Syllabus

Electronic configuration: Various properties of elements in terms of periodic table

Physical and chemical properties of liquids
Chemical equilibrium
Reaction, Kinetics and theories of reaction rates
Chemistry of cement, silicates and limes

Chemistry of polymerization: different types of polymers and their properties,

polymer degradation, elastomers and composite materials.
Introduction to paints and varnishes, pretreatment of the surface, metallic, non-
metallic and organic protective coating, types of paints and their uses.
Adsorption chemistry: surface growth, surface composition, adsorption isotherms;
Metallic bonds; structures of elements and compounds; Defects in crystal.

Dr. Jeasmin Akter

Chapter: Cement, Silicate, and Lime

WELCOME
TO OUR PRESENTATION
ON

Cement
Definition of Cement :

• A cement is a binder, a substance that sets and hardens and can

bind other materials together.

• The word "cement" can be traced back to the Roman term opus
caementicium, used to describe masonry resembling modern
concrete that was made from crushed rock with burnt lime as binder.
 History
Joseph Aspdin, England, in 1824
 Natural Cement

This types of cement can be obtained by burning limestone containing 20-40%

clay and crushing it to powder.

Example-Rosendale Cement.

Natural Cement Natural Cement

Manufacture Of Cement

Raw Materials
 There are Two Process Employed for the Manufacture of Cement

----------Wet Process

----------Dry process (no water; no slurry)

Differs only in the treatment of raw materials

The process to be chosen, depend on the nature of the used raw materials. For example,

wet process used when the percentage of the moisture in the raw materials is high, while, dry process
used when:

The raw materials is so hard (solid) that they do not disintegrate by water
Cold countries, because the water might freeze in the mixture
Shortage of the water needed for mixing process
Mixing and Crushing: B) Wet process
Burning Process: Zones of Rotary Klin
Burning Process: Chemical Reactions in Rotaty Klin Zones

• Calcination Zone :

CaCO3 CaO + CO2

• Clinkering Zone :

2CaO + SiO2 Ca2SiO4 ( Dicalcium silicate – C2S )

3CaO + SiO2 Ca3SiO5 ( Tricalcium silicate – C3S )

3CaO + Al2O3 Ca3Al2O6 ( Tricalcium aluminate – C3A )

4CaO + Al2O3 + Fe2O3 Ca4Al2Fe2O10

(tetracalcium aluminoferrite – C4AF)
Cooling
 Grinding

• Cooled clinkers are ground to fine powder in ball mills

• At final stages of grounding about 2-3% of powdered gypsum is
added.
(This is to avoid setting of cement quickly when it comes in contact with water)

• Tricalcium aluminate (C3A) combines with water very rapidly with the evolution
of large amount of heat. After the initial set, the paste becomes stiff
C3A + 6H2O C3A . 6H2O + Heat

• Gypsum acts as a retarding agent for early setting of the cement

3CaO + Al2O3 + x CaSO4 . 7H2O 3CaO . Al2O3 . xCaSO4 . 7H2O

After initial set Gypsum Tricalcium sulphoaluminate (Insoluble)

Packaging
• Ground cement is stored in silos
• From silos they are automatically packaged into bag which are about 50 Kg
Process parameters for manufacturing a good quality of cement clinker
 Setting and hardening

 When the cement is mixed with water, hydration and hydrolysis reactions of Bogue compounds
of cement begin, resulting in formation of gel and crystalline products.

 These products have the ability to surround inert materials liks sand, bricks, crushed stones, etc.

“ Setting is the stiffening of original plastic mass due to the formation of tobermonite gel”. It
can be divided into 2 stages a) Initial Set b)Final Set

 Initial Set is when paste being to stiffen

 Final Set is when the paste beginning to harden and able to sustain some loads.
 Setting time is affected by cement composition, cement fineness, rate of hydration, and the
ambient temperature

“ Hardening is the development of strength due to formation of crystals”

 Setting and hardening
Unhydrated Cement

Hydration

Crystalline hydration
Metastable Gel
products

Stable Gel Crystalline products

Figure showing setting and hardening of cement

 Setting and Hardening : Chemical Reactions
Sequence of
changes during
setting and Day 1 :
hardening • When cement is mixed with water, hydration of tricalcium aluminate (C3A)
takes place within a day
Cement • The paste becomes rigid, which is known as Initial set or Flash set
+
Water Paste
1st day
3CaO . Al2O3 + 6H2O 3CaO . Al2O3 . 6H2O + 880 kJ/Kg
Hydration of Tricalciumaluminate Hyderated tricalcium aluminate (Crystalline)
C3A and C4F [OR]
7th day C3A + 6H2O C3A . 6H2O + 880 kJ/Kg

Gelation of
• To avoid early setting of C3A , gypsum is added which acts as retarding
C3S
agent
28th day

Gelation of C3A + 3CaSO4 . 2H2O C3A . 3CaSO4 . 2H2O

C2S and C3S Caclium sulpho aluminate
Setting and Hardening : Chemical Reactions

Day – 2 to 7 :
• After hydration of C3A, C3S beings to hydrate to give tobermonite gel and
crystalline Ca(OH)2, which is responsible for initial strength of the cement
• The hydration of C3S gets completed within 7 days

2[3CaO .SiO2] + 6H2O 3CaO.2SiO2 . 3H2O + 3Ca(OH)2 + 500 kJ/Kg

Tricalcium silicate Tobermonite gel Crystalline
[OR]
2C3S + 6H2O C3S2 . 3H2O + 3Ca(OH)2 + 500 kJ/Kg

Tobermonite gel possesses a very high surface area and very high adhesive property
Setting and Hardening : Chemical Reactions

Day – 7 to 28 :
• Dicalcium silicate (C2S) reacts with water very slowly and gets completed in 7
to 28 days

2[2CaO . SiO2 ] + 4H2O 3CaO .2SiO2 . 3H2O + Ca(OH)2 + 250 kJ/Kg

Dicalcium silicate Tobermonite gel Crystalline
[OR]
2C2S + 4H2O C3S2 . 3H2O + Ca(OH)2 + 250 kJ/Kg

• Increase of strength is due to formation of tobermonite gel and crystalling

Ca(OH)2 of both C2S and C3S
Setting and Hardening : Chemical Reactions

• After initial hyderation of tetracalcium alumino ferrite (C4AF) , hardening takes place
through crystallization , along with C2S

4CaO . Al2O3 . Fe2O3 + 7H2O 3CaO . Al2O3 . 6H2O + CaO . Fe2O3 . H2O + 420 kJ/Kg
Tetracalcium alumino ferrite Crystalline Gel
[OR]
C4AF + 7H2O C3A . 6H2O
Rapid Hardening Cement Rapid Hardening
is a kind of cement which achieves strength very fast.

 The strength achieved by Rapid Hardening Cement in 3 days is equivalent to the strength
achieve by Ordinary Portland Cement (OPC) in 7 days.
 The Hardening properties of cement are enhanced with the addition of Tricalcium Silicate.
 The improved early strength is achieved by the fineness of cement.

 It gains high strength in the early days and the formwork can be removed earlier as compared
to other types of cement.
 It requires a short period of curing.
 Rapid hardening cement is used in areas like road pavements so that the traffic can be opened
early. It is also used in manufacturing precast slabs, posts, electric poles, concreting in cold
countries.

 Rapid hardening Cement is Costly.

PPC (Portland Pozzolana Cement)
is a kind of Blended Cement which is produced by either inter grinding
of OPC clinker along with gypsum and pozzolanic materials in certain proportions or grinding the
OPC clinker, gypsum and Pozzolanic materials separately and thoroughly blending them in certain
proportions.

 Higher durability of concrete structure due to less permeability of water.

 More resistance towards the attack of alkalies, sulphates, chlorides, chemicals.
Low heat of hydration.
 Due to high fineness, PPC has better cohesion with aggregates and makes more dense concreteness.
Better surface finish.
 Comparative lower Water-Cement ratio provides an added advantage for the further increase of
compressive strength of the concrete.
Portland Slag Cement (PSC)
Portland Slag Cement (PSC) is manufactured by either inter-grinding in the
Portland cement clinker, Gypsum Granulated Slag or blending the Ground Granulated Blast Furnace
Slag (GGBS) with Ordinary Portland Cement by means of mechanical blenders.

 Reduced plastic shrinkage cracks.

 Smooth surface finish.
 Increased resistance to chlorides, sulphates, carbon
dioxide and such other harmful salts.
 Reduced heat of hydration and thermal cracks.
White Cement
White cement is a hydraulic binder whose physical characteristics correspond to those of
Portland grey cement. It is distinguished by its pure white color. This whiteness is the result of nature, as well
as the rigorous selection of raw materials used in manufacturing and a technologically advanced production
process.

 use in flooring applications in malls, schools, airports and other large buildings, which reduces the
requirement excessive lighting which in turn reduces energy costs.

 White cement can be pigmented to achieve various colors without the

need for paint or stains thus eliminating VOCs.
 Reduction of the heat island effect by using white based mix designs
for the manufacture of
 rooftop pavers, light colored pavers in driveways, walkways, patios
and around pools.
 When concrete products reach the end of their long useful life they
can be recycled and used in the manufacture of other products.
Water- Repellent Cement

•Has greater frost resistance

•Has imperviousness to water than ordinary cement
• Containing the power to minimize the hygroscopicity of cement

High Alumina Cement

• Rapid hardening cement of chocolate colour.

• Manufactured from Bauxite and limestone in special reverberatory
containing 35% of Alumina
• Resists the action of acid and high temperature
• Does not expand on setting
Quick Setting Cement

• Contains less percentage of gypsum

• Costlier than OPC
• Initial and Final Setting Times are 5 minutes and 30 minutes respectively.
• Due to quick setting it is used under water or running water

Colored Cement

• Prepared by adding 5 to 15% of suitable coloring pigment before

the cement is finally grounded.
•Much costlier than OPC
•Widely used for fishing floors , external surfaces etc
Expanding Cement

• Produced by adding an expanding medium like sulpho-aluminate & a

stabilizing agent to the ordinary cement
• Expands whereas other Cements Shrink
• Used for construction of water retaining Structures.
• Employed for repairing the damaged concrete surfaces

Super Sulphate Cement

•Highly resistant to sea water

•Offers resistance to peaty acids
•Used in variety of aggressive conditions like marine work,mass
concrete jobs etc
•Should not be mixed with other cements
Soundness:
Soundness is a physical property of cement paste, which determines the ability of the
cement paste to retain its volume after setting is completed.
The unsoundness is due to the presence of free CaO (lime) and free MgO (magnesia) in cement.
These constituents hydrate very slowly after setting of cement. Since Ca(OH)2 and Mg(OH)2
occupy larger volume, expansion takes place.

The unsoundness may be reduced by;

1- limiting MgO content to less than 5%,
2- fine grinding,
3- thorough mixing,
4- Allow cement to aerate for several days (lime may have hydrated or carbonated in cement).
Additives for cement

 Accelerators: NaCl, CaCl2, some organic substances such as

triethanolamine, some soluble carbonates, silicates, fluorosilicates etc.
 Retarder: CaSO4
 Dispersing agent: Sodium salts of polymers or condensed naphthalene or
sulfonic acid
 Water repelling agents: Soaps, Petroleum oils, Waxes
 Air entrainment agents: Vinsol resin, darex etc. also organic compounds
like natural resin, fats
 Workability agents: bentonite clay, diatomaceous earth, fly ash, clay, finely
divided silica, fine sand, hydrated lime, talc, pulverized stone etc.
 Gas forming agents: Aluminium powder
 Pozzolonic materials: Fly ash, volcanic ash, heat treated raw clays, shale etc
 Others:
Quality Tests on cement are carried out to check the strength and quality of the cement used in
construction. It helps to identify the usage of cement for different purposes based on its durability and
performance.

The following tests are conducted on cement in the laboratory are as follows:

1. Fineness Test:
2. Consistency Test: This test is conducted to find the setting times of cement
3. Strength Test (Compressive Strength Test)
4. Soundness Test: presence of uncombined lime and magnesia in cement.
5. Heat of Hydration Test
6. Tensile Strength Test
7. Lumps in cement: The cement should not contain any hard lumps. These lumps are formed by the
absorption of moisture content from the atmosphere. The cement bags with lumps should be avoided
in construction.
8. Chemical Composition Test
9. Colour Test of Cement: Colour should not be uneven. It should be a uniform.
10. Cement Adulteration Test: should be smooth if you rubbed it between fingers. If not, then it is
because of adulteration with sand.
Fineness:

The greater the surface area of a given volume of cement the greater the hydration.

Chemical Composition Test

Different tests are conducted to determine the amount of various constituents of cement. The
requirements are based on IS: 269-1998, is as follow

 The ratio of the percentage of alumina to that of iron oxide should not be less than 0.66.
 Lime Saturation Factor (LSF), i.e., the ratio of the percentage to that of alumina, iron oxide and silica
should not be less than 0.66 and not be greater than 1.02.
 Total loss on ignition should not be greater than 4%.
 Total sulphur content should not be greater than 2.75%.
 Weight of insoluble residue should not be greater than 1.50%.
 Weight of magnesia should not be greater than 5%
 Fineness: Residue on B.S. 170 mess test sieve should not exceed 10%
 Setting time: Initial setting time should not less than 30 min. Final setting time should not more than 12 h