrete can be used for tall structures without loss of ductility .Silica fume concrete has a very finer phase and good bonding to substrates compared to the ordinary concrete. Studies have shown that the aggregate-cement interface changes in the presence of silica fume . By using silica fume, the bonding to the steel fibres is significantly increased. This is particularly

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useful in the steel fibre-silica fume modified shotcrete which is commonly used in Scandinavia. Short microfibers, such as glass, carbon, polypropylene, steel, and other fibres are used as an admixture in concrete to improve the tensile and flexural properties and reduce the drying shrinkage. Effective use of the fibres, which is consumed in very small quantities such as 0.5% by weight of cement in the case of carbon fibres, needs good dispersion of the fibres. The addition of untreated silica fume to microfibers reinforced cement enhances the degree of fibre dispersion, due to the fine silica fume particles which help the mixing of the microfibers. Silica fume also increases the structure of the fibre-matrix interface and decreases the weakness of the interfacial zone and also the number and size of cracks . 2.4 Effect of silica fume on chemical The reaction of calcium hydroxide with carbon dioxide in the atmosphere results efflorescence, which is a whitish haze. Primary stage of efflorescence occurs while concrete becomes hard. Secondary efflorescence is resulted from the weathering of the hardened concrete. It does not only increase the aesthetic quality of the structures but it can also give an increase in permeability, porosity, and ultimately weaker and less durable concrete. Research has shown that addition of silica fume decreases efflorescence due to the refined pore structure and increased consumption of the calcium hydroxide. The addition of untreated silica fume to steel reinforced concrete enhances the corrosion resistance of the reinforcing steel. Besides that, it also increases the concrete chemical attack resistance, whether the chemical is acid, chloride, and sulphate. These cause reduction in the permeability . According to the literature review , for equal strengths and any concrete strength below 40 MPa, carbonation is higher in silica fume concretes. Concrete above 40 MPa gives a reduction in carbonation rate, but this concrete can be affected by corrosive damage due to the reinforcement. Silica fume concrete is normally utilised when the compressive strength is above 40 MPa .It is an issue as to whether carbonation is a serious risk. Concrete curing procedures are necessary to ensure the optimum performance of the silica fume concrete . Silica fume decreases bleeding significantly, because free water is used in wetting of the large surface area of the silica fume. In addition, silica fume blocks the pores in the fresh concrete and stops water from permeate the surface of the concrete. 2.5 Effect of silica fume on durability The durability of silica fume concrete to freeze thaw is normally satisfactory at silica fume content of less than 20%. Freeze-thaw durability is related to the ability to withstand changes between temperatures above 0C and those below 0 C . Due to the presence of water, which undergoes freezing and thawing and also in turn causes changes in volume, concrete shows a tendency to decrease upon such temperature cycling. Air voids which are called air entrainment are utilised as cushions to accommodate the changes in volume, thereby improving the freeze-thaw durability. The addition of silica fume to mortar enhances the freeze-thaw durability in spite of the poor air void system. Hence, the use of air entrainment is still recommended. The permeability of chloride ions in concrete reduces by the addition of untreated silica fume. In this regard, there is reduction in the water absorbance. These effects are the cause of the microscopic pore structure which produces calcium silicate hydrate from the pozzolanic reaction of silica fume with free lime within the hydration of concrete .

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2.6 Effect of silica fume on temperature Concrete with low thermal conductivity is useful for the thermal insulation of buildings. On the other hand, concrete with high thermal conductivity is useful for decreasing temperature gradients in structures. The thermal stress that is resulted from temperature gradients may cause mechanical property reduction in the structure. Bridges are among the structures that tend to encounter temperature differentials between their top and bottom surfaces. In contrast to buildings which encounter temperature differentials; bridges do not require thermal insulation Hence, concrete of high thermal conductivity is in demand for bridges and related structures. The thermal conductivity can be reduced by the addition of untreated or silane treated silica fume due to the interface between silica fume particles and cement which act as an obstacle against heat conduction. 2.7 Effect of metakaolin on workability Workability of concrete decreases as percentage of metakaolin or silica fume increases from 5% to 11% at intervals of 2% by replacement in OPC .By adding 10 % activated flyash in both the mixes of silica fume and metakaoline workability is improved. 2.8 Effect of metakaolin on strength: Calcium hydroxide accounts for up to 25% of the hydrated Portland cement, and calcium hydroxide does not contribute to the concretes strength or durability. Metakaolin combines with the calcium hydroxide to produce additional cementing compounds, the material responsible for holding concrete together. Less calcium hydroxide and more cementing compounds means stronger concrete. Metakaolin, because it is very fine and highly reactive, gives fresh concrete a creamy, nonsticky texture that makes finishing easier. Metakaolin aggressively consumes calcium hydroxide, acid staining concrete with metakaolin added to it might lead to disappointment. Acid stain needs the calcium hydroxide to react, and without enough of it in the concrete, the acid stain color might not develop enough, or even not develop at all. 2.9 Concrete deterioration caused by external agents Concrete is inherently porous although with good concrete the permeability to gases and liquids is very low. However, the outer skin of concrete cast against shuttering or trowelled in some way is cement and water rich and is more porous than the body of concrete. The skin may be quite thinless than 1mm Agents which are aggressive to cements, e.g. acids and sulphates, can only penetrate concrete when dissolved in water and even aggressive gases only react with the cement hydrates in the presence of water. Two agents associated with the deterioration of concrete are carbon dioxide and chlorides. They do not attack concrete as such (although very high concentrations of chloride may do so) but they promote the corrosion of embedded metals and will be dealt with . It should be pointed out that carbon dioxide (CO2), which causes carbonation, is in practice positively beneficial to concrete since carbonated concrete is stronger and more resistant to penetration by aggressive agents. The confusion arises because excessive carbonation is associated with poor concrete and the benefits of carbonation are not sufficient to turn it into good concrete. 2.9.1. Acid attack Hydrated cement is alkaline and reacts with acids (Harrison, 1987). The effect is generally to dissolve the cement hydrates as calcium salts. For example, hydrochloric acid (HCl) is used

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in the chemical analysis of hardened concrete to dissolve the cement completely, the products being soluble calcium chloride, iron and aluminium chlorides and silicic acid. All cements except HAC are equally susceptible. However, there are a number of mitigating circumstances and in practice acid attack is only a problem in industrial processes, in sewers and in circumstances where the concrete is exposed to rapid flows and considerable volumes of acid. Concrete made with insoluble aggregates, i.e. most of those used other than limestones, exposes progressively less cement hydrate to the acid as acid attack proceeds and the aggregate is exposed. Also the silica in the cement is dissolved as silicic acid but this readily polymerizes to form silica gel which is insoluble and clogs up the pores in the hydrated cement, thus inhibiting further ingress of acid. The aggressiveness of the acid depends on the solubiility of its calcium salt. Thus hydrochloric acid dissolves the cement to form calcium chloride which is very soluble and is consequently very aggressive. In contrast, a natural acid present in acid soils, humic acid, forms calcium humate which has a low solubility and hence the acid is not very aggressive. Oxalic acid forms insoluble calcium oxalate and is totally non-aggressive. The surfaces of the paste exposed to the acid, becomes coated with the insoluble salt so that reaction ceases. Sulphuric acid forms calcium sulphate which has a limited solubility but when the water containing sulphuric acid has a vigorous flow, as may occur in sewers, the calcium sulphate can be physically removed by scouring as well as dissolution and considerable attack can take place. Sulphuric acid can beformed in sewers by biological processes acting on neutral sulphates. Sulphate attack does not appear to occur in acid conditions. Because the acid is neutralized when it reacts the effect is usually limited to the surface but if sufficient acid is present the reaction is progressive so that in extreme cases the concrete is eventually completely destroyed. However, the calcium salts formed may be absorbed into the concrete and give rise to other deterioration mechanisms. For example, hydrochloric acid may leave high concentrations of calcium chloride in the unattacked concrete which can promote corrosion of the reinforcement. A special case of acid attack can be caused by dissolved carbon dioxide in soft water which behaves as a solution of carbonic acid H2CO2. This forms not insoluble calcium carbonate but relatively soluble calcium bicarbonate. Attack is only significant with high flows of soft water saturated with carbon dioxide and is generally a surface effect since precipitation of silica gel as a result of cement hydrate dissolution inhibits further attack. Indeed cases have been observed where such waters acting on limestone aggregate concrete have dissolved the aggregate without significant attack on the cement paste. When a finite quantity of acid is involved the use of limestone aggregate is beneficial since it is itself dissolved by acids and gives extra neutralizing power. There is also a more uniform loss of surface compared with the rough exposed aggregate surface left with insoluble aggregates. However, with continuous flows, attack is more pronounced. 2.9.2. Sulphate attack Two of the components of cement paste, calcium hydroxide and calcium aluminate hydrates, react with sulphate ions in solution. The solid reaction products have larger volumes than the initial compounds so that disruption of the paste occurs. The reaction of calcium hydroxide with dissolved sulphate ions depends on the nature of the sulphate. Chemical reactions are written as equations with the left-hand side of the equation being the reactants and the righthand side the products. The two sides are connected by an arrow denoting the direction of change. However, most ionic reactions do not always go to completion but achieve an equilibrium state and can then proceed in either direction. This is exemplified by the reaction between calcium hydroxide and sodium sulphate:

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Ca(OH)2+Na2SO4 = CaSO4 + 2NaOH The reaction goes from left to right until the concentration of sodium hydroxide (NaOH) builds up sufficiently to stop the reaction. If further NaOH is formed the reaction can then go from right to left. Thus the efflorescence on some clay bricks is caused by the reaction of NaOH from cement hydration reacting with insoluble gypsum (CaSO4) in the brick to form soluble sodium sulphate which can then migrate to the brick surface and, on drying, crystallize. Equation above denotes the equilibrium condition; for example, if the concentration of sodium sulphate is 2% only about one-fifth of the sulphate forms calcium sulphate (Lea, 1970). In contrast, the equation with magnesium sulphate Ca(OH)2+MgSO4 = CaSO4 + Mg(OH)2 goes wholly from left to right, because magnesium hydroxide is very insoluble and therefore the reaction from right to left is insignificantly slow. As a result magnesium sulphate solutions react completely with the calcium hydroxide. When the reaction goes to completion, as with magnesium sulphate, all the free calcium hydroxide may be changed to calcium sulphate. Calcium silicate hydrate gel (C-S-H) is only stable in the presence of calcium hydroxide and so it partially decomposes to give more calcium hydroxide and hydrated silica. Thus with strong solutions of magnesium sulphate not only is there a disruption caused by the physical forces of expansion but there can also be a progressive breakdown of the silicate structure. Ammonium sulphate, usually only encountered in industrial or agricultural environments, is also particularly aggressive because its reaction with calcium hydroxide goes to completion. The ammonium hydroxide formed is continuously evolved as ammonia gas and water. It is clear that calcium sulphate cannot react with calcium hydroxide in a significant manner because both sides of the equation will be the same. This reaction with the calcium hydroxide is an important part of sulphate attack and is the primary reason why magnesium sulphate (and ammonium sulphate) is so much more aggressive than sodium sulphate and calcium sulphate. The theoretical expansion in changing from solid Ca(OH)2 to solid Ca(SO4) is about 2.2 times. Carbonation of hydrated cement will be discussed more fully but the effect is to convert calcium hydroxide to insoluble calcium carbonate, with very little volume change. Calcium carbonate does not participate in reactions with neutral sulphate solutions and thus carbonated concrete is not susceptible to this part of sulphate attack. The better resistance of real concrete to sulphates compared with that expected from consideration of laboratory experiments is probably due to the existence of a carbonated layer at the surface. It is also likely that the presence of dissolved carbonates in seawater makes it less aggressive than its sulphate content would suggest. In a competition for reaction with calcium hydroxide between sulphate and carbonate, the latter will win because of the insolubility of calcium carbonate. The other major reaction involving sulphates is with the calcium aluminate hydrates. Controlled amounts of calcium sulphate are added to Portland cements to control their setting and early behaviour by moderating the rate of reaction of the C3A with water. When excessive amounts of sulphate are incorporated in the fresh concrete the reaction with C3A may be continued after the cement has set and begun to harden. If the expansion caused is greater than the tensile strength of the paste, disruption occurs; the disruption will be extensive because of the wide dispersal of the sulphate. However, if the paste can cope with the forces, expansive or shrinkage-compensated properties can be achieved. When external sources of sulphate are in contact with hardened concrete they can react with the outer surface, but if the concrete is porous they may be absorbed to react further into the body of

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the concrete. In practice, therefore, sulphate attack from external sources is manifested as a progressive weakening and disintegration of the surface. With very porous materials it is possible for the sulphate to be absorbed to such an extent that disruption takes place more generally but such a mechanism is normally only observed in laboratory experiments. As a consequence, concrete which has been damaged by contact with sulphates can be repaired by removal of the outer weakened layers until sound concrete low in sulphates has been reached. 2.9.3. Chlorides attack The passive oxide film formed on steel surfaces in the presence of hydroxide ions can be destroyed by high levels of ions which form soluble iron compounds. Chlorides are abundant and are the most common cause of such depassivation. The C3A phase in Portland cement reacts with the sulphate in the cement to form sulphoaluminates . Chloroaluminates can also be formed and the chloride in these is rather insoluble in pore liquid. Cements containing high levels of C3A can therefore bind some chloride into an insoluble and therefore non-reactive form. Some of the chloride incorporated in fresh concrete as an admixture or from an unwashed marine aggregate can therefore be immobilized to some extent if there is sufficient C3A hydrate present. It appears, however, that if sulphate and chloride are competing for reaction with C3A, the sulphate is more likely to win. Carbonation of chloroaluminates releases the bound chloride into a free mobile form. Chlorides in the outer carbonated zone of concrete can therefore be washed away or alternatively washed into the uncarbonated concrete. Chloride entering concrete from an external source is to some extent analogous to carbonation. If water with a high concentration of chloride is in contact with concrete saturated with chloride-free water diffusion of chloride ions into the concrete will take place in an attempt to produce a uniform chloride concentration in the water. With concrete saturated with seawater, for example, the chloride concentration of the internal water will be lower, because of reaction with the C3A, than that of the body of water external to the concrete and chloride diffusion into the concrete will take place. Of course if concrete saturated with seawater is in contact with fresh water then free chloride ions will diffuse out of the concrete. The diffusion of chloride will be through the water in the capillary pores and, the finer and less continuous the pores, the slower will be the diffusion rate. In practice the ingress of chloride into concrete by diffusion is a relatively slow process and cycles of drying followed by saturation is a much more potent mechanism for the ingress of chloride. Overall, dense concrete of high alkalinity and low permeability can carry higher levels of chlorides without the occurrence of corrosion than permeable carbonated concrete. The risk of reinforcement corrosion associated with carrying levels of chloride content in both uncarbonated and carbonated concrete .

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Chapter 3
MATERIALS AND METHODOLOGY
3.1 Introduction: Cements may be defined as adhesive substances capable of uniting fragments or masses of solid mater to a compact whole (Lea, 1970). Portland cement was invented in 1824 by an English mason, Joseph Aspdin, who named his product Portland cement because it produced a concrete that was of the same color as natural stone on the Isle of Portland in the English Channel. Raw materials for manufacturing cement consist of basically calcareous and siliceous material. The mixture is heated to a high temperature within a rotating kiln to produce a complex group of chemicals, collectively called cement clinker (Neville, 1987). Cement is distinct from the ancient cement. It is termed hydraulic cement for its ability to set and harden under water. Briefly, the chemicals present in clinker are nominally the four major potential compounds and several minor compounds. The four major potential compounds are normally termed as tricalcium silicate (3CaO.SiO2), dicalcium silicate (2CaO.SiO2), tricalcium aluminate (3CaO.Al2O3) and tetracalcium aluminoferrite (4CaO. Al2O3.Fe2O3). The American Society for Testing and Materials (ASTM) Standard C 150, Specification for Portland cement, provides for the following types of Portland cement: Type I General Portland cement Type II Moderate-sulfate-resistant cement Type III High-early-strength cement Type IV Lowheat-of-hydration cement Type V High-sulfate-resistant cement 9 Type I Portland cement is a general cement suitable for all uses where special properties of other cements are not required. It is commonly used in pavements, building, bridges, and precast concrete products. Type II Portland cement is used where precaution against moderate sulfate attack is important where sulfate concentrations in groundwater or soil are higher than normal, but not severe. Type II cement can also be specified to generate less heat than Type I cement. This moderate heat of hydration requirement is helpful when placing massive structures, such as piers, heavy abutments, and retaining walls. Type II cement may be specified when water-soluble sulfate in soil is between 0.1 and 0.2%, or when the sulfate content in water is between 150 and 1500 ppm. Types I and II are the most common cements available. Type III Portland cement provides strength at an early age. It is chemically similar to Type I cement except that the particles have been ground finer to increase the rate of hydration. It is commonly used in fast-track paving or when the concrete structure must be put into service as soon as possible, such as in bridge deck repair. Type IV Portland cement is used where the rate and amount of heat generated from hydration must be minimized. This low heat of hydration cement is intended for large, massive structures, such as gravity dams. Type IV cement is rarely available. Type V Portland cement is used in concrete exposed to very severe sulfate exposures. Type V cements would be used when concrete is exposed to soil with a water-soluble sulfate content of 0.2% and higher or to water with over 1500 ppm of sulfate. The high sulfate resistance of Type V cement is attributed to its low tricalcium aluminate content.

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3.2 Cement Replacement Material With the extensively use of cement in concrete, there has been some environmental concerns in terms of damage caused by the extraction of raw material and CO2 emission during cement manufacture. This has brought pressures to reduce the cement consumption in the industry. At the same time, there are getting more requirements for enhancement in concrete durability to sustain the changing environment which is apparently different from the old days. With the development in concrete technology, cement replacement materials (CRM) have been introduced as substitutes for cement in concrete. Several types of materials are in common use, some of which are by-products from other industrial processes, and hence their use may have economic advantages. However, the main reason for their use is that they can give a variety of useful enhancements or modifications to the concrete properties. All the materials have two common features (Malhotra, 1986): i) Their particle size range is similar to or smaller than that of Portland cement. ii)They are pozzolan material. 3.2.1 Pozzolanic Behavior A common feature of nearly all CRM is that they exhibit pozzolanic behaviour. Pozzolanic materials the materials which contains active silica (SiO2) and is not cementitious in itself but will, in a finely divided form and in the presence of moisture, chemically react with calcium hydroxide at ordinary temperatures to form cementitious compounds (Malhotra, 1983). 3.2.2 Types of Cement Replacement Material The main cement replacement materials in use world-wide are:

Fig.3.1 Silica fume powder

fig.3.2 scanning electron microscope micrograph of silica fume particles at 20000 x

3.2.2.1 Silica fume Silica fume, also referred to as microsilica or condensed silica fume, is a byproduct material that is used as a pozzolan This byproduct is a result of the reduction of high-purity quartz with coal in an electric arc furnace in the manufacture of silicon or ferrosilicon alloy. Silica fume rises as an oxidized vapor from the 2000C (3630F) furnaces. When it cools it condenses and is collected in huge cloth bags. The condensed silica fume is then processed to remove impurities and to control particle size. Condensed silica fume is essentially silicon

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dioxide (usually more than 85%) in noncrystalline (amorphorous) form. Since it is an airborne material like fly ash, it has a spherical shape. It is extremely fine with particles less than 1 m in diameter and with an average diameter of about 0.1 m, about 100 times smaller than average cement particles. Condensed silica fume has a surface area of about 20,000 m2/kg (nitrogen adsorption method). For comparison, tobacco smokes surface area is about 10,000 m2/ kg. Type I and Type III cements have surface areas of about 300 to 400 m2/kg and 500 to 600 m2/kg (Blaine), respectively. The relative density of silica fume is generally in the range of 2.20 to 2.5. Portland cement has a relative density of about 3.15. The bulk density (uncompacted unit weight) of silica fume varies from 130 to 430 kg/m3 (8 to 27 lb/ft3).Silica fume is sold in powder form but is more commonly available in a liquid. Silica fume is used in amounts between 5% and 10% by mass of the total cementitious material. It is used in applications where a high degree of impermeability is needed and in high strength concrete. Silica fume must meet ASTM C 1240. And ACI 234 (1994) and SFA (2000) provide an extensive review of silica fume. It is very fine no crystalline silica manufactured by electric arc furnaces as a by-product of the production of metallic silicon or ferrosilicon alloys. The raw materials are coal, quartz, and woodchips . The smoke that produced from furnace operation is stored and sold as silica fume rather than being land filled. As the silica fume powder particles are hundred times finer than ordinary Portland cement, there might be problems arise when deals with silica fume, such as dispensing consideration, transportation, and storage that must be taken into account. To overcome some of these difficulties, the material is commercially divided in various forms. The difference between these forms is the size of the particle which do not significantly affect the chemical make-up or reaction of material. This difference has effect on the different purposes of use. Thus, careful consideration is needed when choosing the type of silica fume for specific application. The properties of silica fume depend on the type of producing and the process used for its manufacture. It is in form of spherical particle shape. It is a powder with particles having diameters 100 times smaller than Portland cement particles . Silica fume comes in three forms of powder, condensed, and slurry. Its colour varies from light to dark grey which depends on the process in the manufacturing and is influenced by some parameters such as wood chip composition, furnace temperature, ratio of wood chip to the coal used, exhaust temperature, and type of metal produced. For undensified silica fume, bulk density is in range of 200-350 kg/m3. Due to the low bulk density, this form is considered impractical to be utilised in normal concrete production . Undensified silica fume is commonly used in refractory products and formulated bagged material such as mortars, grouts, protective coatings, and concrete repairs system. For this type of silica fume, bulk density is in range of 500 -650 kg/m3.In the densification process the ultra fine particles become loosely agglomerated which makes the size of particles larger. Hence, the powder becomes easier to be used, with less dust compared to the intensified forms. This material is commonly used in those processes that utilise high shear mixing facilities such as concrete roof tile works, pre-cast works, and ready mixed concrete plants with wet mixing units . Silica fume is produced during a high-temperature reduction of quartz in an electric arc furnace when the main product is silicon or ferrosilicon. The chemical process is complex and it depends on the temperature of the producing. The Si formed, initially plays important intermediate roles. At temperatures > 1520 0C SiO2 + 3C = SiC+2CO

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At temperatures > 1800 0C 3SiO2+2SiC = Si+4SiO+2CO The unstable gas diffuses in the furnace where it reacts with oxygen to give the silicon dioxide 4SiO+2O2 = 4SiO2 With the addition of silica fume, the slump loss with time is proportionally increased in concrete mix. Due to the high surface area of silica fume particles in the concrete mix, workability and consistency of concrete decrease . These are restraints against the suitable utilisation of silica fume concrete. However, the consistency of silica fume mortar is significantly increased by either using silane treated silica fume, i.e., silica fume which has been coated by a silane coupling agent prior to incorporation in the mix, or utilising silane as an additional admixture . Vibration reduction is useful for structural stability, hazard mitigation, and structural performance improvement. Effective vibration reduction requires both stiffness and damping capacity. Silica fume is effective for increasing both damping capacity and stiffness. Sound or noise absorption is helpful for numerous structures, such as noise barriers and pavement overlays. The addition of silica fume to the concrete increases the sound absorption ability . 3.2.2.2 METAKAOLIN

Fig.3.3

Metakaolin powder

fig.3.4 scanning electron microscope micrograph of calcined clay particles at 2000x

Calcined clays are used in general purpose concrete construction much the same as other pozzolans. They can be used as a partial replacement for the cement, typically in the range of 15% to 35%, and to enhance resistance to sulfate attack, control alkali-silica reactivity, and reduce permeability. Calcined clays have a relative density of between 2.40 and 2.61 with Blaine fineness ranging from 650 m2/kg to 1350 m2/kg. Calcined shale may contain on the order of 5% to 10% calcium, which results in the material having some cementing or hydraulic properties on its own. Because of the amount of residual calcite that is not fully calcined, and the bound water molecules in the clay minerals, calcined shale will have a loss on ignition (LOI) of perhaps 1% to 5%. The LOI value for calcined shale is not a measure or indication of carbon content as would be the case in fly ash. Metakaolin, a special calcined

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clay, is produced by low temperature calcination of high purity kaolin clay. The product is ground to an average particle size of about 1 to 2 micrometers. Metakaolin is used in special applications where very low permeability or very high strength is required. In these applications, metakaolin is used more as an additive to the concrete rather than a replacement of cement typical additions are around 10% of the cement mass. Natural pozzolans are classified by ASTM C 618 (AASHTO M 295) as Class N pozzolans ACI 232 (2000) provides a review of natural pozzolans. Metakaolin is classified as a new generation of supplementary cementitous material. Supplementary cementitious materials (SCMs) are finely ground solid materials that are used to replace part of the clinker in a cement or cement in a concrete mixture. Use of metakaolin in cement-based systems, provides, beside technical , significant environmental benefits . Metakaolin is unique in that it is not the by-product of an industrial process nor is it entirely natural; it is derived from a naturally occurring mineral, and is manufactured specifically for cementing applications. 3.2.2.2.1 Production of Metakaolin from Kaolin

Fig. 3.5 Raw kaolinite The name kaolin is derived from the Chinese term Kauling meaning high ridge, the name for a hill near Jauchau Fu, where this material was mined centuries ago for ceramics (Hamer, 1977). The main constituent, kaolinite is a hydrous aluminium silicate of the approximate composition 2H2O.Al2O3.2SiO2. Kaolinite is the clay minerals which provide the plasticity of the raw material and change during firing to produce a permanent material. Kaolin is a phyllosilicate, consisting of alternate layers of silica and alumina in tetrahedral and octahedral coordination. This electrically neutral crystalline layer structure, which is a common characteristic of clay minerals, leads to a fine particle size and platelike morphology and allows the particles to move readily over one another, giving rise to physical properties such as softness, soapy feel, and easy cleavage [Kingery, 1976]. Kaolinite is the mineralogical term for hydrated aluminum disilicate, Al2Si2O5(OH)4, the primary constituent of kaolin (40-70%). Other minerals comprising kaolin include quartz, muscovite-like micas, and rutile [Moulin, 2001].

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Fig. 3.6 : Atomic arrangements of (a) Si2O5 and (b) AlO(OH)2

Fig. 3.7 : Perspective drawing of kaolinite with Si-O tetrahedrons on the bottom half and Al-O, OH octahedrons on the top half of the layer Under normal environmental conditions, kaolin is quite stable. However, when heated to temperatures of 650-900 C, kaolin loses 14% of its mass in bound hydroxyl ions. This heat treatment, or calcination, breaks down the structure of kaolin such that the alumina and silica layers become puckered and lose their long-range order. Resulting from this dehydroxylation and disorder is MK, a highly reactive transition phase. MK is an amorphous pozzolan, with some latent hydraulic properties, that is well-suited for use as an SCM [Bensted, 2002]. The calcining temperature plays a central role in the reactivity of the resulting MK product. Ambroise et al. [Ambroise, 1985] studied the effects of calcining temperature on the strength development of MK-lime pastes. These authors found 700 C to be optimal and later showed that calcination below this temperature results in a less reactive material containing more residual kaolinite. Above 850 C, they reported, recrystallization began and reactivity declined, as kaolin had begun to convert to relatively inert ceramic materials, such as spinel, silica, and mullite [Bensted, 2002]. The heating process, illustrated by differential thermal analysis (DTA), is shown in Figure below,

22

Fig. 3.8 DTA thermogram of kaolin Calcining is traditionally carried out in rotary kilns and takes several hours. The use of a fluidized bed process may reduce calcining time to minutes, although both of these methods require grinding of the agglomerated products. Flash-calcining, which consists of rapid heating, often to 1000 C, followed by rapid cooling, may reduce the processing time further -- from minutes to several tenths of a second. Additionally, there is no grinding step required, as the starting material is finely powdered kaolin suspended in a gas [Salvador, 1995]. The MKs examined in this study were produced using vertical hearth fluid bed calciners, into which the clay was fed at the top and the product collected from the bottom. While prolonged soak-calcining at lower temperatures is generally quite effective at removing hydroxyl groups, Salvador [Salvador, 1995] showed that the calcining rate does influence the pozzolanic reactivity of MK. In his study, flash-calcined kaolins had higher water absorption capacities, and thus required more water to achieve suitable workability, suggesting these had a higher initial reactivity than soak-calcined kaolins. Further, at the same water-to-cementitious materials ratio (w/cm), cylinders made with flash-calcined kaolins always performed better in compression than those made with soak-calcined kaolins. Metakaolin is usually produced by thermal treatment, i.e., calcination of kaolin clays within a definite temperature range. The main process important for production high reactivity pozzolana from kaolin clay is calcination. The heating process drives off water from the mineral kaolinite (Al2O3+2SiO2+2H2O), the main constituent of kaolin clay, and collapses the material structure, resulting in an amorphous aluminosilicate (Al2O3 2SiO2), metakaolinite. The process is known as dehydroxylation , and is presented by simple equation: Al 2O 3 2SiO2 2H2O =Al 2O 3 2SiO 2 + 2H 2O (1) The thermal transformation of kaolinite, which has been the subject of a large number of investigations, has shown that the heating parameters such as temperature, heating rate and time, as well as cooling parameters (cooling rate and ambient conditions), significantly influence the dehydroxylation process. The major quantitative criterion for evaluating the performance of kaolinite by thermal treatment is a degree of the dehydroxylation. The development of pozzolanic properties in fired clays mainly depends on nature and abundance of clay minerals in raw materials, on calcination conditions and on the fineness of the final product. The calcinations temperature producing the reactive state is usually in the range of

23

600800 C, and plays a central role in the reactivity of the resulting MK product. On prolonged heating, recrystallization and mullite (3Al2O3.2SiO2) formation take place resulting in the decline of material reactivity. The main characteristic of produced metakaolin, for the use in cement based systems, is its pozzolanic activity, which is defined as ability of material to react with calcium hydroxide in the presence of water to form compounds that have cementitious properties. Pozzolanic activity may be determined by direct and indirect methods . Direct methods are based on the measurement of the amount of lime reacted, which can even be determined by instrumental techniques such as thermogravimetry (TG), differential thermal analysis (DTA), X-ray diffraction (XRD) and calorimetric analysis. Indirect methods are based on the strength development occurring with reaction time. The values of pozzolanic activity indicate how good and effective pozzolan is. Metakaolin reacts with portlandite (CH) to form calcium-silicate-hydrate (C-SH) supplementary to that produced by portland cement hydration. This reaction becomes important within the interfacial transition zone (ITZ) located between aggregate and paste fractions. This region typically contains a high concentration of large, aligned CH crystals, which can lead to localized areas of increased porosity and lower strength.Metakaolin can react with some of the CH produced by cement hydration, thereby densifying the structure of the hydrated cement paste. The rates of pozzolanic reaction and CH consumption in metakaolin systems have been shown to be higher than in silica fume systems, indicating a higher initial reactivity.6 Because this reaction with CH occurs early and rapidly, metakaolin incorporation may contribute to reduced initial and final set times. In addition, this refinement in the ITZ can result in increased strength in metakaolin concrete. As portlandite in the ITZ and elsewhere in the paste is water soluble and is susceptible to deterioration in aggressive chemical environments, metakaolin has great potential for improving concrete durability.4 Also, because the supplementary C-S-H formed during the pozzolanic reaction with metakaolin has a lower Ca/Si ratio than ordinary C-S-H, these products are believed to be better able to bind alkali ions from the pore solution, thus reducing concrete's susceptibility to alkali-silica reaction (ASR). This potential beneficial use of metakaolin is particularly relevant, as silica fume agglomerates have been shown to contribute to ASR expansion in some cases. Metakaolin has also been shown to decrease concrete permeability, which in turn increases its resistance to sulfate attack and chloride ion ingress. Additionally, metakaolin may reduce autogenous and drying shrinkage, which could otherwise lead to cracking. Thus, when used as a partial replacement for portland cement, metakaolin may improve both the mechanical properties and the durability of concrete. In general, metakaolin offers a set of benefits similar to those imparted by silica fume, including comparable strengths, permeability, chemical resistance, and drying shrinkage resistance. Physically, metakaolin particles measure approximately one-half to five micrometers across, making them an order of magnitude smaller than cement grains and an order of magnitude larger than silica fume particles. Both metakaolin and silica fume are typically used to replace 5 to 20 weight % of the cement. Metakaolin is white in color, whereas standard silica fume ranges from dark grey to black (although white silica fume is available at higher cost). This makes metakaolin particularly attractive in colour matching and other architectural applications. For these reasons, metakaolin is increasingly used in the production of highperformance concrete. Here the influence of metakaolin fineness is investigated and the performance of concrete containing one of two metakaolins of different fineness are compared to silica fume concrete and ordinary concrete. Measurements of fresh properties, including slump, setting time, and shrinkage (autogenous, chemical, and free shrinkage) are

24

examined, as well as mechanical performance (compressive strength, splitting tensile strength, flexural strength, elastic modulus) and certain aspects of durability (shrinkage, chloride permeability, sulfate resistance, alkali reactivity). The presence of MK has an immense effect on the hydration of portland cement (PC). When portland cement alone hydrates, typically 20-30% of the resulting paste mass. However, when MK is introduced, it reacts rapidly with these newly forming CH compounds to produce supplementary calcium silicate hydrate (C-S-H). Recalling cement chemistry notation from the basic ,the hydration reactions are as follows: 2C3S + 11H C3S2H8 + 3CH (C-S-H) (CH) 2C2S + 9H C3S2H8 + CH C3A + 3C.H2 + 26H C6A.3H32 (gypsum) (ettringite) 2C3A + C6A.3H32 + 4H 3C4A.H12 (monosulfate) C4A.H12 + 2C.H2 + 16H C6A.3H32 MK [Al2Si2O7] + CH + H C-S-H, C4AH13, C3AH6, C2ASH8 In general, SCMs with higher alumina contents, such as MK, tend to have higher pozzolanic capacities because formation of C-A-H has a high CH demand. This is critical, as CH does not make a significant contribution to concrete strength and can be detrimental to durability. Its elimination or reduction by secondary reaction with MK can greatly enhance concrete performance [Mindess, 2003; Poon, 2002]. Determination of the degree of pozzolanic reaction completed can be accomplished via a selective dissolution procedure, like that developed by Oshawa et al. [Oshawa, 1985] and Li et al. [Li, 1985]. The procedure is based on the assumption that the majority of the unreacted pozzolan is acid insoluble. In a blended cement paste, the pozzolan reacts with CH to form acid soluble hydration products. Thus, it is possible to dissolve the unreacted cement and the hydration products of both the cement and the pozzolan, leaving behind the insoluble residue of the unreacted pozzolan. The degree of pozzolanic reaction completed is defined as the percentage of unreacted pozzolan remaining relative to the initial amount of pozzolan present in the cement paste. Results from such selective dissolution evaluations, carried out by Poon et al. [Poon, 2001], showed that the degree of pozzolanic reaction was higher at a replacement level of 5% MK than at replacement levels of 10% and 20% for all ages. Similar results were observed with silica fume, though the 5% silica fume values were never as high as the 5% MK values. This higher rate of pozzolanic reaction in pastes with a lower replacement level could likely be attributed to the greater amount of cement, and thus higher concentration of CH, available for reaction with the pozzolan.

25

Because MK reacts with and consumes free CH, another method for determining the extent of pozzolanic reaction completed is to measure the remaining CH content in a paste, mortar, or concrete sample. As part of the same study, Poon et al. [Poon, 2001] also determined total CH content of paste samples, both based on the ignited weight and the weight of cement, using differential scanning calorimetry. This was performed in air atmosphere at a heating rate of 10 C/min. The CH content was calculated from the weight loss between 425 C and 550 C. In either case, cements blended with 20% MK showed the least total CH at all ages. MK mixtures showed steadily decreasing CH contents up to 90 days, as illustrated in Figure below :

Fig. 3.9 CH content calculated based on cement weight [Poon, 2001].

3.3. Investigation methodology 3.3.1. Cement : The type cement used is ordinary cement of 53 grade. Tests on Cement: 1.Fineness test 2.Standard Consistency 3.Initial and Final setting time 1.Fineness Test : Fineness of cement determines the rate of hydration reaction. Finer cement reacts faster with water and the rate of development of strength and corresponding heat of hydration is higher. IS Codes prescribing only the values of minimum fineness which are required for different types of cements. Fineness can be determined either by specific surface using air permeability test or it can be determined by actual sieving. In order to ensure the adequate fineness, 100g of cement is hand sieved through 90 IS sieve for 15minutes.

26

The limits of residue on sieve should be as given : For OPC, < 10% For PPC, < 5% 2.Standard Consistency : This test in itself doesnt give any quality parameter of cement but it ascertains the volume of water which is to be added for other tests like initial setting time, final setting time, soundness and strength etc. 3.Setting Time : Setting time means the time required for stiffening of cement paste to a defined consistency. There are two important limits on time scale which are important for setting o f c e m e n t : Initial setting time Final setting time 3.1 Initial setting time : By definition it is the time from addition of water to a time when the paste starts losing its plasticity. The test is conducted using Vicats apparatus. A needle of size 1 mm2 is used for measuring the penetration. 500 g of cement is taken and water equal to 0.85 P is added to make paste and the test is conducted at 27+2C. The needle is lowered till it touches the top surface of paste in the mould and then tightened. The needle is then quickly released and penetration is recorded. Initially it may go down and touch the bottom. As the time passes and the paste stiffens, the penetration of the needle will reduce. The test is repeated till such time when the needle is 5 mm (+0.5 mm) above bottom of mould. This time is called Initial setting time. When the test is repeated, the mould should be slightly displaced so that the needle doesnt penetrate at the same location. 3.2 Final setting time : It is the time from addition of water to the time when paste completely loses its plasticity. The earlier test is continued but with the changed needle. This needle has 26 special attachment such that when the penetration is more than 0.5 mm, there will be two impressions on cement paste, one of main needle and second of a circular cutting edge. But there will be only one impression of main needle when penetration is less than 0.5 mm. Therefore final setting time is the time from addition of water to the time when the penetration is just less than 0.5 mm or when the circular cutting edge fails to make an impression on the cement paste. Ordinary Portland cement of 53 grade conforming to IS: 12269 1987 being used for the experimental investigation. The specific gravity of cement is 3.10 Table 3.1. : Physical Characteristics of Cement Result Permissible limit as per IS:12269
36 % 200min 500min 98% passes through 90 micron sieve ---------->30 min < 600 min

Sr.no 1. 2. 3. 4.

Property

Normal consistency Initial setting time Final setting time Fineness modulus

----------

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3.3.2. Sand and Aggregate The aggregates were selected based on the limitation of BS 881 and 882. The sand used was natural river sand and the aggregate was 12.5 mm and 20 mm crushed granite. These materials will be dried at a temperature of 105C for 24 hours to control the water content in the concrete. 3.3.2.1 Tests on Aggregates: 1. Aggregate impact value 2. Aggregate Crushing Value 3. Shape Test 4. Specific Gravity 5. Moisture content of aggregates 6. Los Angeles Abrasion Value Aggregate Impact Value : Significance of test: The test is to be considered to be an important test to assess the suitability of aggregates as regards the toughness property. Table 3.2. : Allowable limits of Aggregates as per I.R.C. Aggregate impact value (%) Comment <10 10-30 20-30 >35 Exceptionally strong Strong Satisfactory Weak

Sr. No. 1 2 3 4

Aggregate Crushing Value : The aggregate crushing value is an indirect measure of crushing strength of aggregates. Low aggregate crushing values indicate strong aggregates, as the crushed factor is low. Shape Test : The particle shape of aggregates is determined by the percentages of flaky and elongated particles contained in it. In the case of gravel it is determined by its angularity number. Test for Elongation Index : The elongation index of an aggregate is the percentage by weight of particles whose greatest dimension (length) is greater than one and four fifth times (1.8 times) their mean dimension. The elongation test is not applicable to sizes less than 6.3 mm. Flaky & elongated particles are to be avoided. If flaky & elongated aggregates are present in appreciable proportions, the strength would be adversely affected due to possibility of breaking down under loads. Test for Flakiness Index: Significance of test: The flakiness index of aggregates is the percentages by weight of particles whose least dimension (thickness) is less than three-fifth of their mean dimension. The test is not applicable to sizes smaller than 6.3 mm. Specific Gravity of test:

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The specific gravity of aggregate normally used ranges from about 2.5 to 3.0 with an average value of about 2.68. High specific gravity of an aggregate is considered as an indication of high strength. Water absorption of an aggregate is accepted as measure of its porosity. Sometimes this value is even considered as a measure of its resistance to frost action, through this has not been yet confirmed by adequate research. Water absorption value ranges from 0.1% to 2.0% for aggregates. I.R.C has specified the maximum water absorption value as 1.0% for aggregates. Los Angeles Abrasion Value Test : Significance of test: Los Angeles test is very widely accepted as suitable test to assess the hardness of aggregates. The apparatus consists of Los Angeles machine and sieves. Los angeles machine: Los Angeles machine consists of a hollow steel cylinder closed at both ends, having an inside diameter 70cm and an inside length of 50cm mounted on stub shafts about which it rotates on a horizontal axis. An opening is provided in the cylinder for the introduction of test sample. A removable cover of the opening is provided in such a way that when closed and fixed by bolts and nuts, it is dust-tight and the interior surface is perfectly cylindrical. A removable steel shelf projecting radially 8.8cm into the cylinder and extending to the full length of it, is mounted on the interior surface of cylinder rigidly, parallel to the axis. The shelf is fixed at a distance of 125cm from the opening, measured along the circumference in the direction of rotation. Abrasion charge consists of cast iron spheres approximately 4.8cm in dia. and 390445 gm in weight are used. The weight of spheres used as the abrasive charge and the no. of spheres to be used are specified depending on gradation of the aggregates tested. The aggregate grading have been standardised as A, B, C, D, E, F and G for this test and the IS Specifications for the grading and abrasive charge to be used are given in the table A. IS sieve with 1.70mm opening is used for separating the fines after the abrasion test. 3.3.2.2 Coarse aggregate Crushed granite metal with 12.5 mm and retained on 10 mm sieve was used and also 20 mm was used. The sieve analysis of the aggregates was carried out and the same distribution . FM was maintained throughout the experiment The specific gravity of coarse aggregate is 2.68. 3.3.2.3 Fine aggregate Locally available sand was used as fine aggregate. The specific gravity of fine aggregate is 2.50. Table 3.3. Physical property of fine aggregate, coarse aggregate Sr.no Property Fine Aggregate Coarse Aggregate 1 Fineness Modulus 94% finer than 12.5mm , 20mm 4.75mm 2 Specific Gravity 2.50 2.68 3 Crushing Value ------------------16.5 4 Impact Value ------------------5.6 5 Abrasion Value ------------------23.16 Table 3.4. Grading of fine and coarse aggregates

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Sieve sizes
80 40 20 12.5 10

Coarse aggregates % passing

100 93 35 15 5

Sieve sizes
10mm 4.75mm 2.36mm 1.18mm 600micron

Fine aggregates % passing Sieve sizes % passing

100 93.725 61.450 40.375 26.950 300 micron 150 micron 75 micron pan 10.925 4.175 2.85 0.075

3.4 Water : Water is needed for the hydration of cement and to provide workability during mixing and for placing. There is not much limitation for water except that the water must not severely contaminated. In this study, normal tap water was used. Fresh potable water, which is free from concentration of acid and organic substance are used for mixing the Concrete. 3.5. Metakaolin: Metakaolin (Metacem) for the present investigation was obtained from Zigma Internationals The Metakaolin was sieved and the fraction passing 100 IS sieve was used in the experiments.The specific gravity of Metakaolin is 2.54. It is in conformity with the general requirements of pozzolona. Silica fume for the present investigation was obtained from Yash Chemicals, Pune. The silica fume was sieved and the fraction passing 100 IS sieve was used in the experiments. The physical and chemical properties of silica fume , metakaolin and OPC are presented in table listed below: Table no. 3.5 showing the physical and chemical characteristics of materials used Physical property OPC Specific gravity 3.1 Mean grain size (m) 22.5 Specific area cm2/gm 3250 Colour greyish Chemical property Silicon dioxide (SiO2) Calcium oxide (CaO) Magnesium oxide (MgO) Sodium oxide (Na2O) Potassium oxide (K2O) Loss on ignition OPC 20.25 63.61 4.56 0.08 0.51 3.12 <6.0 <1.4 SILICA FUME 2.2 0.15 150000-300000 White SILICA FUME 85 0.2-0.8 0.2-0.8 0.5-1.2 METAKAOLIN 2.54 2.54 150000-180000 Pinkish METAKAOLIN 60-65 0.2-0.8 0.2-0.8 0.5-1.2

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3.6. Concrete Mixes : In this study, the early age properties of fresh concrete and mechanical performance and durability of hardened concrete were examined. All tests were conducted using the following sample groups: (1) an ordinary cement paste or concrete, (2) pastes or concrete substituted with 10% MK by mass. (3) pastes or concrete substituted with 10% silica fume by mass. (4) pastes or concrete substituted with 5% silica fume by mass and 5% MK by mass, (5) pastes or concrete substituted with 5% silica fume by mass and 10% MK by mass, (6) pastes or concrete substituted with 5% silica fume by mass and 15 % MK by mass (7) pastes or concrete substituted with 5% silica fume by mass and 20 % MK by mass 3.6.1.Mixing Procedure : The mixing procedures were divided into three stages. In the first stage, all the binders (cement, metakaolin, silica fume and slag) were weighted accordingly and mixed by hand until all the constituents mixed uniformly. This was to make sure all the binders were mixed thoroughly to produce a homogenous mix. The second stage involves mixing the binders with the aggregates for about 5 minutes. At the final stage, measured water was added into the concrete mix. This step was crucially important to make sure that the water was distributed evenly so that the concrete will have similar water-binder ratios for every cube. After that, the concrete was then poured into the mould. 3.6.2 Preparing Test Cubes : The size of the mould used to produce the cubes was 100 x 100 x 100 mm. Twelve cubes were used for each concrete mix. The concrete was poured into the mould in two layers where each layer was compacted using a steel bar. The cubes were removes from the moulds after 24 hours and cured using sacks in room temperature. 3.6.3 Curing : In this study, the cubes were cured using wetted sacks at room temperature. The cubes were cured until they were ready to be tested at the designated ages. The sacks were kept wetted by pouring water from time to time to enabled the cubes to be cured in a high moisture environment. In order to prevent excessive loss of moisture, the sacks were covered with plastic sheets. 3.7 Accelerated curing: 3.7.1 Introduction: Curing is the process of controlling the rate and extent of moisture lost from concrete during cement hydration. In order to obtain good quality concrete an appropriate mix must be followed by curing in a suitable environment during the early stages of hardening. Curing must be undertaken for a reasonable period of time if concrete is to achieve its potential strength and durability. Curing is essential if concrete is to b perform its intended function over the design life of the structure whereas; excessive curing time may lead to the escalation of construction cost of the project and unnecessary delay. Curing encompasses the control of

31

temperatures as it affects the hydration rate in cement. If within the curing period natural temperatures of concrete are in the acceptable range of values, only the moisture content needs to be controlled. If the natural temperature is outside the acceptable range of values, some means will be required for controlling the temperature of concrete. The curing of concrete is performed both at normal and elevated temperatures also. Curing can be done in a number of ways while the most appropriate means of curing may be dedicated by the site conditions of or the construction method. 3.7.2 Methods of curing: Broadly concrete curing processes can be classified into three categories first is the method in which the moisture loss can be prevented by continuously wetting the exposed surface of concrete, this in turn maintains the requisite quantity of water in the concrete during the early hardening period. This is also called as conventional curing. The second method minimizes moisture loss from the concrete, thus preventing the loss of mixing of water from concrete for example, by covering it with a relatively impermeable membrane. This is known as membrane curing using curing compounds. Finally, that which keeps the surface moist and at the same time, raise the temperature of the concrete, thereby increasing the rate of strength gain. The method is typically used for the pre-cast concrete products called accelerated curing. The best method of curing concrete depend upon the conditions at site or in a plant or availability of curing materials. On the type of job final appearance of the structure and the economics and can be have any one method or a combination of method. Some of the previous investigator have studied the effect of curing methods with and without the use of supplementary cementitious materials on the compressive strength and performance. Whiting and Synder, Nasser et al and Oztekin conducted a study to examine the effectiveness of different types of curing compounds in retaining water for hydration, promoting concrete strength and reducing permeability. These studies were conduced with and without supplementary materials. All compounds performed better than samples with no curing treatment. Tantawi and Gharaibey worked on the early estimation of hardened concrete strength based on accelerated strength. Shobha and Raju investigated the effect of curing compound on different grads of concrete. 3.7.2.1 Curing Methods: Following are few different methods of curing: a) Conventional Curing: The conventional curing involves dipping the specimens in water at 25C at the end of 24 hours of casting after allowing for air drying. b) Accelerated Curing by warm water method: After the specimens have been made they shall be left to stand undisturbed in their moulds in a place free from vibration at a temperature of 25 2C for at least one hour, prior to immersion in the curing tank. The time between the addition of water to the ingredients and immersion of the test specimens in the curing tank shall be at least 11 hours but shall not exceed 31 hours. The specimens in their moulds shall be gently lowered into the curing tank and shall remain totally immersed at 55 2C for a period of not less than 19 hours 50 min. The specimens shall then be removed from the water, marked for identification, removed from the moulds and immersed in the cooling tank at 27 2C before the completion of 20 hours 10

32

minutes from the start of immersion in the curing tank. They shall remain in the cooling tank for a period of not less than one hour. Warm water method: This method was taken into consideration for investigation. c) Accelerated curing by boiling water method: After the specimens have been made, they shall be stored in a place free from vibration, in moist air of at least 90% relative humidity and at a temperature of 27 2C for 23 hours 15 min. from the time of addition of water to the ingredients. The specimens shall then be gently lowered into the curing tank and shall remain totally immerses for a period of 31 hour 5 min. The temperature of the water in the curing tank shall be at boiling (100C) at sea level. The temperature of water shall not drop more than 3C after the specimens are placed and shall return to boiling within 15 min. After curing for 31 hours 5 min. in the curing tank, the specimen shall be removed from the boiling water, removed from the moulds and cooled by immersing in cooling tank at 27 2C for 2hours. 3.7.2.2 Precautions : The following precautions shall be taken: a) The curing tank shall be cleaned and the water renewed periodically so as to prevent accumulation of detritus which may impair the heating or circulating system. b) The use of boiling water imposes the need for safety measures to prevent scalding or eye-burn, resulting from sudden escape of steam, upon opening the cover. Also care shall be exercised when immersing the specimens to avoid splashing of hot water. c) Strict attention shall be given to the protection and storage of the specimens during the initial period of curing. d) Suitable safety devices and indicators shall be provided with the set up. A separate panel or switch-board shall be provided incorporating the thermograph and related heating equipment controls.

3.8 Correlation of results from compressive strength tests on specimens cured by normal and accelerated curing method: Accelerated curing of concrete hastens the process of hydration of cement and as a result, substantial proportion of the strength to be attained in 28 days under normal curing conditions is achieved within a shorter time. The rate and extent of hydration of cement under a particular curing regime depend mainly upon the chemical composition of cement, watercement ratio and mix proportions, which are considered to be important parameters in the correlation of results from compressive strength tests on specimens cured by accelerated curing method and normal curing method.

33

The accelerated curing regime, in itself is another variable in that the higher temperature employed may alter the morphology of the hydration products apart from thermally activating the chemical reactions of hydration of cement. The variability arising from the curing regime to be adopted is eliminated by standardizing them, as is done in this standard. Figure 1 show typical results on the correlation of compressive strength of concrete specimens normally cured and accelerated-cured by the boiling water method and the warm water method respectively. It is found that a correlation exists between the result obtained on concrete specimens, cured by accelerated method and cured by normal method, for mixes employing different materials and mix proportions. It is also found that the strength of concrete after accelerated curing (by either method) is of order of 50% of that obtained on normally cured, 28 days old specimens. When results of concrete with specific ingredients and mix proportions are considered, the dispersion of results is considerably reduced, and the coefficient of variation of results from accelerated curing methods may, in that case, be expected to be of the same order as obtained in normally cured 28 days conventional test. Although the tests have shown that the correlation between results from accelerated curing method and normally cured 28 days conventional test is not materially affected by the chemical composition, fineness and strength of cements, the mix proportions or use of some indigenous admixture, it is preferable to establish the actual correlation under site conditions for the specific materials and mix proportions to be adopted, for use in each case.

34

Fig.3.10 Typical Relation Between Accelerated And 28 day Compressive Strength of Concrete (By Warm Water Method)

35

3.9 Mix design for grade M-40 3.9.1 Initial Parameters: 1) 2) 3) 4) 5) Cement Grade- O.P.C. 53, Ultratech Cement, Concrete Grade-M40. Specific Gravity of Cement- 3.15 Fine Aggregates- Sand-Zone-II Specific Gravity of F.A- 2.50 Coarse Aggregates- 20 mm (60%) 10 mm (40%) 6) Specific Gravity of C.A- 2.68 3.9.2 Mix Design calculations: 1.Target Mean strength (Fck). Fck = fck + K.S Where , fck = Characteristics Compressive Strength at 28 days K = Statistical value for risk factor S = Standard Deviation Fck = 40 + (1.65 5) = 48.25 N/mm2 2. Selection of Water-Cement ratio: So, Assumed W/C = 0.4 (As per IS 456 200) W/C As per IS 20262 we have 0.38 from graph. Therefore, Considering W/C =0.4 3. Selection of Water & Sand content: W/C = 0.4 Taking Cement upto 400 kg/m3 As per IS 456 for M40 grade minimum cement content is 360 kg/m3 Therefore as Weight of Cement taken is 400 kg/m3 . Weight of water = 0.4 400 = 160 kg water Assumed 1kg = 1 liter, Hence Water requirement is 160 liters. Now for M40 as per IS Maximum cement content is 180 kg which is greater than calculated hence ok.

36

4. Calculation of C.A & F.A V = [(W + C/SC) + (1/P F.A/SF.A)] 1/1000 and V = {(W + C/SC) + [1/(1-P) C.A/SC.A]} 1/1000 Now as per IS 20262, 2% is considered as air entrapment V = 1- 0.2 = 0.98 Therefore, Weight of F.A = 680 kg Weight of C.A = 1160 kg Hence, Cement : F.A : C.A = 1 : 1.7 : 2.9 And W/C = 0.4

3.10 Experimental Investigation for Durability concepts regarding Acid Attack on Concrete: The materials used for this purpose is as listed above in and tested as per the code provisions made in the above clauses (4.1 4.4) Even the mixes and mix proportion made according to the requirement is also mentioned in the above clause (4.5). BIS code procedure as per IS: 10262-1982 was followed for finding the mix proportions of all the concrete specimens. Water binder ratio was considered as 0.4 to the optimum. The characteristics, physical and chemical properties of basic materials are listed in table 4.5. The concrete mix used is of grade M40 whose mix proportions are as followed : Concrete grade Materials required in per m3 of concrete Cement (kg) 400 Fine aggregates (kg) 680 Coarse aggregates (kg) 1160 Water requirement (litres)

M40

160

3.10

Testing methods for durability assessment :

The assessment of blended concrete in acidic environment was made based on the performance from visual assessment, mass loss and strength deterioration factor.

37

3.11.1 Visual assessment : Cubical specimens of 150x150 mm were casted for visual assessment and the prepared specimens were cured in water for 28 days and were immersed in 5% HCl solutions for next 30 days. The specimens were positioned so that all sides were in contact with the solutions. The pH5 of the solution was regularly monitored and adjusted to keep constant by replacing the consumed solutions by fresh solutions. The visual observation of acid attack was made as per the performance scale mentioned in Table 4.6 followed by Al-Tamimi.
Table 3.6 Scale of visual deterioration level of concrete specimens immersed in acidic solution

Scale 0 1 2 3 4 5 6

Deterioration level No Attack Very slight attack Slight attack Moderate attack Severe attack Very severe attack Partial disintegration

3.11.2 Mass loss The concrete cubes of 150 mm size were cast for finding the mass loss due to the acid attack. The prepared cubes were cured in water for 28 days and were immersed in 5%HCl solutions for next 30 days. The initial mass and the mass of concrete specimens after the immersion period of 2, 4 weeks were measured for finding the mass loss due to the deterioration of concrete specimens. The average value of three specimens was considered for assessment. 3.11.3 Strength deterioration factor (SDF) The deterioration of concrete cube specimens was investigated by measuring the strength deterioration factor expressed in percentage and it was calculated by using the equation -

Where, fcw is the average compressive strength of concrete cubes cured in water and fca is the average compressive strength of cubes immersed in acid solutions. The compressive strength test was carried out for each specimen in both the solutions after 4 weeks of immersion period. In each test period, the average value of three specimens were tested and reported.

38

Chapter 4
RESULTS AND DISCUSSION OF EXPERIMENTAL WORK
4.1 Introduction Results of fresh and hardened concrete with partial replacement of silica fume and metakaoline in combination are discussed in comparison with those of normal concrete. For the combinations of concrete mixes three cubes were being casted each for varying curing days 3,7,28 days. Test for the same being conducted under compressive testing machine of capacity 2000KN. 4.2 Result of concrete testing for cubes casted : Result of 3days strength of concrete Table 4.1 Strength of plain Concrete (3 days) Sr. No. Area Load (KN) 688.18 680.602 713.925 3 days strength of cubes Strength Avg. Strength (N/mm2) (N/mm2) 30.586 30.855 30.249 31.73

1. 2. 3.

22500

Table 4.2 Strength of 10% Metakaoline Replacement (3 Days) Sr. No. Area Load (KN) 661.95 675.29 672.232 3 days strength of cubes Strength Avg. Strength (N/mm2) (N/mm2) 29.420 29.770 30.013 29.877

1. 2. 3.

22500

Table 4.3 Strength of 10% Silica Fume Replacement (3 days) Sr. No. Area Load (KN) 677.473 673.042 650.182 3 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 30.110 29.640 29.913 28.897

1. 2. 3.

22500

39

Table 4.4 Strength of 5% Silica fume & 5% metakaoline Replacement (3 days) Sr. No. Area Load (KN) 597.19 612.38 610.89 3 days strength of cubes Strength Avg. Strength (N/mm2) (N/mm2) 26.542 26.970 27.217 27.151

1. 2. 3.

22500

Table 4.5 Strength of 5% Silica fume & 10% metakaoline Replacement (3 days) Sr. No. Area Load (KN) 590.10 605.52 604.68 3 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 26.223 26.670 26.912 26.875

1. 2. 3.

22500

Table4.6 Strength of 5% Silica fume & 15% metakaoline Replacement (3 days) Sr. No. Area Load (KN) 664.02 648.08 660.622 3 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 29.512 29.670 30.137 29.361

1. 2. 3.

22500

Table 4.7 Strength of 5% Silica fume & 20% metakaoline Replacement (3 days) Sr. No. Area Load (KN) 582.68 587.54 586.8 3 days strength of cubes Strength Avg. Strength (N/mm2) (N/mm2) 25.897 26.03 26.113 26.08

1. 2. 3.

22500

40

Results of 7 days strength of concrete Table 4.8 Strength of plain cement concrete (7 days)

Sr. No.

Area Load (KN) 855.22 821.7 805.38

1. 2. 3.

22500

7 days strength of cubes Strength Avg. Strength (N/mm2) (N/mm2) 38.01 36.775 36.52 35.795

Table 4.9 Strength of 10 % Metakaoline Replacement (7 days) Sr. No. Area Load (KN) 702.45 715.72 787.05 7 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 31.22 32.67 36.52 34.98

1. 2. 3.

22500

Table 4.10 Strength of 10 % Silica Fume Replacement (7 days) Sr. No. Area Load (KN) 747.0 708.97 711.45 7 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 33.2 32.11 31.51 31.62

1. 2. 3.

22500

Table 4.11 Strength of 5 % Silica Fume & 5 % Metakaoline Replacement (7 days) Sr. No. Area Load (KN) 693.67 697.95 713.7 7 days strength of cubes Strength Avg. Strength (N/mm2) (N/mm2) 30.83 31.20 31.02 31.75

1. 2. 3.

22500

41

Table 4.12 Strength of 5 % Silica Fume & 10 % Metakaoline Replacement (7 days) Sr. No. Area Load (KN) 756.67 776.476 821.92 7 days strength of cubes Strength Avg. Strength (N/mm2) (N/mm2) 33.63 34.89 34.51 36.53

1. 2. 3.

22500

Table 4.13 Strength of 5 % Silica Fume & 15 % Metakaoline Replacement (7 days) Sr. No. Area Load (KN) 773.77 819.22 793.8 7 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 34.39 35.36 36.41 35.28

1. 2. 3.

22500

Table 4.14 Strength of 5 % Silica Fume & 20 % Metakaoline Replacement (7 days) Sr. No. Area Load (KN) 776.925 741.82 739.8 7 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 34.53 33.46 32.97 32.88

1. 2. 3.

22500

42

Result of 28 days strength of concrete Table 4.15 Strength of Plain Cement Concrete (28 days) Area Load (KN) 987.3 918.45 951.525 28 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 43.88 42.33 40.82 42.29

Sr. No.

1. 2. 3.

22500

Table 4.16 Strength of 10 % Metakaoline Replacement (28 days) Sr. No. Area Load (KN) 949.5 942.525 913.275 28 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 42.20 41.56 41.89 40.59

1. 2. 3.

22500

Table 4.17 Strength of 10 % Silica Fume Replacement (28 days) Sr. No. Area Load (KN) 860.850 940.725 838.350 28 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 38.26 39.11 41.81 37.26

1. 2. 3.

22500

Table 4.18 Strength of 5 % Silica Fume & 5 % Metakaoline Replacement (28 days) Sr. No. Area Load (KN) 1017.675 1009.125 1093.050 28 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 45.23 46.22 44.85 48.58

1. 2. 3.

22500

Table 4.19 Strength of 5 % Silica Fume & 10% Metakaoline Replacement (28 days) Sr. No. Area 28 days strength of cubes Load Strength Avg. Strength (KN) (N/mm2) (N/mm2) 1062.675 47.23 47.56 1053.450 46.82 1094.175 48.63

1. 2. 3.

22500

43

Table 4.20 Strength of 5 % Silica Fume & 15 % Metakaoline Replacement (28 days) 28 days strength of cubes Load Strength Avg. Strength (KN) (N/mm2) (N/mm2) 1. 1192.95 53.02 22500 52.11 2. 1154.025 51.29 3. 1170.450 52.02 Table 4.21 Strength of 5 % Silica Fume & 20 % Metakaoline Replacement (28 days) Sr. No. Area Load (KN) 940.50 951.975 920.250 28 days strength of cubes Strength Avg. Strength 2 (N/mm ) (N/mm2) 41.80 41.67 42.31 40.9 Sr. No. Area

1. 2. 3.

22500

4.3 Strength behaviour of PCC against other cementitious materials for various durations Table 4.22 Results of Plain Cement Concrete for Various Durations For Plain Cement Concrete Sr. No. Area of Cubes Duration Strength (N/mm2) 1. 3 days 30.885 22500 2. 7 days 36.775 3. 28 days 42.33

For P.C.C
Compressive Strength (MPa) 50 40 30 20 10 0 3 7 Duration Fig. 4.1 compressive strength of P.C.C 28 For P.C.C

44

Discussion: As shown in table, Within 3 days concrete achieves more than half strength of designed strength. After 7 days it achieves nearly about 90% strength of designed strength. After 28 days it achieves full strength of designed strength. Table 4.23 Results of 10 % Replacement by Metakaoline for Various Durations For 10 % Replacement by Metakaoline Area of Cubes Duration 3 days 7 days 28 days P.C.C. Strength (N/mm2) 30.885 36.775 42.33

Sr. No. 1. 2. 3.

22500

Strength (N/mm2) 29.77 32.67 41.56

45 40 35 30 25 20 15 10 5 0 3 7 Duration 28

Compressive Strength (Mpa)

P.C.C 10 % Replacement by Metakaoline

Fig. 4.2 Strength of cement by 10 % Replacement by Metakaoline Discussion: As shown in table, Within 3 days concrete strength is almost equal to P.C.C. After 7 days strength of P.C.C is greater than concrete replacement by 10% metakaoline which is the turning point of increase in strength. After 28 days it achieves nearly 103% strength of design strength.

45

Table 4.24 Results of 10 % Replacement by Silica Fume for Various Durations For 10 % Replacement by Silica Fume Area of Cubes Duration 3 days 7 days 28 days P.C.C. Strength (N/mm2) 30.885 36.775 42.33

Sr. No. 1. 2. 3.

22500

Strength (N/mm2) 29.64 32.11 39.11

45 Compressive Strength (Mpa)

40
35 30 25 20 15 10 % Replacement by Silica Fume P.C.C

10
5 0 3 7 Duration 28

Fig. 4.3 Results of 10 % Replacement by Silica Fume Discussion: As shown in table, After 10% replacement by silica fume the strength achieves within 3 days is almost equal to strength of P.C.C. At 7 days strength of P.C.C is greater than 10% replacement by silica fume, after this sudden increasing of strength gain. But after 28 days it achieves about 97% strength of design strength which is slightly less than strength obtained by 10% replacement by metakaoline.

46

Table 4.25 Results of 5 % Replacement by Silica Fume & 5 % Metakaoline for Various Durations For 5 % Replacement by Silica Fume & 5 % Metakaoline Sr. No. Area of Cubes Duration Strength (N/mm2) 1. 3 days 26.97 22500 2. 7 days 31.20 3. 28 days 46.22 P.C.C. Strength (N/mm2) 30.885 36.775 42.33

50 Compressive Strength (Mpa) 45 40 35 30 25 20 15 10 5 0 3 7 Duration 28 5 % Replacement by Silica Fume & 5 % Metakaoline P.C.C

Fig. 4.4 Results of 5 % Replacement by Silica Fume & 5 % Metakaoline Discussion: As shown in table, After replacement by 5% each of silica fume & metakaoline strength achieves in 3 days is less than P.C.C. But after 7 days strength of concrete rapidly increase as days goes on increasing this is due to the property of both silica fume & metakaoline. At 28 days concrete achieves about 115% strength of design strength which is far better than 10% replacement by silica fume. Increasing of strength after 28 days indicate that 5% silica fume is an optimum percent to improve the compressive strength of concrete.Which also provide an idea about that we can increase the percentage of metakaoline to gain greater strength.

47

Table 4.26 Results of 5 % & 10 % Replacement by Silica Fume & Metakaoline for Various Durations For 5 % & 10 % Replacement by Silica Fume & Metakaoline Sr. No. Area of Cubes Duration Strength (N/mm2) 1. 3 days 26.67 22500 2. 7 days 34.89 3. 28 days 47.56 P.C.C. Strength (N/mm2) 30.885 36.775 42.33

50 45 Compressive Strength (Mpa) 40 35 30 25 20 15 10 5 0 3 7 Duration 28 5 % & 10 % Replacement by Silica Fume & Metakaoline

P.C.C

Fig. 4.5 Results of 5 % & 10 % Replacement by Silica Fume & Metakaoline Discussion: As shown in table, As usual P.C.C strength is greater than 5% & 10% replacement by silica fume & metakaoline in 3 days. After attending 3 days concrete strength linearly increase and achieves about 87% of design strength at 7 days. As shown in the graph after 7 days strength suddenly increases upto 28 days and gain 118% of design strength slightly greater than previous strength by 3%.

48

Table 4.27 Results of 5 % SF& 15 % MK Replacement for Various Durations For 5 % & 15 % Replacement by Silica Fume & Metakaoline Sr. No. Area of Cubes Duration Strength (N/mm2) 1. 3 days 29.67 22500 2. 7 days 35.36 3. 28 days 52.11 P.C.C. Strength (N/mm2) 30.885 36.775 42.33

60 Compressive Strength (Mpa) 50 40 30 20 10 0 3 7 Duration 28 5 % & 15 % Replacement by Silica Fume & Metakaoline P.C.C

Fig. 4.6 Results of 5 % & 15 % Replacement by Silica Fume & Metakaoline Discussion: As shown in table, After 3days strength of P.C.C & replacement concrete by 5% silica fume and 15% metakaoline are nearly equal. Similarly at 7 days strength of P.C.C & replacement concrete are almost equal; achieves about 88% strength of designed strength. After 7 days, strength of 5% & 10% replacement by silica fume & metakaoline are drastically increasing upto 28 days nearly about 130% strength of designed strength which is the highest strength achieved about all. From the above result its conclude that 5% silica fume & 15% metakaoline are the optimum percentage which provide 30% additional compressive strength to normal concrete

49

Table 4.28 Results of 5 % & 20 % Replacement by Silica Fume & Metakaoline for Various Durations For 5 % & 20 % Replacement by Silica Fume & Metakaoline Sr. No. Area of Cubes Duration Strength (N/mm2) 1. 3 days 26.03 22500 2. 7 days 33.46 3. 28 days 41.67 P.C.C. Strength (N/mm2) 30.885 36.775 42.33

45
Compressive Strength (Mpa) 40 35 30 25 20 15 10 5 0 3 7 Duration 28 5 % & 20 % Replacement by Silica Fume & Metakaoline P.C.C

Fig. 4.7 Results of 5 % & 20 % Replacement by Silica Fume & Metakaoline Discussion: As shown in result table, Typically strength of 5% silica fume & 20% metakaoline are slightly less than P.C.C. Again at 7 days strength of P.C.C is greater which was almost equal in case of 5% silica fume & 15% metakaoline. After 28 days strength become nearly equal obtained about 104% strength of designed strength. From this result its conclude that by increasing the percentage of silica fume & metakaoline above 5% & 10% does not give further compressive strength to concrete. Therefore 5% silica fume & 10% metakaoline are the optimum percentage of replacement of sand.

50

Following are the few graphs showing the comparative study of compressive strength 3 DAYS compressive strength(Mpa)
31 30.8 30.6 30.4 30.2 30 29.8 29.6 29.4 29.2 29 3 DAYS compressive strength(Mpa)

OPC 30.885

OPC+10%MK 29.77

OPC+10%SF 29.64

Fig.4.8 Comparison of 3 days Compressive Strength (MPa) between OPC, OP+10% MK & OPC+10% SF.

3 DAYS compressive strength(Mpa)

30 29 28 27

26
25 24 3 DAYS compressive strength(Mpa) 5SF+5MK 26.97 5SF+10MK 26.67 5SF+15MK 29.67 5SF+20MK 26.03

Fig 4.9 Comparison of 3 days Compressive Strength (MPa) between (5% SF+5% MK), (5% SF+10% MK), (5% SF+15% MK) & (5% SF+20% MK)

51

7 DAYS compressive strength(Mpa)

38 37 36

35
34 33 32 31 30 29 7 DAYS compressive strength(Mpa) OPC 36.775 OPC+10%MK 32.67 OPC+10%SF 32.11

Fig.4.10 Comparison of 7 days Compressive Strength (MPa) between OPC,(OP+10% MK) & (OPC+10% SF).

7 DAYS compressive strength(Mpa)

36

35
34 33 32 31 30 29 7 DAYS compressive strength(Mpa) 5SF+5MK 31.2 5SF+10MK 34.89 5SF+15MK 35.36 5SF+20MK 33.46

Fig.4.11 Comparison of 7 days Compressive Strength (MPa) between (5% SF+5% MK), (5% SF+10% MK), (5% SF+15% MK) & (5% SF+20% MK)

52

28DAYS compressive strength(Mpa)

43 42 41 40 39

38
37 28DAYS compressive strength(Mpa)

OPC 42.33

OPC+10%MK 41.56

OPC+10%SF 39.11

Fig.4.12 Comparison of 28 days Compressive Strength (MPa) between OPC, (OPC+10% MK) & (OPC + 10% SF) 28 DAYS compressive strength(Mpa)
60 50 40 30 20 10 0 28 DAYS compressive strength(Mpa)

5SF+5MK 46.22

5SF+10MK 47.56

5SF+15MK 52.11

5SF+20MK 41.67

Fig.4.13 Comparison of 28 days Compressive Strength (MPa) between (5% SF+5% MK), (5% SF+10% MK), (5% SF+15% MK) & (5% SF+20% MK)

53

60 50 40 30 20 10 0 OPC 3 DAYS compressive strength(Mpa) 7 DAYS compressive strength(Mpa) 28DAYS compressive strength(Mpa) 30.885 36.775 42.33

OPC+10% OPC+10% 5SF+10M 5SF+15M 5SF+20M 5SF+5MK MK SF K K K 29.77 32.67 41.56 29.64 32.11 39.11 26.97 31.2 46.22 26.67 34.89 47.56 29.67 35.36 52.11 26.03 33.46 41.67

Fig. 4.14 Effect on compressive strength as per curing days on various % of cement replacement . Discussion : This above graph shows the direct comparison between all the proportion taken quantitively for analysis. According to this it clearly show the benefits of using silica fume and metakaolin as a combination for substitute as a cementitious material.

54

Table 4.29 The following table shows the comparative study of compressive as well as the tensile strength of the cubes casted: Sr. Replacement levels (%) Compressive Strength (MPa) Split No. Tensile test result Silica Fume Metakaolin 3 days 7 days 28 days 28 days 1. 0 0 30.885 36.775 42.33 4.157 2. 10 0 29.77 32.67 41.56 3.287 3. 0 10 29.64 32.11 39.11 4.67 4. 5 5 26.97 31.20 46.22 2.55 5. 5 10 26.67 34.89 47.56 4.16 6. 5 15 29.67 35.36 52.11 3.86 7. 5 20 26.03 33.46 41.67 3.67 Fig.4.15 Effect on split tensile strength at 28 days curing on various % of cement replacement 28 days split tensile strength (Mpa)
5 4.5 4 3.5 3 2.5 2 1.5 1 0.5 0 OPC 28 days split tensile 4.157 strength (Mpa)

OPC+1 OPC+1 5SF+5 5SF+10 5SF+15 5SF+20 0%MK 0%SF MK MK MK MK 3.289 4.67 2.55 4.16 3.86 3.67

Discussion: As shown in the graph, At 28 days split tensile strength of O.P.C & 5% Silica fume & 10% metakaoline replacement concrete nearly equal there are no changes in split tensile strength. But 5% each replacement of silica fume & metakaoline show lowest split tensile strength of above all, while compressive strength remained greater than O.P.C. From above graph 10% replacement by silica fume provide the highest split tensile strength.

55

4.4. Behaviour of concrete in terms of compressive strength when tested in conventional and accelerated curing : Table .4.30. Showing effect of curing methods on concrete strength Mix Designation Concrete Grade Days of curing 28 28 28 28 Compresssive strength (N/mm2) Conventional 47.56 Conventional 52.11 Accelerated(Warm 39.23 water method) Accelerated(Warm 43.63 water method) Method of curing

5%SF+10%MK 5%SF+15%MK 5%SF+10%MK 5%SF+15%MK

M40 M40 M40 M40

Fig.4.16 Comparison between types of curing for compressive strength Comparison between types of curing for compressive strength
60 50 40

30
20 10 0 28 days conventional curing strength 28 days accelerated curing strength 5SF+10MK 47.56 39.23 5SF+15MK 52.11 43.63

Discussion: As shown in the graph, the compressive strength of concrete in 28 days is more in Conventional curing test as compared to accelerated curing test. From these results we can conclude that to achieve good strength of concrete conventional curing is better as compare to accelerated curing but even accelerated curing can produce effective results on proper control mixes.

The curing achieved here is0 done by the warm water method in which the temperature of

water being maintained at 55 C and kept fully immersed for appx. 20 hrs. As the curing is not done like immersing in water for longer period of time the gain in strength is quite appreciable.

56

4.5. Characteristics of concrete when placed in acidic solution : a. Effect on concrete by visual assessment : Table 4.31. Showing the effect of acid solution on concrete by visual inspection Mix Designation Concrete Grade 30 days cured specimen tested in 5% HCl solution in accordance with table no.4.6 OPC M40 4-5 0PC+10%MK M40 3-4 0PC+10%SF M40 2-3 5%SF+5%MK M40 3-4 5%SF+10%MK M40 2 5%SF+15%MK M40 2-3 5%SF+20%MK M40 4

Discussion :
Table above shows the summery of the visual assessment of the specimens after 4 weeks immersed in 5% HCl solutions. The edges and surfaces of all the specimens were maintained without any disintegration while immersed in acidic solutionand are observed for a period of 30 days. From the table, it was observed that the OPC specimen suffered a greater degree of acid attack than those of blended specimens in acid solutions. The deterioration of PCC specimens was ranging from severe attack to very severe attack in 5%HCL solution. Due to the expansive reactions, the specimens disintegrate and turned into a white pulpy mass in addition to peeling. The acid diffuses into concrete structure destroys the cement gel binder and forming soft and soluble gypsum (calcium sulphate hydrate), which reacts with C3A to form ettringite. The formation of secondary ettringite results in a substantial expansion of PCC specimens and leads to increase the degree of acid attack. The reduction of Ca(OH)2 in blended concrete reduces the formation of secondary ettringite and reduces the expansion of concrete specimens. The blended concrete specimens containing 5%SF+15%MK has suffered a moderate attack in 5% HCl solution. The 5%SF+10%MK blended concrete has shown slight attack in 28 days cured specimens. This is due to the development of dense concrete mass by reducing the micro pores and its sizes.

57

b. Effect of concrete specimen by mass loss due to acidic action: Table 4.32. Showing the effect of acid solution on concrete by loss of mass Mix Designation Concrete Grade Weight of Weight of Loss of mass Concrete blocks Concrete blocks of concrete due before after 30 days to acidic immersion in immersion in reaction acid solution acid solution (%) (kg) (kg) OPC M40 8.750 8.130 7.085 0PC+10%MK M40 8.560 8.180 4.439 0PC+10%SF M40 8.600 8.230 4.302 5%SF+5%MK M40 8.550 8.195 4.152 5%SF+10%MK M40 8.500 8.200 3.529 5%SF+15%MK M40 8.650 8.310 3.931 5%SF+20%MK M40 8.560 8.180 4.439 Fig.4.17 & 4.18. Showing graph of mass loss of concrete in acid solution
weight of concrete blocks (kg) 8.8 8.7 8.6 8.5 8.4 8.3 8.2 8.1 8 7.9 7.8 OPC

5%SF+ 5%SF+ 5%SF+ 0PC+1 0PC+1 5%SF+ 10%M 15%M 20%M 0%MK 0%SF 5%MK K K K 8.56 8.6 8.55 8.5 8.65 8.56

Weight of Concrete blocks before immersion in acid solution (kg) Weight of Concrete blocks after 30 days immersion in acid solution (kg)

8.75

8.13

8.18

8.23

8.195

8.2

8.31

8.18

8 7 6 5 4 3 2 1 0 OPC

% loss of mass in concrete

0PC+10 %MK 4.439

0PC+10 %SF 4.302

5%SF+5 5%SF+1 5%SF+1 5%SF+2 %MK 0%MK 5%MK 0%MK 4.152 3.529 3.931 4.439

Loss of mass of concrete due to acidic reaction (%)

7.085

58

Discussion : Figures above display the results of mass loss of control (OPCC) and blended concrete due to acid attack and the mass loss is consider as a function of time. The resistance of cement based materials to chemical attack is mainly due to permeability and alkalinity of concrete mass. The OPC mix suffered the most deterioration in terms of mass loss when immersed in 5% HCl solutions. The mass loss at 30 days cured M40 grade PCC specimens was 7.085%. reaches the 10% loss level within two weeks of immersion period in 5% H 2SO4. During the curing period, level of mass loss increases and it shows that the hydration process of cementitious materials was not fully completed within 28 days curing. The development of blended concrete with upto 20% MK replacement level reduces the mass losses considerably. The mass loss of specimens was approximately reduces 30% 40% mass loss of PCC when immersed in 5% HCl solutions. The minimum mass loss was observed in 5%SF+10%MK concrete only. The M40 grade specimens were shown only less than 10% mass loss within the observation period of 4 weeks. The results show that the resistance against the acid attack increased when cement replaced by SF and MK and the main reason for the increased acid resistance of blended concrete investigated was the formation of dense hardened cement paste and aggregate interface with low porosities. The formation of unstable ettringite causes the concrete matrix to be more porous and susceptible to the acid attack through the capillary pores . The development of ternary blended concrete with the optimum replacement levels shows the reduction of secondary unstable ettringite and reduces the acid attack considerably.

59

c. Effect of concrete specimen by strength loss due to acidic action: Table 4.33. Showing the effect of acid solution on concrete by strength loss Mix Designation Concrete 28 days Compressive Loss of Grade compressive strength of strength of strength on concrete cubes concrete due normal curing immersed in to acidic (N/mm2)(fcw) acidic solution reaction of 5% HCl (%) (N/mm2) (fca) OPC M40 42.33 32.44 23.36 0PC+10%MK M40 41.56 35.78 13.90 0PC+10%SF M40 39.11 35.12 10.20 5%SF+5%MK M40 46.22 36.44 21.16 5%SF+10%MK M40 47.56 44.00 7.48 5%SF+15%MK M40 52.11 44.00 15.56 5%SF+20%MK M40 41.67 33.78 18.93 Fig.4.19 & 4.20. Showing variation of loss of strength graphically
Compressive strength of cured concrete cubes 60 50 40 30 20 10 0 OPC 28 days compressive strength 42.33 for normally cured cubes compressive strength of 32.44 blocks cured in acidic solution 0PC+ 10% MK 41.56 35.78 0PC+ 10%S F 39.11 35.12 5%SF +5% MK 46.22 36.44 5%SF +10% MK 47.56 44 5%SF +15% MK 52.11 44 5%SF +20% MK 41.67 33.78

% loss of compressive strength

25 20

15 10
5 0 OPC 0PC+1 0%MK 0PC+1 0%SF 5%SF+ 5%MK 5%SF+ 10%M K 7.48 5%SF+ 15%M K 15.56 5%SF+ 20%M K 18.93

loss of compressive strength due to acidic action (%)

23.36

13.9

10.2

21.16

Discussion :

60

 The reduction of compressive strength due to acid attack was expressed in the form of strength deterioration factor (SDF). Figures above show the SDF at30 days cured specimens of M40 grade concrete immersed in 5% HCl solution. The PCC specimens are severely affected the acid attack and hence the SDF values of PCC specimens were more than 23%. The rate of change SDF for PCC specimen was observed as rapid change up to 4 weeks of immersion period. The SDF for 5%HCl were shown in figures above. Meantime the minimum SDF value of 7.48% was observed in 28 days cured M40 grade concrete after the immersion period of 4 weeks. The addition of SF and MK in concrete specimens consumes Ca(OH)2 and develop the secondary hydration products (C-S-H gel) which reduces the micro pores of concrete and makes dense concrete mass. The ternary blended concrete specimens are less affected than that of the binary and control concrete mixes immersed in 5% HCl solutions. The presence of SF offered the resistance against permeability during early ages and the MK contents prevents the entry of acidic solutions during the latter ages. The ternary blended combination increases the impermeability of concrete in the higher order and hence the observed SDF values were very less than that of the other mixes.

61

Chapter-5
CONCLUSION
Compared to the findings of other studies, it appears that the results of this study do not cohere with some of the studies although there are some studies agree the optimum metakaolin replacement is around 10%. Still now the optimum percentage of silica fume alone in testing produced good results for replacement by upto 10 % where as some study shows that the optimum is upto 7% . Nevertheless there has been less information regarding the effect on combination for both when replaced as a combined blend. These variations are not surprising as the products of hydration and pozzolanic activity depend on the Portland cement composition, the purity of the metakaolin and the silica fume along with the water-binder ratio. In this study, the kaolin samples have silica and alumina content of 81% in accordance with silica fume influence .It is considered that the kaolin has a high purity and high kaolinite content. As a result, 15% replacement is sufficient to reduce the calcium hydroxide to the minimum level and attains the highest compressive strength in 28 days. From the study, it is clearly reveals that the strength performance of metakaolin is influenced. The performance of metakaolin has increased with the increment in replacement levels until it reach the optimum strength. Subsequently, the concretes strength is further enhanced by the pozzolanic reaction.

From the study, it can be concluded that: Metakaolin is an effective pozzolan and results in enhanced early strength and ultimate strength of concrete. Similarly the silica fume used has also enhanced the strength with age of concrete. The compressive strength of young concrete, say from 1 to 3 days is however for the control mix was greater but the mix with 5%SF +15%MK also shows good enhancement of compressive strength. Thus the compressive strength so achieved for 28 days is highest for the mix of 5%SF and 15% MK in combination. Thus proving that the maximum replacement can be upto 20 % of cement which can boost the realization of making better and maximum replacement so as to make the construction work worth effective as well as pollution free. With such type of multiple formulas even the wastes out of the factories could be effectively used for the recycling and have proper beneficiary utilization. This is the century for where the demand of construction has grown larger and larger also will look for cost effective. With this study it shows that even the tensile strength can be improved. The maximum tensile strength so obtained is for the 10% replacement by SF . Silica fume which is known as highly impermeable material also indulges its properties in the blend and provides effective solutions to leakages in concrete. Also for the accelerated curing the results shown were compared between the two best proportions within the blend. It gives appropriately fair results with maximum gain of strength upto 80% . Thus it also proves that conventional method of curing being time consuming gives better results for strength gain than any other methods.

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The PCC specimens of M40 grade concrete were severely deteriorated after immersion in 5%HCl solutions up to 4 weeks. The 28 days cured binary blended concrete specimens were suffered moderate acid attack. The 28 days cured ternary blended concrete specimens were suffered slight acid attack. The mass loss within the concrete was the maximum for OPC condition where as moderate for the binary and least for the ternary conditions. Thus as the acid concentration was being maintained throughout the immersion period of 4 weeks in HCl solution still it shows appropriate mass loss and strength deterioration. Even during strength deterioration the most drastically affected was the OPC cubes where as the least affected was the ternary cubes. Thus it proves that when cement is blended with certain pozzolanic materials it gives better results against durability and is safer than the normal cement concrete .

Thus in order to ensure that the project was a intilization of whether the blended concrete can work better and as per the results and conclusion it can be stated that this blend can give effective results and in mere future can be used with worth.

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Photographs related to experimental work done regarding the project

Mixing of ingredients to make concrete cubes

Slump cone test taken in order to ensure the water content and compatibility of concrete

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Figure shows the vibration of the cube mould after being casted to required volume

Figure shows the compressive test being carried out on blocks after curing for sufficient period

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Figure shows the compressive test being carried out on blocks after curing for sufficient period

Figure shows the compressive test being carried out on blocks after curing for sufficient period

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Figure shows the compressive test being carried out on blocks after curing for sufficient period

Failure of concrete cubes at optimum loading condition

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Failure of concrete cubes at optimum loading condition

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BIBLIOGRAPHY
A review for characterization of silica fume and its effects on concrete properties by Mohammad Panjehpour1*, Abang Abdullah Abang Ali1, Ramazan Demirboga1, Dunster, A.M., Parsonage, J.R. and Thomas, M.J.K. (1999). Pozzolanic Reaction of Metakaolinite and Its Effects on Portland Cement Hydration. J. Mater. Sci: 13451350. Kostuch, J.A., Walters V. and Jones, T.R. (2000) High Performance Concretes Incorporating Metakaolin: A Review. University of Dundee. D.D.L.Chung (2002), Review improving cement-based materials by using silica fume, Journal of material science, composite materials research laboratory, state university of New York at Buffalo, USA M. Mazloom, A.A. Ramezanianpour, J.J. Brooks (2004), Effect of silica fume on mechanical properties of high-strength concrete. H. Abdul Razak, H.S. Wong (2004), Strength estimation model for high-strength concrete incorporating metakaolin and silica fume. S.Bhanja, B.Sengupta (2004), Influence of silica fume on the tensile strength of concrete. Cement and concrete research Jadavpur University Kolkata, West Bengal, India. Ali Behnood, Hasan Ziari (2007), Effect of silica sume addition and water to cement ratio on the properties of high-strength concrete after exposure to high temperature. Properties of concrete with metakaolin and fly ash as partial replacement to Cement Supriya K. Nalawade, Hemalata K. Munot, Balkrishna Dawari Assistant Professor, College of Engineering Pune-411005 Brooks JJ, Megat Johari MA (2001) Effect of metakaolin on creep and shrinkage of concrete. Cem Concr Comp Bai J, Sabir BB, Wild S, Kinuthia J (2000) Strength development in concrete incorporating PFA and metakaolin Guneyisi E, Mermerdas K (2007) Comparative study on strength, sorptivity, and chloride ingress characteristics of aircured and water-cured concretes modified with metakaolin. Mater Struct A comparative study of the effects of Silica fume, metakaolin and pfa on the Air content of fresh concrete G Christodoulou , School of Technology, University of Glamorgan, Pontypridd, CF37 1DL, UK

Pozzolanic and Cementitious materials, Ed.V.M. Malhotra and P.K Mehta, Gordon and Preach Publishers, 1996.

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Sabir B.B, Wild S. and Khatib J. On the workability and strength development of metakaolin concrete In International Congress on Concrete in the service of Mankind, Concrete for Environment Enhancement and Protection, Theme 6, Waste Materials and Alternative Products, University of Dundee (eds R.K Dhir and D.T. Dyer) Spon, London, 1996, pp.651662. Comparison of Two Metakaolins and a Silica Fume Used as Supplementary Cementitious Materials J.M. Justice, L.H. Kennison, B.J. Mohr, S.L. Beckwith, L.E. McCormick, B. Wiggins, Z.Z. Zhang, and K.E. Kurtis Chan YN, Luo X, Sun W (2000) Compressive strength and pore structure of high performance concrete after exposed to high temperature up to 800_C. Cem Concr .

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