Portland Cement

Cement is a binder, a substance that sets and hardens independently, and can bind other
materials together.
Cements used in construction can be either hydraulic or non-hydraulic. Hydraulic cements
(e.g., Portland cement) set and harden because of hydration and hydrolysis reactions between
the anhydrous cement powder and water. Non-hydraulic cement such as slaked limes
(calcium hydroxide mixed with water) harden due to the carbonation reaction by carbon
dioxide present naturally in the air. Cement alone cannot be used for construction work. It is
used as a mixture with sand and crushed stones. It may be used as mortar or concrete.
Portland cement: It is a fine ground product obtained by calcination of proper proportions of
calcareous and argillaceous materials at 1500 OC without addition of any substances except
gypsum.

Manufacture of cement
Rotary kiln method
Portland cement is manufactured by mixing lime and clay. The raw materials used for the
manufacture of Portland cement are given below.
(i) Calcareous materials: These materials supply lime, for example, limestone (contains
65%–80% CaCO3), chalk, calcite and waste calcium carbonate from industrial processes.
(ii) Argillaceous materials: These materials supply silica, iron oxide and alumina, for
example, clay, marl, shale, etc. All these materials should have 2.5 to 4 times more silica than
alumina.
(iii) Gypsum CaSO4.2H2O
(iv) Powdered coal as fuel.
The manufacture of Portland cement involves the mixing of calcareous and argillaceous
substances in the required ratio. The mixture is heated to 1400 °C–1600 °C (fusion point).
The clinkers so obtained are cooled, powdered and mixed with 2% to 5% gypsum. The
various steps involved in the manufacture process are
• Mixing
• Burning
• Cooling
• Grinding
• Packing
1. Mixing of raw materials
The raw materials are ground and then mixed either by (a) dry process or (b) wet process
a) Dry process The calcareous and argillaceous substances are ground separately without
adding water. Each of these is stored in a separate hopper. The two are then mixed in the
proper ratio by automatic weighing machines and then the dry powdered mixture (moisture
2%) is fed into the furnace.
b) Wet process In this method the calcareous substances are ground dry and stored in silos.
The argillaceous substances are washed to remove impurities and then ground. The
calcareous and argillaceous substances are mixed in the presence of water (30%–40%) to get
free flowing slurry. The slurry is then led into the correcting basin where its chemical
composition is adjusted to the proper ratio. The slurry is stored in big storage tanks before
being fed into the furnace.

Burning is usually done in a rotary kiln, which is a long steel cylinder (length: 90-120 m and
diameter 2–4 m) lined with refractory bricks. It is slightly inclined towards the exit end and is
mounted on rollers. It rotates gradually to enable proper mixing of the raw material. The
material is introduced in the kiln from the upper end. The kiln is heated by burning pulverised
coal and the temperature is maintained at 1600 °C–1700 °C. The material introduced from the
upper end moves downwards due to inclination and rotatory movement of the kiln. The
various chemical reactions taking place are as follows.
(a) Drying zone: This is the upper one-fourth portion of the kiln where the temperature is
100–500 °C. This zone is known as the drying zone because all the moisture from the slurry
is removed here. The dry material moves down the kiln.
(b) Calcination zone: It is the middle part of the kiln and the temperature here is about 1000
°C. All the organic matter burns here and calcium carbonate decomposes to form CaO and
CO2.
CaCO3 CaO + CO2
CO2 escapes out and the material acquires the shape of lumps.
(c) Burning zone or clinkering zone: It is the hottest and lowermost portion of the kiln. The
temperature here is 1400 °C–1600 °C. In this zone, the mixture melts chemical reaction
between lime and clay takes place forming calcium aluminates and silicates. The reactions
taking place are given below.
2CaO + SiO2 2CaO.SiO2 or Ca2SiO4
(Dicalcium silicate C2S)
3CaO + SiO2 3CaO.SiO2 or Ca3SiO5
(Tricalcium silicate C3S)
3CaO + Al2O3 3CaO. Al2O3 or Ca3Al2O6
(Tricalcium aluminate C3A)
4CaO+ Al2O3+ Fe2O3 4CaO. Al2O3.Fe2O3 or Ca4 Al2Fe2O10
(Tetracalcium aluminoferrite C4AF)
These aluminates and silicates combine together to form small, round, greyish stones called
clinkers.
Cooling zone The clinkers produced above are cooled by a stream of air and the hot air so
produced is used for drying the coal before pulverisation.
Grinding The cooled clinkers are ground in ball mill with the addition of 2%–5% gypsum.
Finely ground clinkers set very quickly when they come in contact with water. Gypsum
(CaSO4.2H2O) acts as a retarding agent and delays this setting. When cement is mixed with
water, the initial set takes place due to hydration of tricalcium aluminate.
Packing and supply The cement coming out of the grinding mill is stored in concrete storage
called silos.
Chemical composition of cement:
The properties of cement depend upon the relative proportions of the components present.
The properties can be modified by varying the amount of these constituents.

Name of the Chemical Abbreviation Average% Setting Heat of

compound formula time hydration
Tricalcium 3CaO. Al2O3 C3A 10 1day 210cal/gm
Aluminate
Tetraclacium 4CaO. C4AF 10 1day 100
aluminoferrite Al2O3.Fe2O3 cal/gm
Tricalcium 3CaO.SiO2 C3S 45 7 days 120
Silicate cal/gm
Dicalcium 2CaO.SiO2 C2S 25 28 60 cal/gm
silicate days
Setting and hardening of cement:
When cement is mixed with water and allowed to stand, it changes to a hard rigid mass. This
is known as setting. Setting refers to a change from a fluid state to a rigid state due to initial
gel formation. Gradually, the rigid mass gains strength to form a compact rock-like material.
This development of strength due to crystallisation is called hardening.
Setting and hardening takes place due to hydration and hydrolysis reactions of the various
constituents of cement. It is believed that hardening takes place due to interlocking of the
crystalline products formed during hydration.
Setting occurs within 24 hours, whereas hardening requires 15 to 30 days. It is believed that
the setting times of C3A, C4AF, C3S and C2S are 1 day, 1 day, 7 days and 28 days,
respectively.
The chemical reactions taking place during setting and hardening are as follows.
(i) Initial setting Initial setting refers to the beginning of the cement paste setting. When
cement is mixed with water, the paste becomes stiff immediately. This immediate stiffening
after mixing, making proper placing and finishing impossible is called ‘flash set’. It is due to
hydration of tricalcium aluminate (C3A). It is accompanied by evolution of considerable heat.

(a) 3CaO.Al2O3 + 6 H2O 3CaO.Al2O3.6H2O + 210 Cal/gm

Tricalcium aluminate Hydrated tricalcium aluminate crystals
or, C3A + 6 H2O C3A .6 H2O + 210 Cal/gm
Flash set is not desirable as it causes loss of workability of cement and prevents hydration of
the other constituents of cement. Gypsum is added to retard flash set or initial set.
3CaO. Al2O3 + x H2O + y CaSO4.2H2O 3CaO. Al2O3 .3CaSO4.30–32H2O
(Tricalcium sulphoaluminate)
C3A + x H2O + y CaSO4.2H2O C3A. 3CaSO4. 30–32 H2O
Gypsum reacts with C3A forming insoluble tricalcium sulphoaluminate, which does not
hydrate rapidly.

b) Tetracalcium aluminoferrite also undergoes hydrolysis forming crystalline products.

4CaO. Al2O3.Fe2O3 + 7 H2O 3CaO.Al2O3.6 H2O + CaO. Fe2O3. H2O + 100 cal/gm
C4AF + 7 H2O C3A .6 H2O + CF. H2O + 100 cal/gm
(Crystals) (Gel)
c) Hydration of C3S also starts within 24 hours and is completed in 7 days.
2(3CaO.SiO2) + 6 H2O 3CaO.2SiO2.3 H2O + 3 Ca(OH)2 + 120 cal/gm
2C3S + 6 H2O C3S2.3 H2O + 3 Ca(OH)2 + 120 cal/gm
Tricalciumsilicate Tobermorite gel

It refers to the beginning of hardening and gain of strength. Hardening starts after ~10 h and
continues for several months. Hydration of dicalcium silicate occurs slowly between 7 to 28
days.
d) 2(2CaO.SiO2) + 4 H2O 3CaO.2SiO2.3 H2O + Ca(OH)2 + 60 cal/gm
2C2S + 4 H2O C3S2.3 H2O + Ca(OH)2 + 60cal/gm
dicalcium silicate Tobermorite gel
Tobermorite gel serves as a bonding material between cement particles because of large
surface area and high binding energy. It is the main component that gives strength to cement.
Ca(OH)2 does not contribute to strength but brings the pH value above 12 and is good for
corrosion protection of steel.
As the hydrolysis and crystallisation proceed, the strength and hardness of cement increases.
The process takes nearly 28 days.

Refractories

Refractories are inorganic, non-metallic materials that can withstand high temperatures
without undergoing physicochemical changes while remaining in contact with molten slag,
metals and gases. They are mostly used in lining of furnaces, kilns, crucibles, etc., which are
generally heated to a very high temperature.
Characteristics of a good refractory
A good refractory should possess the following characteristics.
• It should be chemically inert to the corrosive action of gases, liquids and slags.
• Its physical, chemical and mechanical properties should not undergo substantial changes at
high temperature.
• Its refractoriness (fusion temperature) should be high.
• It should be resistant to the abrasive action of flue gases, molten metal’s, etc.
• It should not undergo cracking or deformation due to non-uniform expansion or contraction.
• It should not contaminate the material with which it is in contact.

Classification of refractories:
(i) Acid refractories They are those which consist of acidic materials like silica and
aluminium
silicate. They are not attacked by acidic materials but are generally attacked by basic
materials,
for example, silica, alumina and fireclay refractories. Steel industries are the biggest
consumer
of silica refractories.
(ii) Basic refractories They are made of basic materials like CaO, MgO, etc. They are
not
attacked by basic or neutral media but are easily attacked by acidic materials, for example,
magnesite, dolomite, chrome–magnesite refractories.
(iii) Neutral refractories They are not attacked neither by acidic nor by basic
materials, hence
they constitute the most satisfactory furnace lining. Examples of neutral refractories include
graphite, chromite (FeO. Al2O3), zirconia (ZrO2) and carborundum (SiC).
Properties of Refractories:
Refractoriness: It is the ability of a material to withstand high temperature without
appreciable deformation or softening. It is generally measured by the softening or fusion
temperature of the material.
A refractory material should have a softening temperature (refractoriness) higher than the
operating temperature of the furnace.
Measurement of refractoriness (Seger cone test): As a refractory material is a mixture of
several oxides, they do not have a sharp fusion temperature. Refractoriness is determined by
the pyrometric cone test or the seger cone test. It is expressed in terms of pyrometric cone
equivalent (PCE).

Softening temperature > Operating temperature

(Material to be used as refractory)

Refractoriness under load or Strength:

 Refractories used in furnaces have to withstand high pressure and varying loads of the
charges at high operating temperature.
 It is, therefore, essential that refractory materials must also possess high mechanical
strength, even at operating temperature, to bear the maximum possible load, without
breaking.
 Some refractories like FIRECLAY, High Alumina Bricks softens gradually over the
range of temperature, but under appreciable load, they collapse, far below their true
fusion point, as determined by segar cone test.
 On the other hand, other refractories such as Silica Bricks softens over a relatively
narrow range of temperature and exerts good load bearing characteristics close to their
fusion points.
 Refractoriness Under Load test is performed by heating a refractory specimen of size
5 cm2 and 75 cm height under a constant load of 3.5 to 1.75 kg/cm2.
 It is heated in a carbon residue furnace at a standard rate of 10oC/min. the
temperature at which 10% deformation occurs is noted as RUL value.

Dimensional stability:
 It is the ability of a refractory material to resist any permanent volume change when it
is exposed to high temperatures for a prolonged period of time.
 Irreversible changes may result either in the contraction or expansion of a refractory.
 Permanent expansion occurs when one crystalline form of refractory is transformed
into another crystalline form of low density.
Quartz tridymite crystobilite
(sp.gr = 2.65) (sp.gr = 2.26) (sp.gr = 2.32)
  Permanent contraction due to i) melting of low fusible constituents forming liquid
causing shrinkage, example fireclay. ii) transformation of one crystalline form into
another more dense form, example magnesite brick.
amorphous MgO Periclase (crystalline)
(sp.gr = 3.05) (sp.gr = 3.54)
Shrinkage in magnesite brick due to increase in density.

Porosity:
 All refractories contain pores, either due to manufacturing methods or deliberately
made ( by incorporating saw-dust or cork during manufacture).
 Porosity is the ratio of its pore’s volume to the bulk volume.

W = Wt. of saturated specimen.

D = Wt. of Dry specimen.
A = Wt. of saturated specimen submerged in water.
 Porosity is an important property of refractory bricks, because it affects many other
characteristics, e.g. chemical stability, strength, abrasion-resistance and thermal
conductivity.
 In a porous refractory, molten charge, slags, gases etc. are likely to enter more easily
to a greater depth and may react and reduces the life of the refractory material.
 However, porosity increases resistance to thermal spalling.
 A good refractory in general has low porosity.

Thermal spalling:
 Breaking, cracking, peeling off or fracturing of a refractory brick or block, under high
temperature. So good refractory must show a good resistance to thermal spalling.
 Spalling is caused by rapid changes in temperature, which causes uneven expansion
and contraction within the mass of refractory, thereby leading to development of
internal stresses and strains.
 Spalling may also be due to slag penetration into the refractory brick, thereby causing
variation in the coefficient of expansion.
 Spalling can be decreased by
• Using high porosity, low coefficient of expansion and good thermal conductivity
refractory bricks. Avoid sudden temperature changes. By over firing the
refractories at high temparature for a sufficiently long time, whereby mineral
inversion takes place making the material less susceptible to uneven expansion or
contraction, when heated.

Thermal Conductivity:
 In industrial operations, refractories of both low and high thermal conductivities are
required, depending upon type of furnace.
 A good heat conductivity of the refractory material is desirable for effective heat
transmission in furnace construction. Example coke oven walls, muffle furnace.
 The densest and least porous brick have the highest thermal conductivity, owing to the
absence of air-voids.
 On the other hand, in porous bricks, the entrapped air in the pores, acts as a non-heat
conducting material. Example rotary kilns.
 For making porous refractory bricks, the refractory material is mixed with a liberal
amount of carbonaceous material, then mould into bricks and burnt. The
carbonaceous material burns off; leaving behind minute voids, which enhances the
insulating quality.

Thermal Expansion:
 Solid materials on heating, expands and on cooling it contracts.
 So in the designing of the practical furnaces, a refractory material should have least
possible thermal expansion as the expansion affects all dimensions (e.g. length, area,
volume) of the body.

Chemical Inertness:
 A refractory should be selected that is chemically inert in use and does not form
fusible products with slags, fuel ashes, furnace gases, etc. usually, the environment in
most furnaces are either acidic or basic.
 It is not recommended to employ Acid refractory in contact with an alkaline (basic)
product or vice-versa.

Resistance to abrasion and erosion:

 It should be least abraded by the descending charge, flue gases escaping at high
speeds, particles of carbon, grit, etc.
 Abrasion of refractory material leads to erosion due to the chemical reaction between
the slag and the refractory lining.
 Refractory material should have abrasion resistance.

Conditions leading to failure of refractory material:

A refractory material can collapse if
 Refrocteriness is less than the working temperature of the furnace.
 Thermal expansion is high.
 There are rapid charges in the temperature of the furnace.
 The refractory brick is heavy weight.
 The refractory brick is not properly fired.
 The brick undergoes considerable change in volume at high temp.
 If refractory is acidic when basic reactants/products are being processed and basic
when acidic materials are being treated.

Silica bricks:
 They contain 90-95% SiO2 to which about 2% lime is added to improve binding
properties. Example quartzite, sand, etc.
 They are yellow in color with brown specks.
 They are acidic in nature and suitable for acidic environment.
 Porosity is low (17-25%)
 They can withstand a load of about 3.5 kg/cm2 up to 1500-1600oC.
 Their fusion temperature is about 1750oC.
 They are light and posses high rigidity and strength.
 Used in lining of roof arches of open hearth furnaces, coke ovens. Used in iron and
steel industries.

Magnesite:
 Magnesite refractories are chemically basic materials, containing at least 85%
magnesium oxide. These are made from naturally occurring magnesite (MgCO3) and
Silica (SiO2).
 They can be used up to 2,000oC without load and up to 1,500 oC under load.
 They possess good crushing strength, good resistance to basic slags, but have lot of
spalling due to their sensitiveness to sudden chages of temp.
 Their resistance abrasion is poor.
 Used where high temp. is required to be maintained, together with great resistance to
basic materials.
 Refining furnaces for gold, silver and platinum etc.
 Their chief use in steel industry foe lining of basic converters and open hearth
furnaces.

Carborundom(SiC) bricks:
 It is made by mixing sand(60%) and coke (40%) with the addition of some saw-dust
and a little salt calcined at 1500oC.
 Clay-bonded SiC refractories can be used up to 1750oC.
 Self-bonded bricks has high refractoriness, superior strength, high abrasion resistance
and high chemical inertness etc.
 They are used for partition walls of chamber kilns, coke ovens, muffle furnace, etc.
 Moreover, due to their high electrical conductivity, they are used as heating elements
in furnaces.