SETTING OF CEMENT

INTORDUCTION
In the most general sense of the word, cement is a binder, a substance which sets and hardens independently, and can bind other materials together. The most important use of cement is the production of mortar and concrete - the bonding of natural or artificial aggregates to form a strong building material which is durable in the face of normal environmental effects.

CEMENT
Cement is the most common type of cement in general usage in many parts of the world, as it is a basic ingredient of concrete, mortar, stucco and most non-specialty grout. It is a fine powder produced by grinding Portland cement clinker (more than 90%), a limited amount of calcium sulfate which controls the set time, and up to 5% minor constituents (as allowed by various standards). "Portland cement clinker is a hydraulic material which shall consist of at least two-thirds by mass of calcium silicates (3CaO.SiO2 and 2CaO.SiO2), the remainder consisting of aluminium- and iron-containing clinker phases and other compounds. Normally, an impure limestone which contains SiO2 is used. The CaCO3 content of these limestones can be as low as 80%. Secondary raw materials (materials in the rawmix other than limestone) depend on the purity of the limestone. Some of the secondary raw materials used are: clay, shale, sand, iron ore, bauxite, fly ash and slag. When a cement kiln is fired by coal, the ash of the coal acts as a secondary raw material. Cement is essentially a finely ground mixture of calcium silicates (3CaO.SiO2) and aluminates (3CaO.Al2O3) which sets to a hard mass when treated with water. This property makes cement capable of joining rigid masses like bricks, stones, tiles etc. into coherent structures. The cements have property of setting and hardening under water due to certain physicochemical process and are, therefore, called hydraulic cements. During setting of cement, the physical changes taking place are gel formation and crystallization and chemical changes are hydration and hydrolysis.

The process of solidification of cement paste involves:

(i) Setting, and (ii) Hardening.
Setting is stiffening of the original plastic mass into initial gel formation. After setting, hardening starts due to gradual start of crystallization in the interior of the mass. The strength developed by cement at any time depends upon the amount of gel formed and the extent of crystallization. A mixture of cement, sand, small pieces of stone (gravel) and water are known as concrete and sets to an extremely hard structure.

(3)

TYPES OF CEMENTS
(A). The various types of Cement on the basis of Chemical compositions are:1. Pozzolan-lime cements. Mixtures of ground pozzolan and lime are the cements used by the Romans, and are to be found in Roman structures still standing (e.g. the Pantheon in Rome). They develop strength slowly, but their ultimate strength can be very high. The hydration products that produce strength are essentially the same as those produced by Portland cement. 2. Slag-lime cements. Ground granulated blast furnace slag is not hydraulic on Its own, but is activated by addition of alkalis, most economically using lime. They are similar to pozzolan lime cements in their properties. Only granulated slag (i.e. water-quenched, glassy slag) is effective as a cement component. 3. Supersulfated cements. These contain about 80% ground granulated blast furnace slag, 15% gypsum or anhydrite and a little Portland clinker or lime as an activator. 4. Calcium aluminate cements are hydraulic cements made primarily from limestone and bauxite. The active ingredients are monocalcium aluminate and Mayenite. Strength forms by hydration to calcium aluminate hydrates. 5. Portland cements. Portland cement, is made primarily from limestone, certain clay minerals, and gypsum, it is made by heating limestone with small quantities of other materials (such as clay) to 1450C in a kiln. The resulting hard substance, called clinker, is then ground with a small amount of gypsum into a powder to make Ordinary Portland Cement.

(4)

(B). Various types of Cement on the basis of Setting of cement are:1. Hydraulic cements.Hydraulic cements are materials which set and harden after combining with water, as a result of chemical reactions with the mixing water and, after hardening, retain

strength and stability even under water. The key requirement for this is that the hydrates formed on immediate reaction with water are essentially insoluble in water. Most construction cements today are hydraulic, and most of these are based upon Portland cement, which is made primarily from limestone, certain clay minerals, and gypsum, in a high temperature process that drives off carbon dioxide and chemically combines the primary ingredients into new compounds. The reaction and the reaction products are referred to as hydration and hydrates or hydrate phases, respectively. As a result of the immediately starting reactions, a stiffening can be observed which is very small in the beginning, but which increases with time. After reaching a certain level, this point in time is referred to as the start of setting. The consecutive further consolidation is called setting, after which the phase of hardening begins. 2. Non-Hyraulic cements.They dont require the availability of water to set into a hard compressed material. Some of the cement categorised under it are Calcium aluminate cements, Supersulfated cement etc.

MATERIALS USED WITH CEMENT

1. Fly Ash
Fly ash is the finely divided mineral residue resulting from the combustion of coal in electric generating plants. Fly ash consists of inorganic, incombustible matter present in the coal that has been fused during combustion into a glassy, amorphous structure.

2. Rice husk
Rice husks are a class A insulating material because they are difficult to burn and less likely to allow moisture to propagate mold or fungi. It was found out that rice husks when burned produced amounts of silica. For these reasons it provides excellent thermal insulation.

3. Lime mortar
Lime mortar is created by mixing sand, slaked lime and water. Limestone is burnt in a kiln to form quicklime. The quicklime is then slaked (mixed with water) to form slaked lime, either in the form of lime putty or of hydrated lime powder. This is then mixed with sand and water to form mortar. (5)

SETTING AND HARDENING OF CEMENT

The setting and hardening of cement occurs in various steps, abiding all the chemical reactions taking place in it. 1. When water is mixed with cement, the product sets in a few hours and hardens over a period of weeks. 2. These processes can vary widely depending upon the mix used and the conditions of curing of the product, but a typical cement mixture sets in about 6 hours, and develops a compressive strength of 8 MPa in 24 hours. The strength rises to 15 MPa at 3 days, 23 MPa after a week and 35 MPa at 30 days. In principle, the strength continues to rise slowly as long as water is available for continued hydration, but concrete is usually allowed to dry out after a few weeks, and this causes strength growth to stop. 3. Setting and hardening of cement is caused by the formation of water-containing compounds, forming as a result of reactions between cement components and water. 4. Usually, cement reacts in a plastic mixture only at water/cement ratios between 0.25 and

0.75. The reaction and the reaction products are referred to as hydration and hydrates or hydrate phases, respectively. 5. As a result of the reactions (which start immediately), a stiffening can be observed which is very small in the beginning, but which increases with time. The point in time at which it reaches a certain level is called the start of setting. The consecutive further consolidation is called setting, after which the phase of hardening begins. 6. Stiffening, setting and hardening are caused by the formation of a microstructure of hydration products of varying rigidity which fills the water-filled interstitial spaces between the solid particles of the cement paste, mortar or cement. 7. The behavior with time of the stiffening, setting and hardening therefore depends to a very great extent on the size of the interstitial spaces, i. e. on the water/cement ratio. 8. The hydration of these compounds and the properties of the calcium silicate hydrates produced are therefore particularly important. The simplified reaction of alite with water may be expressed as: 2Ca3OSiO4 + 6H2O --- 3CaO.2SiO2.3H2O + 3Ca(OH)2 This is a relatively fast reaction, causing setting and strength development in the first few weeks. 9. The reaction of belite is: 2Ca2SiO4 + 4H2O ---3CaO.2SiO2.3H2O + Ca(OH)2 This reaction is relatively slow, and is mainly responsible for strength growth after one week. 10. Calcium sulfates dissolve completely and alkali sulfates almost completely. Short, hexagonal needle-like ettringite crystals form at the surface of the clinker particles as a result of the reactions between calcium- and sulphate ions with tricalcium aluminate. 11. This third period (accelerated period) starts after approximately four hours and ends after 12 to 24 hours. During this period a basic microstructure forms, consisting of C-S-H needles and C-S-H leafs, platy calcium hydroxide and ettringite crystals growing in longitudinal shape. Due to growing crystals, the gap between the cement particles is increasingly bridged. The density of the microstructure rises and the pores fill: the filling of pores causes strength gain.

PHYSICAL PROPERTIES OF CEMENT

STRENGTH OF CEMENT
Concrete has relatively high compressive strength, but significantly lower tensile strength (about 10% of the compressive strength). As a result, concrete always fails from tensile stresses even when loaded in compression. The practical implication of this is that concrete elements subjected to tensile stresses must be reinforced. The ultimate strength of concrete is influenced by the water-cement ratio (w/c) [watercementitious materials ratio (w/cm)], the design constituents, and the mixing, placement and curing methods employed. All things being equal, concrete with a lower water-cement (cementitious) ratio makes a stronger concrete than a higher ratio. The characteristics of the cementitious content, coarse and fine aggregates, and chemical admixtures determine the water demand of the mix in order to achieve the desired workability. The 28 day compressive strength is obtained by determination of the correct amount of cementitious to achieve the required water-cement ratio. Only with very high strength concrete does the strength and shape of the coarse aggregate become critical in determining ultimate compressive strength. The internal forces in certain shapes of structure, such as arches and vaults, are predominantly compressive forces, and therefore concrete is the preferred construction material for such structures.

ELASTICITY
The modulus of elasticity of concrete is relatively linear at low stress levels but becomes increasingly non-linear as matrix cracking develops. The elastic modulus of the hardened paste may be in the order of 10-30 GPa and aggregates about 45 to 85 GPa. The concrete composite is then in the range of 30 to 50 GPa.

EXPANSION AND SHRINKAGE

Concrete has a very low coefficient of thermal expansion. However if no provision is made for expansion very large forces can be created, causing cracks in parts of the structure not capable of withstanding the force or the repeated cycles of expansion and contraction. As concrete matures it continues to shrink, due to the ongoing reaction taking place in the material, although the rate of shrinkage falls relatively quickly and keeps reducing over time (for all practical purposes concrete is usually considered to not shrink any further after 30 years). The relative shrinkage and expansion of concrete and brickwork require careful accommodation when the two forms of construction interface. Because concrete is continuously shrinking for years after it is initially placed, it is generally accepted that under thermal loading it will never expand to it's originally-placed volume.

ADMIXTURES AND COMPATIBILITY

Admixtures are chemicals added to concrete in small quantities for a specific function (for example water-reducing, set-retarding, or set-accelerating). These chemicals affect the hydration and/or are adsorbed by the cement particles. Certain combinations of chemicals and cement properties may adversely affect the setting behavior and be deemed incompatible. Examining the chemistry of the hydration reactions and the components of the cement can give clues to the source of the incompatibility.

STRENGTH GAIN
The ultimate compressive strength and rate of strength development of concrete is strongly influenced by the chemical reactivity of the portland cement. Varying hydration rates of the different cement compounds can help explain how the relative proportions of these compounds affect the rate of strength gain. For instance, the C2S reacts slowly and contributes to longterm strength gain. C3S, on the other hand, has a much faster hydration rate, and contributes to higher early-strength gain. Thus, cement with a higher proportion of C3S as is the case with most of todays cements will tend to have a higher early strength, and allow for early form removal or post-tensioning. Graph plotted b/w strength of the cement compositions vs. the time provided to it for setting.

Effect of quality of sand on the setting of cement mortar. Sand obtained from different sources has different qualities. For example, sea sand obtained from sea contains some unwanted salts and retards the setting of cement and is unsuitable for making mortar. On the other hand, pit sand obtained from pits in the soil and river sand obtained from the river bed are considered excellent for preparing mortar and concrete. Effect of time on setting of cement mortar. Time has an important role on the strength developed by cement mortar. When a cement sand paste in the ratio 1:3 in the water is allowed to dry, the strength of the solid mass keeps on increasing with increase in the time

given for setting. It acquires nearly full strength in 28 days.

WEARING OF CEMENT
1. Aggregate expansion
Various types of aggregate undergo chemical reactions in concrete, leading to damaging expansive phenomena. The most common are those containing reactive silica, that can react (in the presence of water) with the alkalis in concrete (K2O and Na2O, coming principally from cement). Among the more reactive mineral components of some aggregates are opal, chalcedony, flint and strained quartz. Following the reaction (Alkali Silica Reaction or ASR), an expansive gel forms, that creates extensive cracks and damage on structural members. On the surface of concrete pavements the ASR can cause pop-outs, i.e. the expulsion of small cones (up to 3 cm about in diameter) in correspondence of aggregate particles. When some aggregates containing dolomite are used, a dedolomitization reaction occurs where the magnesium carbonate compound reacts with hydroxyl ions and yields magnesium hydroxide and a carbonate ion. The resulting expansion may cause destruction of the material. Far less common are pop-outs caused by the presence of pyrite, an iron sulfide that generates expansion by forming iron oxide and ettringite. Other reactions and recrystallizations, e.g. hydration of clay minerals in some aggregates, may lead to destructive expansion as well.

2. Sea water effects

Concrete exposed to sea water is susceptible to its corrosive effects. The effects are more pronounced above the tidal zone than where the concrete is permanently submerged. In the submerged zone, magnesium and hydrogen carbonate ions precipitate about 30 micrometers thick layer of brucite on which a slower deposition of calcium carbonate as aragonite occurs. These layers somewhat protect the concrete from other processes, which include attack by magnesium, chloride and sulfate ions and carbonation. Above the water surface, mechanical damage may occur by erosion by waves themselves or sand and gravel they carry, and by crystallization of salts from water soaking into the concrete pores and then drying up. Pozzolanic cements and cements using more than 60% of slag as aggregate are more resistant to sea water than pure Portland cement.

3. Bacterial corrosion
Bacteria themselves do not have noticeable effect on concrete. However, anaerobic bacteria (Thiobacillus) in untreated sewage tend to produce hydrogen sulphide, which is then oxidized by aerobic bacteria present in biofilm on the concrete surface above the water level to sulphuric acid which dissolves the carbonates in the cured cement and causes strength loss. Concrete floors lying on ground containing pyrite are also at risk. Using limestone as the aggregate makes the concrete more resistant to acids, and the sewage may be pretreated by ways increasing pH or oxidizing or precipitating the sulphides in order to inhibit the activity of sulphide utilizing bacteria.

4. Chemical attacks
1. Carbonation & leaching
Due to some chemical reactions taking place on the surfaces of the concrete some times the cement mixtures yield SO2 and CO2 gases. This mostly is visible when the concrete is exposed to various forms of chemical attacks in form of acid rains.

2. Chlorides
Chlorides, particularly calcium chloride, have been used to shorten the setting time of concrete. However, calcium chloride and (to a lesser extent) sodium chloride have been shown to leach calcium hydroxide and cause chemical changes in Portland cement, leading to loss of strength, as well as attacking the steel reinforcement present in most concrete.

3. Sulphates
Sulphates in solution in contact with concrete can cause chemical changes to the cement, which can cause significant microstructural effects leading to the weakening of the cement binder.

4. Physical damage
Physical damages of concrete can already occur during the casting and de-shuttering processes. The corners of beams for instance, can damage during the removal of its shutter because these areas are less effectively compacted by means of vibrations. Other physical damages can be caused by the use of steel shuttering without base plates. The steel shuttering pinches the top surface of a concrete slab due to weight of the next slab being constructed.

PROJECT
Experiment to study Setting of Cement
OBJECTIVE OF PROJECT
In this project, we will study the setting of mixtures of cement with lime and sand and the effect of relative proportion of their masses, the effect of time and the effect of quality of the sand on the strength of cement mortar.

Experiment-1
AIM
To study the setting of mixtures of cement with lime, sand of different qualities, rice husk, flyash, etc. (with respect to volume and strength).

REQUIREMENTS
Beakers, glass rod, weights, small wooden boxes or empty matchboxes. Lime, pits sand, river sand, Portland cement, fly ash, rice husk.

PROCEDURE
1. Prepare the sets of mixtures of various compositions as given in the following table. 2. Take each of the mixtures in different beakers and prepare their pastes by adding minimum quantity of water. 3. Take 10 empty matchbox inner cases and marks them from 1 to 10. 4. Transfer the prepared pastes immediately into the matchboxes and compact them by pressing with hand. 5. Spray water from time to time over the pastes so that they are always moist. 6. Take out the slabs after three days and test for its strength. For that hold a weight on the slab. See if the slab breaks or not. If it does not break then take 20 g weight and drop it from the same height. This way keep on increasing the weight and not down the minimum weight required to break the slab.

OBSERVATIONS
Table. Effect of various types of sand on strength of slab S.No. Composition of mortar (Ratio by volume of various components) Minimum weight required to break the slab Cement River sand Pit sand Lime Fly-ash Rice-husk 1. 1 3 - - - - 175 g 2. 1 6 - - - - 175 g 3. 1 - 3 - - - 375g 4. 1 - 6 - - - 225 g 5. 1 6 - - 1 - 125 g 6. 2 9 - - 1 - 275 g 7. 1 3 - 1 - - 325 g 8. 1 3 - 2 - - 275 g 9. 1 1 - - - 1 375 g 10. 1 3 - - - 2 275 g

CONCLUSION
After 3 days. 1. The sample showing the maximum strength is the sample mixture of cement and rice husk, which is in the weight ratio of 1:1 (375 g). 2. The sample showing the minimum strength is the sample mixture of cement and river sand with weight ratio 1:3 or 1:6 (175 g).

Experiment-2
AIM
To study the setting of mixtures of cement with sand, lime and fly-ash with respect to time and strength.

RREQUIREMENTS
Beakers, glass rod, weights, small wooden boxes or empty match boxes. Lime, pits sand, river sand, Portland cement, fly-ash, rice husk.

PROCEDURE
1. Prepare mixtures of the various compositions as given in the following table. 2. Take each of the mixtures in different beakers and prepare their pastes by adding minimum quantity of water. 3. Take nine empty matchbox inner cases and mark them from 1 to 9. 4. Fill three cases with paste of each composition. 5. Spray water from time to time over the pastes so that they remain moist all the time. 6. After three days take out one slab of each composition and test for their strength by the method described in the previous method. 7. Similarly, take out a set of three slabs after 7 days and then after 30 days and test for their strengths.

OBSERVATIONS
Table - Effect of setting time cement on strength
S.No. Composition of mixtures Minimum weight required to break the slab after 3 Days 7 Days 30 days 1. Cement: River sand1: 3 175 g 275 g 2375 g 2. Cement: River sand: Fly-ash2: 9 : 1 275 g 175 g 1575 g 3. Cement: River sand: Lime1: 3 : 1 325 g 325 g 1875 g

CONCLUSIONS
After 3 days 1. After 3 days of setting of cement the sample of cement, which shows maximum strength, is the mixture of 1:3:1 weight by ratio of cement, river sand and fly-ash (325 g).

2. The sample, which shows least strength is, Cement along with river sand, is in ratio of 1:3 by weight (175 g). After 7 days 1. Now the sample showing maximum strength is the sample mixture of cement, river sand and lime with weight ratio of 1:3:1 respectively (325 g). 2. Now the sample showing least strength is the sample mixture of cement, river sand and flyash with weight ratio of 2:9:1 respectively (175 g). After 30 days 1. The slab showing maximum strength is, the sample mixture of cement and river sand with weight ratio of 1:3 respectively (2375 g). 2. The slab showing minimum strength is, the sample mixture of cement, river sand and flyash with weight ratio of 2:9:1 respectively (1575g). Therefore, its shows that the strength of the slab increases with increase in the setting time allowed.

COMBINED RESULT
The strength of cement sample need not depend on the addition of the impurity, but also depends on the type of time provided to the sample to make sure that it is well set. The strength also depends on the combination of time and type of impurities added to it and hence subjecting the sample to necessary tasks. As mentioned earlier the setting of cement involves the structure-based reactions taking place in the cement composition. Thus, we observe that in certain compositions, the strength after 3 days may be high but after many days of setting of cement, the cement may become weak eg. 1. The cement sample of composition of cement and fly-ash which had strength of 275g in 3 days, but after 30 days its strength was found our to be 1575 g which is the least in comparison to all other samples. 2. Also the composition of river sand and cement shows minimum strength in the beginning but through the passage of time the composition mixture become stronger and stronger. In comparison to other samples after 3 days of setting the strength of the cement is 175 g initially but after 30 days it becomes 2375 g which is a phenomenal increase. Below is a table that relates changes in cement to changes in concrete. The complex interactivity of all the properties of cement means that it is not possible to quantify the effects discussed. The intention of this table is to provide general guidance and trends rather than fixed relationships. Thus, proves that the cement properties does not necessarily depend on the materials and time of setting period allowed to it. Concrete Properties Cement Characteristic* Increasing C3S (decreasing C2S) Increasing C3A (decreasing C4AF) Increasing alkalies Increasing sulfate Increasing minor components Increasing fineness Increasing steepness of particle size distribution Admixture incompatibility Possible Possible Possible Possible Possible Air content Increases Decreases Bleeding Decreases Decreases Decreases Chloride binding Increases Chloride permeability Decreases Heat of hydration Increases Increases Increases Increases Reactivity with SCM Increases Increases

Risk for ASR Increases Setting time Decreases Decreases Flash set possible Changes Increases for some like F-and P2O5 Decreases Decreases Shrinkage Decreases Decreases Increases Slump loss Increases Decreases Increases Strength Increases Increases Early strengths up, late strengths down Increases Increases Sulfate resistivity Decreases Water requirement Increases Increases Increases Increases Increases Workability Decreases Decreases Decreases * Assuming only a change in one given component. This is unlikely to happen in reality because of the complexity of the portland cement system. For example, a change in clinker sulfate is almost always accompanied by a change in alkali content. A change in gypsum content is likely to be associated with a change in fineness as the plant operator seeks to control setting times and early strengths.