CIVE 1002(Y) ENGINEERING MATERIALS

Hydraulic BindersPROPERTIES OF MATERIALS

Mrs B K Ramjeeawon

Lecture Outline
Hydraulic binder: cement
Manufacture of Portland Cement Basic Chemistry of Cement Hydration of Cement Heat Of Hydration And Strength Tests On Cement Types Of Portland Cement

Brief History
Cementing materials have been used since ancient Egyptian and Roman times. Egyptians used calcined impure gypsum while Romans and Greeks used calcined limestone Later sand, crushed stone or brick and broken tiles were added to this lime and water mixture producing the first concrete in history Because of limited use of lime under water, Romans have ground together lime and a volcanic ash or finely ground burnt clay tiles

Brief History
The active silica and alumina in the ash and the tiles combined with the lime producing Pozzolanic cement The name was derived from the village of Pozzuoli near Vesuvius, where the volcanic ash was first found. The quality and use of cement declined in the Middle Ages It was only in the 18th century that John Smeaton recognised the importance of clay in good quality mortar; he was the first to understand the chemical properties of hydraulic lime

Manufacture of Portland Cement

Portland cement was developed in 1824 and derives its name from Portland limestone in Dorset because of its close resemblance to this rock after hydration has taken place. The basic raw materials used in the manufacture of Portland cements are calcium carbonate, found in calcareous rocks such as limestone or chalk, and silica, alumina and iron oxide found in argillaceous rocks such as clay or shale.

Manufacture of Cement Wet Process

Mixing may be in dry or wet state; wet process is used, in general, for softer materials such as chalk or clay. Water added to produce slurry which is eventually led off to a kiln Clinker formed by diffusion between solid particles, therefore intimate mixing essential for producing uniform cement

Intimate grinding and mixing of the raw materials in certain proportions

Slurry fed at the upper end of the kiln and clinker is discharged at the lower end where fuel is injected; with temperature increasing progressively, slurry undergoes a number of changes as it travels down the kiln

Burning of this mixture at very high temperature to produce clinker

Manufacture of Cement contd

Done on a steel cylinder, with a refractory lining, slightly inclined to the horizontal and rotates continuously about its own axis 3.5m dia and 150m long At 100oC, water evaporates; at about 850oC CO2 is given off and at about 1400oC incipient fusion takes place in the firing zone where calcium silicates and calcium aluminates are formed in the resulting clinker

Burning of this mixture at very high temperature to produce clinker

Clinker allowed to cool and then ground, with 1 to 5 percent of gypsum (calcium sulphate) to required fineness

Grinding it into powder form

CEMENT

Manufacturing Process

Manufacture of Cement
Different types of Portland cements are obtained by varying the proportions of the raw materials, the temperature of burning and the fineness of grinding. And, in some cases, by intergrinding the clinker with other recognised materials such as PFA (pulverished-fuel ash) or granulated blastfurnace slag.

Gypsum is added to regulate the setting of concrete when mixed with water, which would otherwise set much too quickly for general use. Certain additives may also be introduced for producing special cements, e.g., calcium chloride is added in the manufacture of extra-rapid-hardening-cement.

Manufacture of Cement
Dry or semi-dry process is used for the harder rocks such as limestone and shale. The constituent materials are crushed into powder form and, with a minimum amount of water, passed into an inclined rotating nodulising pan where nodules are formed. These are known as raw meal. This is fed into a kiln and thereafter the manufacturing process is similar to the wet process although a much shorter kiln is used. It should be noted that the dry and semi-dry processes are more energy efficient than the wet process.

Manufacture of Portland Cement

The grinding of the clinker produces a cement powder which is still hot and this hot cement is usually allowed to cool before it leaves the cement works. A wide range of cement is produced by incorporating other materials during manufacture including air-entraining cement and combinations of Portland Cement with mineral additions.

Cement
The different cements used for making concrete are finely ground powders and all have the important property that when mixed with water, a chemical reaction (hydration) takes place which, in time, produces a very hard and strong binding medium for the aggregate particles. The following table shows the different types of concrete. Of these, Portland Cement is the most widely used, the others being used where concretes with special properties are required.

Basic Chemistry of Cement

All Portland Cements contain the same active compounds only the proportion of each is different:
Tricalcium silicate, C3S 3CaO.SiO2 Dicalcium silicate, C2S 2CaO.SiO2 Tricalcium aluminate, C3A 3CaO.Al2O3 Tetracalcium aluminoferrite, C4AF 4CaO.Al2O3.Fe2O3

 The calculation of the potential composition of Portland cement is based on the work of R H Bogue and others. The Bogue Composition:
C3S = 4.07(CaO) 7.60(SiO2) 6.72(Al2O3) 1.43(Fe2O3) 2.85(SO3) C2S = 2.87 (SiO2) 0.754(3CaO.SiO2) C3A = 2.65(Al2O3) 1.69(Fe2O3) C4AF = 3.04(Fe2O3)

Chemical Composition

Terms in bracket represent the percentage of the given oxide in the total weight of cement

 It is to be noted that the Bogue composition underestimates the C3S content (and overestimates the C2S) because other oxides replace some of the CaO in C3S Three minor compounds of cement amounting to not more than a few % of the weight of cement:
MgO, TiO2, Mn2O3, K2O and Na2O

Chemical Composition

The oxides of potassium and sodium, known as the alkalis, have been found to react with some aggregates, the products causing disintegration of concrete; they also affect the rate of gain of strength of cement

Main Compounds: Role in Cement

The silicates, C2S and C3S, are the most important compounds, which are responsible for the strength of hydrated cement paste. In reality the silicates are not pure compounds contain minor oxides in solid solution. These oxides have significant effects on the atomic arrangements, crystal form and hydraulic properties of the silicates The presence of C3A in cement is undesirable: it contributes little or no to the strength of cement, except at early ages.

Role in Cement
However, C3A is beneficial in the manufacture of cement in that it facilitates the combination of lime and silica. C4AF is also present in small quantities, and compared with the other components, it does not affect the behaviour significantly. However, it reacts with gypsum to form calcium sulphoferrite and its presence may accelerate the hydration of the silicates

Main Compounds in Portland Cement

Hydration of Cement
The two silicates, C3S and C2S, which are the most stable of these compounds, together form 70 to 80 percent of the constituents in the cement and contribute most to the physical properties of concrete. When cement comes into contact with water, C3S begins to hydrate rapidly, generating a considerable amount of heat and making a significant contribution to the development of the early strength, particularly during the first 14 days.

Hydration of Cement
In contrast C2S, which hydrates slowly and is mainly responsible for the development in strength after about 7 days, may be active for a considerable period of time. It is generally believed that cements rich in C2S result in a greater resistance to chemical attack and a smaller drying shrinkage than do other Portland cements. The contents of C3S and C2S are interdependent.

Hydration of Cement
The hydration of C3A is extremely exothermic and takes place very quickly, producing little increase in strength after about 24 hours. Of the four principal compounds, tricalcium aluminate, C3A, is the least stable and cements containing more than 10% of this compound produce concretes which are particularly susceptible to sulphate attack. Tetracalcium aluminoferrite, C4AF, is of less importance than the other three compounds when considering the properties of hardened cement mortars or concrete.

Hydration of Cement
There are two ways in which compounds present in cement may react with water:
True reaction of hydration: direct addition of water molecules onto the compounds Hydrolysis: breaking down of water molecules into hydrogen and hydroxyl ions and reaction of these ions with the compounds of cement

It is convenient, however, to apply the term hydration to all reactions of cement with water

Hydration of Cement
Le Chatelier observed that the products of hydration of cement are chemically the same as the products of hydration of the individual compounds under similar conditions - later confirmed by Steinour (1952), and Bogue and Lerch (1934). The products of hydration of cement have a low solubility in water indicated by the stability of hardened cement paste in contact with water The hydrated cement bonds firmly to the unreacted cement

 Main hydrates are:

Hydration of Cement

calcium silicate hydrates denoted as C-S-H (previously referred to as tobermorite gel), and tricalcium aluminate hydrate. C4AF believed to hydrate to tricalcium aluminate hydrate and an amorphous phase

Hydration of silicates (by hydrolysis):

2C3S + 6H C3S2H3 + 3Ca(OH)2
2C2S + 4H C3S2H3 + Ca(OH)2 Product of hydration is the microcrystalline hydrate C3S2H3 and some lime separating out as crystalline Ca(OH)2

Hydration of Cement
The hydration of C3S does not proceed at a constant rate.
There is an initial rapid release if calcium hydroxide into the solution leaving an outer layer of calcium silicate hydrate. This is followed by a dormant period during which little hydration takes place (C-S-H forms a coating on C3S) Eventually the coating ruptures because of the pressure of the products of hydration, and hydration speeds up again. Further slowing down: diffusion becomes the controlling factor

 The hydration of C3A with water is very violent and leads to immediate stiffening of the paste (flash set). Even with addition of gypsum, the rate of reaction is quicker than that of calcium silicates
Gypsum (CaSO4.2H2O) reacts with C3A to form insoluble calcium sulphoaluminate, and eventually a tricalcium aluminate hydrate is formed There is some evidence that the hydration of C3A is retarded by Ca(OH)2 liberated by the hydrolysis of C3S (product forms a protective coating on the surface of unhydrated grains of C3A)

Hydration of Cement

Component elements O2
Component oxides

Schematic Representation of Hydration

Si Ca Al
CaO SiO2
C2S

Fe

Al2O3 Fe2O3
C3A C4AF

Cement compounds C3S

Portland cements
Hydration products

Various types
C-S-H gel Ca(OH)2

 The amount of gypsum added to the clinker is crucial and needs careful control as an excess leads to expansion and consequent disruption of the set cement paste. Amount depends on:
C3A content and indirectly on the fineness of cement Alkali content of cement

Addition of Gypsum

Optimum gypsum content is determined on the basis of the heat of hydration, so that a desirable rate of early reaction occurs and little C3A is available for reaction after all the gypsum has combined

Addition of Gypsum
Amount of gypsum expressed as weight of SO3 present - limited by BS12:1978 to The presence of dehydrated products of gypsum in cement any lead to false set:
When gypsum is interground with too hot clinker formation of hemihydrate (CaSO4. H2O) or anhydrite (CaSO4) are formed When cement containing these dehydrated products are mixed with water, these hydrate to form gypsum. Thus plaster set takes place with stiffening of the paste

2.5% when C3A content is not more than 5% 3% when C3A content exceeds 5%

Heat of Hydration
The hydration of cement is exothermic (like many chemical reactions) Heat of hydration defined as the quantity of heat (J) per gram of unhydrated cement, evolved upon complete hydration at a given temperature For usual range of Portland cements:
of total heat liberated between 1 and 3 days in 7 days, and 90% in 6 months

The heat of hydration depends on the chemical composition of the cement

Heat of Hydration
Total heat of hydration sum of heats of hydration of individual pure compounds, when their respective proportions by mass are hydrated separately. Typical values are: Compound Tricalcium silicate Dicalcium silicate Tricalcium aluminate Tetracalcium aluminoferrite Heat of Hydration (J/g) 502 260 867 419

Therefore reducing the proportions of C3A and C3S will result in a decrease in the heat of hydration

Heat of Hydration
Points to be noted:
There is no relation between the heat of hydration and the cementing properties of the individual compounds. The fineness of cement affects the rate of heat development but not the total amount of heat liberated.

The total amount of heat liberated can be controlled in a concrete mix by varying the quantity of cement added (the richness)

Strength Development
There are two classical theories of hardening or gain of strength of cement:
Le Chatelier (1882) states that the products of hydration of cement have a lower solubility than the original compounds, so that the hydrates precipitates from a supersaturated solution. The precipitate is in the form of interlaced elongated crystals with high cohesive and adhesive properties Colloidal theory by Michaelis (1893) states that the crystalline aluminate, sulpho-aluminate and hydroxide of calcium give the initial strength.

Strength Development
(Michaelis contd) The lime-saturated water then attacks the silicates and forms a hydrated calcium silicate which, being almost insoluble, forms a gelatinous mass. This hardens gradually as a result of water loss (either by external drying or hydration of inner unhydrated cement grains).

Modern knowledge has shown that both theories are plausible and the colloidal behaviour is a function of the size of the surface area of particles rather than the non-regularity of their internal structure

Strength Development
In the case of Portland cement:
When mixed with large amount of water: cement produces within a few hours a solution supersaturated with calcium hydroxide and containing concentrations of C-S-H in metastable condition. This precipitates in agreement with Le Chateliers theory The subsequent hardening may be due to the withdrawal of water from the hydrated material as postulated by Michaelis

Strength Development of Pure Compounds

80
Compressive Strength (MPa)

C3S

70 60 50 40 30 20 10 0 0 60 120 180 Age (days) 240 300

C2S

C3A C4AF360

Strength Development
Convenient rule to strength development:
C3S contributes most to strength development during first 28 days C2S influences later gain in strength After about 1 year, both compounds contribute approximately equally to strength

 Term used to describe the stiffening of the cement paste In strict terms, setting refers to a change in state from fluid to rigid During setting, there is some strength gain but, for practical purposes it is convenient to distinguish between setting and hardening Hardening refers to the gain of strength of a set cement paste Two stages are used to describe the state reached by cement on hydration: initial set and final set

Setting of Concrete

Setting
Caused by the selective hydration of cement compounds First two compounds to react are C3A and C3S. With the addition of gypsum, C3S sets first when mixed with water and exhibits an initial set C2S stiffens in a more gradual manner The setting process is accompanied by temperature changes in the cement paste Initial set corresponds to a rapid rise in temperature Final set corresponds to the peak temperature

Setting
False set: abnormal premature stiffening of cement within minutes of mixing with water No appreciable heat evolved and remixing of the cement paste without the addition of water restores plasticity of the paste without a loss of strength Potential causes:
Hydration of dehydrated products of gypsum (as detailed previously) Presence of alkalis in cement: these may carbonate during storage and then on hydration, the alkali carbonates react with Ca(OH)2 liberated by hydrolysis of C3S to form CaCO3. This precipitates and induces a rigidity of the paste

Setting
Activation of C3S by aeration at moderately high humidities: water is adsorbed on the grains of cement and these freshly activated surfaces can combine very rapidly with more water during mixing producing false set

Flash set: takes place in cement with insufficient gypsum to control the rapid reaction of C3A with water.
Can only be overcome by adding more water and reagitating the mix. The addition of water causes a reduction in strength

Tests on Cement
Tests undertaken to ensure that the cement produced is of desired quality and conforms to national or international standards:
Chemical composition (beyond scope of lecture) Fineness Consistence of standard paste Setting time Soundness Strength of cement

Fineness of cement
The rate of hydration depends on the fineness of cement particles and for rapid development of strength, a high fineness is necessary However, increased fineness involved increased costs:
For grinding Increased gypsum requirement Effect on other properties, such as workability of fresh concrete and long-term behaviour

Fineness measured by the determination of the specific surface (in m2/kg)

Fineness
Direct approach: measure particle size distribution by sedimentation or elutriation The method is based on Stokes law giving the terminal velocity of fall under gravity of a spherical particle in a fluid medium Two methods:

Wagner turbidimeter: concentration of particles under suspension at a given level in kerosene is determined under a beam of light Air permeability (Lea and Nurse) method: measurement of the pressure drop when dry air flows at a constant velocity through a bed of cement of known porosity and thickness

Consistence of standard paste

Neat cement of standard paste consistence has to be used in setting time and soundness tests Therefore it is necessary to determine the water content, for any given cement, which will produce a paste of standard consistence Consistence is measured by the Vicat apparatus Standard consistence is the point at which a plunger penetrates to a point 5 1mm from the bottom of the mould. Water content measured are typically in the range of 26 to 33%

Setting time
The Vicat apparatus is also used for this test Initial set is the time since mixing with water when the paste has stiffened sufficiently for the needle to penetrate to a point 5 1mm from the bottom of the mould Minimum time of 45 minutes prescribed for ordinary and rapid-hardening Portland cement Final set is the time, since mixing with water, at which a specific needle makes an impression on the surface of the cement paste in a specified manner This is required by BS not to exceed 10 hours for ordinary, rapid hardening Portland cement

Setting time
Approximate relationship between initial and final setting times: Final time (min) = 90 + 1.2 x initial time (min) Since setting is affected by temperature and humidity, certain values are prescribed by BS as control namely:
Mixing at room temperature of 20 2o and min. relative humidity of 65% Curing or storing at same temperature and max. relative humidity of 90%

Soundness
Cement paste is required to have volume stability, i.e. it should not undergo large volume change once it has set Disruptive expansion of cement may occur due to reactions with free lime, magnesia and calcium sulphate cements exhibiting these types of expansion are classified as unsound Different tests prescribed for detecting different deleterious materials present;
Le Chateliers accelerated test (BS): detecting unsoundness due to free lime only

Soundness
Autoclave test (ASTM): sensitive to both magnesia and free lime No test available for detection of calcium sulphate but its content can be easily determined by chemical analysis

Strength
Strength tests are not made on neat cement paste because of difficulties in obtaining good specimens and in testing with a consequent large variability of test results Tests are done on cement-sand mortar or concrete of prescribed proportions Compressive strength tests are more common

 The different types exhibit different properties when mixed with water Ordinary Portland Cement (OPC):
Most common cement Used where there is no exposure to sulphates in the soil or groundwater Typical fineness of about 275m2/kg

Types of Portland cement

Rapid-hardening Portland Cement

Similar to OPC Develops strength rapidly; has a higher C3S content (up to 70%) and higher fineness (minimum of 325m2/kg)

Types of Portland Cement

Used principally when formwork need to be removed early It should not be used in mass concrete construction or in large structural sections Same setting time as OPC Marginally higher cost than OPC

Special rapid-hardening PC
Highly rapid-hardening Fineness ranging from 700 to 900m2/kg Higher gypsum content Used for early prestressing and urgent repairs

Types of Portland Cement

Low-heat Portland cement:
It has a low heat of hydration: 250J/g at age of 7 days and 290J/g at 28 days Developed in the US for use in large gravity dams Slower development of strength than OPC due to lower content of C3S and C3A Portland pozzolan cement of low-heat variety

Sulphate-resisting cement:
Low C3A content (limited to 3.5%) so as to avoid sulphate attack from outside the concrete Minimum fineness of 250m2/kg

 Has the advantage of being relatively low heat (not much higher than low-heat cement) Higher cost due to special composition of raw materials, therefore not for general use

Types of Portland Cement

Portland blast-furnace cement

Produced when intergrinding or blending PC clinker with ground granulated blastfurnace slag Hydration is initiated when lime liberated in the hydration of PC provides the correct alkalinity Used in various proportions (refer to table earlier) Similar to OPC wrt fineness, setting times and soundness

Types of Portland Cement

However, lower early strength than OPC with similar later strength Typical uses in mass concrete due to lower heat of hydration and in sea-water construction due to better sulphate resistance (lower C3A content) than OPC

White or coloured PC
Use for architectural purposes Made with china clay and requires special precautions during grinding Therefore it is costly twice as much as OPC

Types of Portland Cement

Portland-pozzolan cement
Use of PFA or fly ash a pozzolan (a siliceous or siliceous/aluminous material, which when in finely divided form and in the presence of moisture, react with lime at ordinary temperature to form compounds with cementitious properties) Slow gain in strength and require curing over a comparatively long period High long-term strength Use of PFA improves sulphate resistance Pozzolans may often be cheaper than PC Main advantage lies in slow hydration and therefore low rate of heat development