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UNIT 1
CEMENT
M. Irfaan Mungroo
Civil Engineering Department
JSS ATE, Mauritius
CONCRETE TECHNOLOGY
Unit 1
Cement
VTU SYLLABUS
Cement,
Chemical composition,
hydration of cement,
Types of cement,
manufacture of OPC by wet and dry process (flow charts only)
Testing of cement - Field testing, Fineness by sieve test and Blaine's air
permeability test, normal consistency, testing time, soundness,
Compression strength of cement and grades of cement,
Quality of mixing water.
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Cement
CEMENT
Cement can be defined in many ways as follows:
i.
It is any material that hardens and becomes strongly adhesive after application.
ii.
iii.
HISTORY OF CEMENT
The term Portland cement was first used in 1824 by Joseph Aspdin, a British cement-maker,
because of the resemblance between concrete made from his cement and Portland stone, which
was commonly used in buildings in Britain.
At that time cements were usually made in upright kilns where the raw materials were spread
between layers of coke, which was then burnt.
The first rotary kilns were introduced about 1880. Portland cement is now almost universally used
for structural concrete.
CHEMICAL COMPOSITION
The raw materials used for the manufacture of cement consist mainly of:
i)
Lime (CaO)
ii)
Silica (SiO2)
iii)
Alumina (Al2O3)
iv)
magnesia (MgO),
ii)
iii)
These oxides interact with one another at high temperature to form more complex compounds.
The relative proportions of these oxide compositions are responsible for influencing the various
properties of cement in addition to the rate of cooling and fineness of grinding.
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Oxide
Name
% Content
CaO
Lime
60 67
SiO2
Silica
17 25
Al2O3
Alumina
38
Fe2O3
Iron Oxide
0.5 6
MgO
Magnesia
0.1 4
Alkalies
0.4 1.3
SO3
Sulfuric anhydride
1.3 3.0
As mentioned earlier, the oxides present in the raw materials when subjected to high temperature
combine which each other to form complex compounds. The identification of the major compounds
is largely based on R.H Bogues work and hence it is called Bogues Compounds.
The four compounds usually regarded as major compounds are:
Name of compound
Formula
Abbreviated Formula
Tricalcium silicate
3CaO. SiO2
C3S
Dicalcium silicate
2CaO.SiO2
C2S
Tricalcium aluminate
3CaO.Al2O3
C3A
Tetracalcium aluminoferrite
4CaO.Al2O3.Fe2O3
C4AF
It is to be noted that for simplicitys sake, abbreviated notations are used. C stands for CaO, S stands
for SiO2, A for Al2O3, F for Fe2O3 and H for H2O.
The equations suggested by Bogue for calculating the percentages of major compounds are given
below:
i.
ii.
iii.
iv.
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The oxide composition of a typical Portland Cement and the corresponding Composition are
calculated below:
For CaO = 63%, SiO2 = 20%, Al2O3 = 6%, Fe2O3 = 3%, MgO = 1.5%, SO3 = 2% and K2O and Na2O = 1%,
the calculated compound composition using Bogues equation are:
C3S = 54.1
C2S = 16.6
C3A = 10.8
C4AF = 9.1
HYDRATION OF CEMENT
When Portland cement is mixed with water its chemical compound constituents undergo a series of
chemical reactions that cause it to harden. This chemical reaction with water is called "hydration".
Each one of these reactions occurs at a different time and rate. Together, the results of these
reactions determine how Portland cement hardens and gains strength.
Hydration starts as soon as the cement and water are mixed. Each compound produces different
products when it hydrates.
a) Tricalcium silicate (C3S) hydrates and hardens rapidly and is largely responsible for initial
set and early strength. Portland cements with higher percentages of C3S will exhibit higher
early strength.
b) Tricalcium aluminate (C3A) hydrates and hardens the quickest. It liberates a large amount of
heat almost immediately and contributes somewhat to early strength. Gypsum is added to
Portland cement to retard C3A hydration. Without gypsum, C3A hydration would cause
Portland cement to set almost immediately after adding water.
c) Dicalcium silicate (C2S) hydrates and hardens slowly and is largely responsible for strength
increases beyond one week.
d) Tetracalcium aluminoferrite (C4AF) hydrates rapidly but contributes very little to strength.
Its use allows lower kiln temperatures in Portland cement manufacturing. Most Portland
cement color effects are due to C4AF.
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Compounds
Reaction Time
Strength
Heat Liberated
C3S
Moderate
High
High
C2S
Slow
Low
C3A
Fast
Low
Very High
C4AF
Moderate
Low
Moderate
HEAT OF HYDRATION
The reaction of cement with water is exothermic and liberates a considerable amount of heat. This
liberation of heat is called heat of hydration.
On mixing cement with water, a rapid heat evolution occurs lasting a few minutes. This is probably
due to the reaction of solution of aluminates and sulphates. This initial heat evolution ceases
quickly when the solubility of aluminate is depressed by gypsum.
Heat of hydration is most influenced by the proportion of C3S and C3A in the cement but it is also
influenced by water-cement ratio, fineness and curing temperature.
For usual range of Protland cements, about 50% of the total heat is liberatedd between 1 and 3
days, about 75% in 7 days and nearly 90% in 6 months.
The table below shows the heat hydration of the four major compounds of cement.
Compound
90 days
13 years
C3F
58
104
122
C2F
12
42
59
C3A
212
311
324
C4AF
69
98
102
When C3S and C2S reacts with water, calcium silicate hydrate, (C-S-H) and Calcium
hydroxide Ca(OH)2 are formed.
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Calcium silicate hydrates are the most important products as they determine the good
properties of concrete.
The product of hydration of both C3S and C2S are the same.
2 (3CaO. SiO2) + 6 H2O 3 CaO. 2SiO2. 3H2O + 3 Ca (OH)2
2C3S + 6 H C3S2H3 + 3 Ca (OH)2
Or it can be written as
The corresponding weights are:
100 + 24 75
49
Similarly,
2 (2CaO. SiO2) + 4 H2O 3 CaO. 2SiO2. 3H2O + Ca (OH)2
Or it can be written as
The corresponding weights are:
22
C3S reacts readily with water and produces more heat on hydration. It is responsible for
early strength of concrete. A cement with more C3S content is better for cold weather
concreting. The quality and density of calcium silicate hydrate formed out of C3S is slightly
inferior to that formed by C2S.
C2S hydrates slowly. It is responsible for later strengths of concrete. It produces less heat of
hydration. The calcium silicate formed is rather dense and the quality of the product of C2S
is better than that produced in the hydration of C3S.
CALCIUM HYDROXIDE
The other product of hydration of C3S and C2S is calcium hydroxide Ca (OH)2. It constitutes
20 25 % of the volume of solids in the hydrated paste.
The presence of Ca (OH)2 affects the durability of concrete. It also reacts with sulphates
present in soils and water to form calcium sulphate with further reacts with C 3A and causes
deterioration of concrete. This is known as sulphate attack.
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To reduce the quantity of Ca (OH)2 in concrete and its bad effects, it is concerted into
cementitious product by using blending materials such as fly ash, silica fumes.
The reaction of pure C3A is very fast and this may lead to flash set. To prevent flash set,
Gypsum is added at the time of grinding.
Their presence is harmful to the durability of concrete especially where the concrete is
vulnerable to concrete attack.
The amount of gypsum added has significant bearing on the quantity of aluminate in the
cement. The maintenance of aluminate to sulphate ratio balances the normal setting
behaviour of cement.
TYPES OF CEMENT
The rapid increase in sophistication of design and construction techniques and the greater
attention to variations in regional and job conditions have created demand for modifications of
certain properties of concrete. This has resulted in the development of several "types" of Portland
cement and a greater use of concrete admixtures1.
The production of a different type of Portland cement involves certain adjustments in the
manufacturing process; mainly the selection of raw materials, chemical proportions, special
additives, and degree of grinding.
The following are the common types of cement:
TYPES OF CEMENT
Ordinary Portland
Cement (OPC)
1
i)
ii)
iii)
OPC 33 Grade
OPC 43 Grade
OPC 53 Grade
INFORMATION
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grade cement, if the 28 days strength is not less than 43 N/mm2,
it is called 43 grade cement and if the 28 days strength is not less
than 53 N/mm2, it is called 53 grade cement.
ii)
iii)
iv)
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It is also necessary that this cement should not be stored for more
than a month.
Sulphate Resisting
Cement
To remedy the sulphate attack, the use of cement with low C3A
content is found to be effective.
Such cement with low C3A and low C4AF content is known as
sulphate resisting cement. It usually has a high silicate content.
ii)
iii)
iv)
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Portland Pozzolana
Cement
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process, at ordinary temperature, to form compounds possessing
cementitious properties.
This cement is made by mixing a small amount of an airentraining agent with ordinary Portland cement clinker at the
time of grinding.
10
11
The raw materials used are high purity limestone, china clay and
silica sand.
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The raw materials needed for the manufacture of Portland cement are calcareous
materials such as limestone or chalk and argillaceous material such as shale or clay.
ii.
iii.
iv.
cooling the clinker and grinding to fine powder with addition of about 3 5 %
gypsum.
There are two processes known as wet and dry processes depending on whether the mixing
and grinding of raw materials is done in wet or dry conditions.
It is a long cylinder rotating about its axis once every minute or two. The axis is inclined at a slight angle, the
end with the burner being lower. The rotation causes the raw material to gradually pass along from where it
enters at the cool end, to the hot end where it eventually drops out and cools.
2
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7) The rotary kiln is a thick steel cylinder of diameter ranging from 3m to 8m, lined with
refractory materials, mounted on rollers and capable of rotating on its own axis.
8) When the slurry is sprayed on the hot surface of the flexible chains, it loses moisture and
becomes flakes. These flakes peel off and fall on the floor.
9) The rotation of the rotary kiln causes the flakes to move from the upper end towards the
lower end of the kiln subjecting itself to higher and higher temperature.
10) In the hottest part of the kiln, the raw materials get combined to form small masses of size 3
20 mm known as clinkers.
11) The clinker drops into a rotary cooler where it is cooled under controlled conditions and is
stored in silos and bins.
12) The cooled clinker is then ground in a ball mill with the addition of 3 5 % gypsum to
prevent flash setting of the cement.
13) The particles are crushed to the required fineness, separated by currents of air and stored
in storage silos where the cement is bagged or filled in barrels.
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TESTING OF CEMENT
Testing of cement can be divided into two categories:
i)
Field Testing
ii)
Laboratory Testing
1) FIELD TESTING
It is sufficient to subject the cement to field tests when it is used for minor works. The following are
the field tests:
a) Open the bag and take a good look at the cement. There should not be any visible lumps and
the colour of the cement should normally be greenish grey.
b) Thrust your hand into the bag. It must give you a cool feeling and there should not be any
lump inside.
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c) Take a pinch of cement and feel between the fingers. It should give a smooth and not gritty
feeling.
d) Take a handful of cement and throw it on a bucket full of water. The particles should float
for some time before they sink.
e) Take about 100g of cement and a small quantity of water and make a stiff paste. From the
stiff paste, pat a cake with sharp edges. Put it on a glass plate and slowly take it under water
in a bucket. See that the shape of the cake is not disturbed while taking it down the bottom
of the bucket. After some 24 hours, the cake should retain its original shape and at the same
time, it should also set and gain some strength.
If a sample of cement satisfies the above field tests, it may be concluded that the cement is not bad.
2) LAB TESTING
The following tests are usually conducted in the lab:
a) Fineness test
b) Consistency test
c) Setting time test
d) Strength Test
e) Soundness test
1. FINENESS TEST
Theory
The fineness of cement has an important bearing on the rate of hydration and hence, the rate of
gain of strength. Finer cement offers greater surface area for hydration and hence, faster
development of strength. The disadvantage of fine grinding is that it is susceptible to early
deterioration.
Test
Fineness of cement is tested in two ways:
i)
By sieving
ii)
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a) Sieve Test
-
Weigh correctly 100g of cement and take it on a 90 microns (0.09 mm) standard sieve. (1
micron = 0.001 mm)
Continuously sieve the sample giving circular and vertical motion for a period of 15 minutes.
ii)
Apply a very thin film of light mineral oil to the cell interior. Place the perforated disc on the
ledge in cell. Place two new filter paper discs on the perforated disc.
Fill the cell with mercury. Level the mercury to the top of the cell with a glass plate.
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Cement
Remove the top filter paper from the permeability cell and compress a trial quantity of 2.80 g of
cement into the space above filter paper to the gauge line in the cell. Place the other filter paper
above the cement bed.
Fill the remaining space in the cell above the filter paper with mercury. Level the mercury to the
top of the cell with a glass plate and remove mercury from the cell and weigh it, M2.
Calculate the volume occupied by the cement bed in the cell from the following equation.
V = (M1-M2)/D,
Where D = Density of mercury (13.54 g/cm3)
Average at least two volume determinations that agree to within 0.005cm3 and record this
value.
iii)
- Take an amount (W) of standard cement so as to give the cement bed of porosity e=0.500.
W = (1-e)V or W = 0.500V
-
Place the perforated disc on the ledge at the bottom of the cell and place on it a new filter paper
disc. Place the weighed quantity of standard cement, W, in the cell taking care to avoid loss.
Tap the cell to level the cement. Place a second new filter paper disc on the leveled cement.
Compress the cement with the plunger until the plunger collar is in contact with the top of the
cell. Slowly withdraw the plunger a short distance, rotate 900, repress the cement bed, and then
slowly withdraw.
Attach the permeability cell to the manometer tube with an air tight connection and slowly
evacuate the air in the manometer U-tube until the liquid reaches the top mark, then tightly
close the valve.
Start the timer when the bottom of the meniscus reaches next to the top mark and stop the
timer when the bottom of the meniscus reaches the bottom mark. Record the time t and temp.
of the test.
Repeat the whole procedure on two further samples of the same reference cement. Calculate
the average time of the three determinations. Then calculate the apparatus constant using the
formula given below.
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Where,
K=Apparatus constant
S0=Specific surface of reference cement
0=Density of reference cement
t0=Mean of three measured times
0=Air viscosity at the mean of the three temperatures.
iv)
-
Determination of fineness
Repeat the steps (1 to 6) as done in determination of apparatus constant, but this time using the
cement whose fineness is to be calculated.
Where,
S = Specific surface area
K = Apparatus constant
= Density of cement
t = Time
2. CONSISTENCY TEST
-
To find out the initial setting time, final setting time, soundness and strength of cement, a
parameter known as standard consistency has to be used.
The consistency of a cement paste is defined as that consistency which will allow a Vicat
plunger having 10 mm diameter and 50 mm length to penetrate to a depth of 33 35 mm from
the top of a mould.
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The apparatus is used to find out the % of water required to produce a cement paste of
standard consistency. The standard consistency is also called the normal consistency.
Take about 500 g of cement and prepare a paste with a weighed quantity of water
(about 24% by weight of cement) for the first trial.
ii)
The paste must be prepared in a standard manner and filled into the Vicat mould within
3 5 minutes.
iii)
After completely filling the mould, shake the mould to expel air.
iv)
v)
vi)
Conduct a 2nd trial (about 25% of water) and find out the depth of penetration of the
plunger.
vii)
Similarly, conduct trials with higher and higher water/cement ratio until the
penetration of the plunger reaches 33 35 mm.
viii)
That particular % of water which allows the plunger to penetrate only to a depth of 3335 mm is known as the % of water needed to produce a cement paste of standard
consistency.
ix)
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x)
3. Setting Time
The setting time of cement has been divided into initial setting time and final setting time.
The initial setting time of cement is regarded as the time elapsed between the moment that water is
added to the cement to the time that the paste starts losing its plasticity.
The final setting time is the time elapsed between the moment water is added to the cement and the
time when the paste has completely lost its plasticity and has attained sufficient firmness to resist
certain definite pressure.
The Vicat apparatus used for the consistency test is used for the setting time test as well. The
following procedures are adopted:
i.
Take 500g of cement sample and mix it with 0.85 times the water required to produce
cement paste of standard consistency. (0.85 P)
ii.
The paste should be put into the Vicat mould in specified manner within 3 5 minutes.
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iii.
Start the stop watch the moment water is added to the cement. The temp. of water and
that of the room shall be within 27oC 2 oC.
Lower the needle gently and bring it in contact with the surface of the test block and
quickly release. Allow it to penetrate into the test block.
v.
In the beginning, the needle will completely pierce through the test block. But after
some time, when the paste starts losing its plasticity, the needle may penetrate only to a
depth of 33 35 mm from the top.
vi.
The period elapsing between the time when water is added to the cement and the time
at which the needle penetrates the test block to a depth equal to 33 35 mm from the
top is taken as initial setting time.
viii.
The cement shall be considered as finally set when, upon lowering, the attachment
gently covers the surface of the test block, the centre needle makes an impression while
the circular cutting edge of the attachment fails to do so.
ix.
In other words, the paste has attained such hardness that the centre needle does not
pierce through the paste more than 0.5mm.
4. STRENGTH TEST
Strength tests are not made on neat cement paste because of difficulties of excessive
shrinkage and subsequent cracking of neat cement.
Procedures:
i.
Take 555g of standard sand, 185 g of cement (cement to sand ratio is 1:3) in a nonporous enamel tray and mix them with a trowel for one minute, then add water of
quantity (0.25P + 3.0) % of combined weight of cement and sand and mix the three
ingredients until the mixture is uniform in colour.
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ii.
The time of mixing should not be less than 3 mins nor more than 4 mins.
iii.
Immediately after mixing, the mortar is filled into a cube mould of size 7.06 cm. The
area of the face of the cube will be equal to 50 cm2
iv.
v.
Keep the compacted mould at a temperature of 27oC 2 oC and at least 90% relative
humidity for 24 hours.
vi.
After 24 hours, the cubes are removed from the mould and immersed in clean fresh
water until taken out for testing.
vii.
Three cubes are tested for compressive strength at 3, 7 and 28 days, the periods being
reckoned from the completion of vibration.
viii.
The compressive strength shall be the minimum force at which the cement cubes break
at 28 days.
5. SOUNDNESS TEST
The testing of soundness of cement is to ensure that the cement does not show any appreciable
subsequent expansion, else this will cause serious difficulties to the durability of the cement
structures.
The unsoundness of cement is due to the presence of excess lime, excess magnesia or excessive
proportion of sulphates.
Le chatelier apparatus is used to find the soundness of cement.
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Le Chatelier apparatus consists of a small split cylinder of spring brass or other suitable
metal. It is 30 mm in diameter and 30 mm high.
On either side of the split are attached two indicator arms 165 mm long with pointed ends.
Cement is mixed with 0.78 times the water needed for standard consistency (0.78 P) in a
standard manner and filled into the mould.
The whole assembly is immersed in water and a temperature of 27oC - 32oC and kept there
for 24 hours.
After this period of time, the distance between the indicator points are measured.
The water is heated and brought to boiling point in about 25 30 minutes and is kept
boiling for 3 hours.
The mould is then removed from the water, allowed to cool and the distance between the
indicators is again measured.
The difference between these two measurements represents the expansion of cement.
This must not exceed 10 mm for OPC. If it exceeds, then the cement is unsound.
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3. Water is also needed for the hydration of the cementing materials to set and harden during
the period of curing.
Besides its quantity, the quality of mixing water used in concrete has important effects on fresh
concrete properties, such as setting time and workability; it also has important effects on the
strength and durability of hardened concrete.
Potable water as mixing water:
The common specifications regarding quality of mixing water is water should be fit for drinking.
Such water should have inorganic solid less than 1000 ppm (parts per million). This content
leads to a solid quantity of 0.05% of mass of cement and w/c (water / cement) ratio is 0.5,
resulting in small effect on strength.
But some water which are not potable may be used in making concrete with any significant
effect.
Dark colour or bad smell water may be used if they do not possess deleterious substances.
Chlorides
500
SO3
1000
1000
Turbidity
2000
A simple way of determining the suitability of such water is to compare the setting time of
cement and the strength of mortar cubes using the water in question with the corresponding
results obtained using known suitable or distilled water.
Such tests are recommended when water for which no service record is available containing
dissolved solids in excess of 2000 ppm or, in excess of 1000 ppm.