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Manufacture of Portland Cement

Limestone Grinding Preheaters &

quarrying storage and precalciners
(crushing) blending

Cements
Storage Burning
Other raw
and final kiln
materials
blending
Construction Materials and Testing gypsum
CE152P Clay/shale Grinding
quarrying Finish
storage and
grinding
(crushing) blending

Storage

Manufacture of Portland Cement Manufacture of Portland Cement

I.  Raw Materials II.  Preparation of Materials

•  Limestone •  Quarrying
•  Calcium carbonate •  Crushing Wet Process
•  Most common source of calcium oxide •  Storage
•  Iron-bearing aluminosilicates •  Drying
•  Used as the primary source of silica
•  Grinding
•  Clay and silts are preferred, finely divided state Dry Process
•  Shale, schists, and other argillaceous rocks are also used
•  Proportioning
•  Final Grinding

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Manufacture of Portland Cement Manufacture of Portland Cement

III.  Burning Process IV.  Final Processing

•  Clinker, which is the material that emerges from the kiln,
emerges and is in the form of dark-gray porous nodules (6
to 50 mm in diameter).
•  Final blending will improve the uniformity of performance of
the product by averaging out small differences in chemical
composition and burning conditions.
V.  Quality Control

(Mindess et al., 2002)

Typical Oxide Composition of a

Composition of Portland Cement General-purpose Portland Cement
Chemical Name Mineral Name Chemical Shorthand Weight Percent
Formula Notation Oxide Shorthand Notation Common Name Weight Percent
Tricalcium Alite 3CaOŸSiO2 C3S 55 CaO C lime 64.67
silicate SiO2 S silica 21.03
Dicalcium silicate Belite 2CaOŸSiO2 C2S 18 Al2O3 A alumina 6.16
Tricalcium Aluminate 3CaOŸAl2O3 C3A 10 Fe2O3 F ferric oxide 2.58
aluminate
MgO M magnesia 2.62
Tetracalcium Ferrite 4CaOŸAl2O3ŸFe2 C4AF 8
K2O K 0.61
aluminoferrite O3 alkalis
Na2O N 0.34
Calcium sulfate Gypsum CaSO4Ÿ2H2O CS̅H2 6
dihydrate SO3 S̅ sulfur trioxide 2.03
Calcium Portlandite CaOŸH2O CH - CO2 C̅ carbon dioxide -
hydroxide H2O H water -
The missing percentages may be accounted by the impurities. (Mindess et al., 2002) (Mindess et al., 2002)

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Bogue Calculation Bogue Calculation

•  Calculation of the phases from Case I: A/F ≥ 0.64 Case II: A/F < 0.64
the composition
C3S = 4.071C − 7.600S − 6.718A C3S = 4.071C − 7.600S − 4.479A
•  After Robert H. Bogue who first
emphasized the advantages of −1.430F − 2.852S −2.859F − 2.852S
knowing the compound C2 S = 2.867S − 0.7544C3S C2 S = 2.867S − 0.7544C3S
composition of a portland cement
•  ASTM C 150 C3 A = 2.650A −1.692F C3 A = 0
•  Quantities represent the C4 AF = 3.043F C4 AF = 2.100A +1.702F
percentages by weight
https://www.researchgate.net/profile/
Paul_Stutzman/publication/251774396/figure/ With the previous table:
fig2/AS:298066063183874@1448075895255/ C3S = 52.6%; C2S = 20.6%; C3A = 12.0%; C4AF = 7.9%
Fig-2-Robert-H-Bogue-was-the-first-Director-of-
the-Portland-Cement-Association.png

Seatwork
•  Calculate the compound composition for a Portland
cement having the following oxide analysis:
1.  C = 64.15%; S = 21.87%; A = 5.35%; F = 3.62%; S̅
2.53%
=
Hydration of
2.  C = 64.15%; S = 21.37%; A = 5.35%; F = 3.62%; S̅
2.53%
3.  C = 64.15%; S = 21.87%; A = 6.02%; F = 2.63%; S̅
=

=
Cement
2.84% Cements
4.  C = 63.54%; S = 23.09%; A = 3.61%; F = 6.38%; S̅ = Construction Materials and Testing
2.29% CE152P

To be submitted at Blackboard (April 24, 2018)

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Characteristics of Hydration Rates of Hydration of the

of the Cement Compounds Cement Compounds
Compounds Reaction rate Amount of heat
liberated
Contribution to Cement •  C3A and C3S are the most reactive compounds
Strength Heat Liberation
C3S Moderate Moderate High High
•  C2S reacts much more slowly
C2S Slow Low Low initially, Low •  Gypsum slows the early rate of hydration of C3A.
high later
C3A + CS̅H2 Fast Very High Low Very high
C4AF + CS̅H2 Moderate Moderate Low Moderate

(Mindess et al., 2002)

(in pastes of the pure compounds)

Rates of Hydration of the Rates of Hydration of the

Cement Compounds Cement Compounds
•  No quantitative data available for C4AF; hydration of
C4AF + gypsum + water is slower than C3S; hydration
of C4AF without gypsum is faster
(Mindess et al., 2002)
(Mindess et al., 2002)

(in pastes of the pure compounds) (in a Type I cement paste)

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Rates of Hydration of the Compressive Strength Development in

Cement Compounds Pastes of the Pure Cement Compounds
•  Alite (impure C3S) and belite (impure C2S) react more •  Calcium silicates
rapidly than they do as pure pastes provide most of the
•  Ferrite (C3AF) hydrates more slowly than C3S strength developed by
portland cement.
•  C3S provides most of
the early strength (first

(Mindess et al., 2002)

three to four weeks).
•  Both C3S and C2S
contribute equally to
ultimate strength.
(Mindess et al., 2002)
(in a Type I cement paste)

Rate of Hydration
•  The hydration reactions of portland cement are all
exothermic.
•  During the hardening process, the concrete is being
continually warmed by the internal heat generated.
•  The contribution of each compound to the overall rate
of heat of evolution is a function of the heat of
ASTM Types
hydration, rate of hydration, and the fraction of the Cements
compound in the cement. Construction Materials and Testing
H 3 days = 240(C3S)+50(C 2S)+880(C3 A)+290(C 4 AF) CE152P
H1 year = 490(C3S)+225(C 2S)+1160(C3 A)+375(C 4 AF)

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ASTM Types ASTM Types

According to ASTM standard , there are five basics It is possible to add some additive to Portland Cement
types of Portland Cement: to produce the following types
1.  Regular cement , general use , called Ordinary Portland Ø Portland blastfurnace cement – Type IS
Cement (OPC) – Type I Ø Pozzlanic cement – Type IP
2.  Moderate sulphate resisitance , moderte heat of Ø Air-entrained Cement – Type IA
hydration – Type II
3.  Rapid-hardening Portland Cement,High early strehgth –
Type III
4.  Low heat Portland Cement – Type IV
5.  High Sulphate –resisting Portland cement – Type V

ASTM Types
Classification Characteristics Applications
Specifications
Type I General purpose Fairly high C3S content for good
early strength development
General construction
(buildings, bridges,
and Tests of
Portland
pavements, precast units, etc)
Type II Moderate sulfate Low C3A content (<8%) Structure exposed to soil or
resistance (Modified water containing sulfate ions

Type III
cement)
High early strength
(Rapid-hardening)
Ground more finely, may have
slightly more C3S
Rapid construction, cold
weathering concreting
Cement
Type IV Low heat of hydration Low content of C3S (<50%) and Massive structures such as Cements
(slow reacting) C3A dams
Construction Materials and Testing
Type V High sulfate Very low C3A content (<5%) Structure exposed to high
resistance levels of sulfate ions CE152P
White White color No C4AF, Low MgO Decorative (otherwise has
properties similar to type I)

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Specifications and Tests Chemical Requirements

•  Production of portland cement requires strict quality
control which led to establishment of the
requirements of cement.
•  Development of “standard” tests to ensure quality
•  In North America, American Society for Testing and
Materials (ASTM) developed common tests to
provide information.

ASTM C 150

Physical Requirements Fineness

•  The fineness to which the cement is ground can have
a considerable effect on the behavior of the cement
during hydration:
1.  The rate of hydration increases with increasing fineness
which leads to both a higher rate of strength gain and a
higher rate of evolution of heat
2.  Increasing fineness tends to decrease the amount of
bleeding but at high fineness the amount of water
required for workability for non-air-entrained concrete is
increased, which results in increased drying shrinkage

ASTM C 150

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Fineness Fineness
•  The fineness to which the cement is ground can have I.  Particle-size distribution
a considerable effect on the behavior of the cement II.  Specific surface of the particles
during hydration:
3.  At high cement fineness reduces the durability of
concrete to freeze-thaw cycles
4.  An increased fineness requires a greater amount of
gypsum for proper set control, owing to the increased
availability of C3A for reaction

Methods to Determine
Particle Size Distribution Fineness (Specific Surface)
•  The fineness is easily determined as the residue on •  Turbidimeter Test (ASTM C 115)
sieve No. 200 mesh (75 µm). •  Air Permeability Test (ASTM C 204)

https://www.globalgilson.com/content/images/thumbs/ https://www.humboldtmfg.com/product-images/std/H-3805.png
0012428_8-sieve-brassstainless-full-height-no-200-
mesh.jpeg https://5.imimg.com/data5/MT/YJ/MY-3796626/blaine-air-permeability-
apparatus-500x500.jpg

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Wagner Turbidimeter Method Wagner Turbidimeter Method

•  ASTM C 115 •  Readings are taken at given times and heights below
•  Measures specific surface involving preparation of a the surface of the kerosene.
suspension of cement in kerosene in a tall glass •  Assumptions:
container i.  The particles are spherical
•  Based on Stokes’ Law which when a small sphere ii.  The flow is truly viscous
falls through a viscous medium under the action of iii.  Particles in the range of 0 to 7.5 µm have a uniform size
gravity, it ultimately acquires a constant velocity of of 3.75 µm

g = acceleration due to gravity

2ga 2 ( d1 − d2 ) a = radius of the sphere
V= d1 = density of the sphere
9η d2 = density of the viscous medium
ŋ = viscosity

234 CEMENT MANUFACTURER'S HANDBOOK

21.02 Fineness of Portland Cement by Turbidimeter (Wagner)

234 CEMENT MANUFACTURER'S HANDBOOK

21.02 Fineness
This formula of applicable
is only PortlandtoCement by specific
cement with Turbidimeter (Wagner)
gravity of 3.15.

Wagner Turbidimeter Method

38/-(2.O- log/so)
Sample
C 115 – 96a (2003)
This formula is only applicable to cement with specific gravity of 3.15.
1.5 + 0.75 log I + log Z + log Z + logZ - 9.5 logZ, 8.3 Operation of Turbidimeter—Operate the turbidimeter TABLE 4 Illustrative Form for Recording Turbidimeter Test Data
•  Specific surface, s, is calculated by the equation:
15 10 15 45

apparatus in accordance with the following procedure: and Calculation of Specific Surface

8.3.1 With retarding filter and sedimentation tank contain- NOTE—Values shown are for purpose of illustration only.
ing approximately 100 mL of clear kerosine in the light path, Sample identification sample X
Passing 45-µm (No. 325) sieve, r, corrected, T 90.4
adjust the light to the intensity, Ir, as determined in 7.1.3 by
38/-(2.O- log/so) Calibration factor, K 33.9
where * taking repeated readings at 1-min intervals until an unchanging
value indicates that the lamp and the photoelectric cell are in
Meter reading through filter alone, µA:
Before test 17.5
1.5 + 0.75 log I 15 + log Z 10 + log Z 15 + logZ 45 - 9.5 logZ, equilibrium. Remove the tank, check, and record the intensity After test 17.5
Weight of sample tested, g 0.25
of the lamp. Particle
I, µA log I
Size, µm
NOTE 13—To protect the microammeter, the lamp shall be turned on
50 17.3 ... 1.238A
S = specific surface of sample (cm /g) 2 only with a suspension or the retarding filter in position to reduce the light
intensity to a value within the range of the microammeter. A freshly 45 17.4 1.241
40 17.6 1.246
r = corrected weight percent of sample passing the No. 325 (45/u) charged storage battery should be momentarily short-circuited to reduce 35 17.9 1.253
where sieve.
the voltage to constant value. If the microammeter indication continues to 30 18.4 1.265
fluctuate, look for loose connections in the lamp and photoelectric cell 25 19.1 1.281
20 20.1 1.303
Z , Z , . . . , Z = microammeter reading, AtA, corresponding to par-
7 5 1 0 5 0
circuits, see that the rheostat contacts are clean, and make certain that the
lamp, socket, and reflector are rigidly fixed in their mounting. 15 21.6 1.334
10 23.9 1.378
ticle diameters 7 . 5 , 1 0 , . . . , 50/j. 8.3.2 Weigh the sample of cement in the appropriate amount 7.5 25.6 ... 1.408A
0.75 3 1.408 = 1.056
and record the weight to the nearest 0.0002 g. Prepare a 1.500
S = specific surface of sample (cm /g) 2
suspension in accordance with 8.2. Sum =
9.5 3 1.238 =
12.857
11.761
8.3.3 Place the shelf level pointer at the 30–50 µm position.
r = corrected weight percent of sample passing the No. 325 (45/u)
*only applicable to cement with specific gravity of 3.15
Difference = 1.096
S = (33.9 3 90.4 3 0.762)/1.096 = 2131 cm2/g
8.3.4 Fill the buret to the predetermined height with kero-
sieve.
Peray, Kurt E.. (1979). Cement Manufacturer's Handbook - 21.4 Particle Size Distribution.
sine from the same lot and at the same temperature as the A
(Round to 2130 cm2/g or 213 m2/kg)
For convenience in calculation, log I50 and log I7.5 are recorded in a separate
kerosine used in the suspension, and start oscillation of the tank
Z , Z , . . . , Z = microammeter reading, AtA, corresponding to par-
Chemical Publishing Company Inc..
7 5 1 0 5 0 containing the suspension in accordance with 8.2.2. Continue
column.

ticle diameters 7 . 5 , 1 0 , . . . , 50/j.
21.03 Table of Logarithms for
Turbidimeter Microammeter Readings
This table has been developed to simplify the physical testers task in
calculating the specific surface of a sample. The table should be copied
21.03
and posted on or near Table of Logarithms for
the turbidimeter.
Turbidimeter Microammeter Readings
This table has been developed to simplify the physical testers task in10.1 Calculation of Specific Surface:
calculating the specific surface of a sample. The table should be copied10.1.1 Calculate the turbimetric specific surface as follows:
and posted on or near the turbidimeter.
the oscillation until the kerosine drains to the zero line on the
buret; then stop the agitation. Immediately place the tank in
position in the path of the light beam.
8.3.5 Immediately remove the retarding filter from the light
path and close the cabinet door.
8.3.6 Read the microammeter to the nearest 0.1 µA at the
instant the kerosine in the buret drains past marks 50, 45, 40,
35, and 30.
8.3.7 Raise the shelf successively to the marks 25, 20, 15,
10, and 7.5 on the pointer scale, reading the microammeter at
each position as the kerosine drains past the corresponding
mark on the buret.
8.3.8 Lower the shelf to the 30–50 µm position. Replace the
filter in the path of the light beam, remove the tank, and check
the intensity of the lamp. If the microammeter indication has
shifted more than 0.3 µA from the initial setting through the
filter alone, the test must be repeated.
9. Data Recording
9.1 The form shown in Table 4 is suggested for the
recording of turbidimeter data and for the calculation of
specific surface.
10. Calculation
S 5 K F 1.5 1 0.75 log I 1 log I 1 log I
r~2 2 log I50!
G
7.5 10 15
where:
S = specific surface of the sample, m2/kg,
K = calibration factor as determined in 7.1.4
r = corrected weight percent of sample passing the 45-µm
(No. 325) sieve (Note 14), and I7.5, I10, I15...,
I50 = microammeter readings, µA, that correspond to
the particle diameters 7.5, 10, 15 ···, 50 µm.
NOTE 14—The value of K as determined in 7.1.3 applies only to a
material having the density of portland cement (approximately 3.15
3
Mg/m or g/cm3). For any other material, the corresponding value must be
calculated for this factor which, in the derivation of the formula, varies
inversely as the density of the particles (g/cm3).
10.1.2 To calculate the specific surface values in square
metres per kilogram, multiply the surface area in cm2/g by the
factor of 0.1.
10.1.3 Round values in cm2/g to the nearest 10 units (in
m2/kg to the nearest unit).
10.2 Specific Surface From First Turbidity Reading I50—
This test method may be used for successive determinations
from the same plant, provided that the same size test samples
are used and that there is no great change in fineness, color, or
other properties of the cement. Under these conditions the
specific surface of a sample may be calculated from the first
turbidity reading, I50, by using the following equation:
S 5 c~2 2 log I50! (3)
where:
S = specific surface of the sample, m2/kg,
I50 = microammeter reading corresponding to particle di-
9

... 1 log I45 – 9.5 log I50 (2) ameter of 50 µm, and
c = transmittancy constant for the particular plant.

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236 CEMENT MANUFACTURER'S HANDBOOK

21.04 Particle Size Distribution

The turbidimeter test data can be used to calculate the particle size dis-
tribution of a cement sample. For a detailed description of the calculations

Example
refer to the Appendix of the specification ASTM C-115, Part 9. The work-

Wagner Turbidimeter Method sheet below can be used in the computation of this particle size distribu-
tion.

•  Particle-size Percent by weight

fraction cummulative
•  Determine the specific surface and the particle size
distribution of the log U s - log / . . X 47.5 =
distribution of the cement sample given below.
sample can be
5 0 =

log 7 o - l o g / 4 5 = . . X 42.5 = .... Particle Size I

4 ..
*
calculated using the log / 3 5 - l o g / 4 0 =
log / 3 0 -log/35 =
..
..
. .
. .
X 37.5 = . . . .
X 32.5 = ....
50 11.0
turbidimeter test log I s - l o g / 3 0 =
2 .. . . X 27.5 = 45 11.4
log I O - l o g / 2 5 = . . X 22.5 = ....
data. 40 11.8
2 ..
log/is - l o g / 2 0 = •. . . X 17.5 = . . . .
log Ao - l o g / i s = . . .. X 12.5 = 35 12.1
log/7^ -log/ = .. . . X 8.8 =
2.00
1 0

X 3.8 = ....
30 13.1
- log / 7 . 5 = . . . .

total je =t
25 14.8
20 15.6
r
F =
total x
15 17.2
10 19.9
Fractional percent = Fx 1

7.5 21.6
Note: r = percent passing the 325 mesh sieve (45/1)

Blaine Air-Permeability Fineness of Cement

•  ASTM C 204 •  Both Wagner and Blaine methods provide an
•  Based on the relationship between the surface area acceptable way of measuring surface areas.
of the particles in a porous bed and the rate of fluid •  The Blaine value is generally about 1.5 times the
flow through the bed Wagner value because of the different theories
involved.
•  The Blaine method is more commonly used, but in
cases of dispute the Wagner method is deemed to
14 ε 3 Ai S = specific surface (cm2/g) govern.
S= D = powder density
D (1− ε ) υQ ε = porosity of the bes
A = cross-sectional area
i = hydraulic gradient
ν = kinematic viscosity
Q = rate of flow

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Specific Gravity ANNOUNCEMENT

•  The specific gravity of a given volume
Quiz # 1 on Cements

https://www.humboldtmfg.com/product-images/lrg/H-3400.png
material is the ratio of its mass to the mass
of an equal volume of water.
•  The specific gravity of cement shall not be May 3, 2018
less than 3.1.

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