4. PORTLAND CEMENTS
History
Joseph
Aspdin, a British stone mason
October 21, 1824
Discovered an artificial cement
Heating a mixture of finely ground limestone
and clay in his kitchen stove
Calcination
5. PORTLAND CEMENTS
History
Aspdin
named the product Portland Cement
It resembled a famous stone quarried on the
Isle of Portland off the British Coast
He laid the foundation for today's portland
cement industry
6. PORTLAND CEMENTS
What is the difference between
cement and concrete?
Cement
Actually
an ingredient of concrete.
Closely controlled chemical combination of
calcium, silicon, aluminum and iron
Lime and silica make up about 85% of the
finished product mass.
7. PORTLAND CEMENTS
Concrete
Basically
a mixture of aggregates and paste
Aggregates are sand and gravel or crushed
stone; the paste is water and portland
cement
Gets stronger as it gets older
8. PORTLAND CEMENTS
Hydration
Cement
comprises from 10 to 15 percent of
the concrete mix, by volume.
Through this process, the cement and water
harden and bind the aggregates into a
rocklike mass.
This hardening process continues for years.
9. PORTLAND CEMENTS
Portland Cement
The product obtained by pulverizing clinker
consisting essentially of hydraulic calcium
silicates, usually containing one or more forms
of calcium sulfate as an interground addition.
12. PORTLAND CEMENTS
Reactions during
Clinker Formation
Temperature
(° C)
Reaction
Heat Change
100
Evaporation of free water
Endothermic
500 and above
Evolution of combined water from clay
Endothermic
900 and above
Crystallization of amorphous dehydration
products of clay
Exothermic
900 and above
Evolution of carbon dioxide from calcium
carbonate
Endothermic
900 – 1200
Main reaction between lime and clay
Exothermic
1250 – 1280
Commencement of liquid formation
Endothermic
1280 and above
Further formation and completion of cement
compounds
Endothermic
on balance
13. PORTLAND CEMENTS
Types of Portland Cements
Type
I (Regular portland cements)
- General purpose cement suitable for all uses.
It is used in general construction projects such
as buildings, bridges, floors, pavements, and
other precast concrete products.
14. PORTLAND CEMENTS
Types of Portland Cements
Type
II (Moderate-heat-of-hardening and
sulfate-resisting portland cements)
- Generates less heat at a slower rate and has a
moderate resistance to sulfate attack.
- Heat evolved should not exceed 295 and 335
J/g after 7 and 28 days
respectively.
15. PORTLAND CEMENTS
Types of Portland Cements
Type
III (High-early strength [HES] cements)
- Made from raw materials with a lime-to-silica
ratio higher than that of Type I cement and are
ground finer than Type I cements.
- It contains higher proportion of tricalcium
silicate.
16. PORTLAND CEMENTS
Types of Portland Cements
Type
IA
Similar to Type I with the addition of air-entraining
properties.
Type IIA
It is identical to Type II and produces airentrained concrete.
Type IIIA
It is an air-entraining, high-early-strength cement.
17. PORTLAND CEMENTS
Air entrainment
-
-
intentional creation of tiny air bubbles in concrete
bubbles are introduced into the concrete by the
addition to the mix of an air entraining agent,
surfactant (surface-active substance, type of
chemical that includes detergents).
primary purpose is to increase the durability of the
hardened concrete, especially in climates subject
to freeze-thaw.
18. PORTLAND CEMENTS
Types of Portland Cements
Type
IV (Low-heat portland cements)
- It has a lower percentage of C3S, C3A, low heat
of hydration and develops strength at a slower
rate than other cement types
- Ideal for use in dams and other concrete
structures where there is little chance for heat to
escape.
19. PORTLAND CEMENTS
Types of Portland Cements
Type
V (Sulfate-resisting portland cements)
- Used only in concrete structures that will be
exposed to severe sulfate action, principally
where concrete is exposed to soil and
groundwater with a high sulfate content.
20. PORTLAND CEMENTS
Manufacturing Procedures
Two types of materials needed for production:
Calcareous (Rich in calcium)
- Limestone [includes aragonite, marble, chalk]
- Cement rock [includes marl]
Argillaceous (Rich in silica)
- Clay
- Shale
21. PORTLAND CEMENTS
Closed-circuit grinding – in preparing the raw
materials, the fines are passed on and the
course material returned
Open-circuit grinding – the raw materials are
ground continuously until its mean fineness has
reached the desired value
23. PORTLAND CEMENTS
Grinding Hookups
c. two-stage setup with primary compartment closed-circuited
d. efficient two-or three-compartment circuit closed with screen
and air separator
24. PORTLAND CEMENTS
Grinding Hookups
e. highly efficient three-stage system closed-circuited in each
stage
f. single-stage mill closed circuited with rake classifier
26. PORTLAND CEMENTS
Wet process (original one) is being replaced by
the dry process (new plants) because of the
saving in heat, accurate control and the mixing
of the raw mixture it affords. Wet process has
slurry formation due to water added to it. The
dry process does not require the addition of
water.
27. Isomeric flowchart for manufacture of
portland cement by dry and wet processes
PORTLAND CEMENTS
28. PORTLAND CEMENTS
Analyses of Portland Cements (in %)
CaO
SiO2
Al2O3
Fe2O3
MgO
Alkali
Oxides
SO3
0.66
2.90
1.40
0.82
2.26
1.73
Regular Cement (Average of 102)
Min
Max
Ave
61.17
66.92
63.85
18.58
23.26
21.08
3.86
7.44
5.79
1.53
6.18
2.86
0.60
5.24
2.47
High-Early Strength (Average of 8): High C3S
Min
Max
Ave
62.17
67.50
64.60
18.0
22.9
19.9
4.10
7.50
6.00
1.70
4.20
2.60
----------
----------
2.20
2.70
2.30
Low-Heat-of-Hardening (Average of 5): Lower C3S and C3A,
Higher C2S and C4AF
Min
Max
Ave
59.30
61.50
60.20
21.90
26.40
23.80
3.30
5.40
4.90
1.90
5.70
4.90
----------
----------
1.60
1.90
1.70
29. PORTLAND CEMENTS
Functions of Compounds
C3 A
Causes set but need
retardation (by gypsum)
C3 S
Responsible for early strength
(at 7 or 8 days)
C2S and C3S
Responsible for final strength
(at 1 year)
Fe2O3, Al2O3, Mg and alkalies
Lower clinkering temperature
31. CEMENT MANUFACTURE
Quarry
dumper
loader
Quarry face
1. BLASTING
2.TRANSPORT
storage at
the plant
crushing
conveyor
3. CRUSHING & TRANSPORTATION
1. BLASTING : The raw materials that are used to manufacture cement (mainly limestone and clay) are
blasted from the quarry.
2. TRANSPORT : The raw materials are loaded into a dumper.
3. CRUSHING AND TRANSPORTATION : The raw materials, after crushing, are transported to the plant by
conveyor. The plant stores the materials before they are homogenized.
32. CEMENT MANUFACTURE
Raw grinding and burning
storage at
the plant
Raw mill
conveyor
Raw mix
1. RAW GRINDING
preheating
kiln
cooling
clinker
2. BURNING
1. RAW GRINDING : The raw materials are very finely ground in order to produce the raw mix.
2. BURNING : The raw mix is preheated before it goes into the kiln, which is heated by a flame that
can be as hot as 2000 °C. The raw mix burns at 1500 °C producing clinker which, when it leaves the
kiln, is rapidly cooled with air fans. So, the raw mix is burnt to produce clinker : the basic material
needed to make cement.
33. CEMENT MANUFACTURE
Grinding, storage,
packing and dispatch
Gypsum and the secondary additives are added
to the clinker.
clinker
storage
Finish grinding
1. GRINDING
silos
dispatch
bags
2. STORAGE, PACKING, DISPATCH
1.GRINDING : The clinker and the gypsum are very finely ground giving a “pure cement”. Other secondary
additives and cementitious materials can also be added to make a blended cement.
2. STORAGE, PACKING, DISPATCH :The cement is stored in silos before being dispatched either in bulk or in
bags to its final destination.
35. OTHER CEMENTS
For many corrosive conditions, portland cement
is unsuitable. Hence many special cements
have been developed, of which are industrially
important
36. OTHER CEMENTS
Pozzolans
-
-
-
A material which is not cementitious in itself
but which becomes so upon admixture with
lime
The early strength of such a cement is lower
than portland cement, but within a year the
strengths are equal
It resists the corrosive action of saline solutions
and seawater much better than portland
cement
37. OTHER CEMENTS
High Alumina
Cements
-
-
Calcium aluminate cement
Made by fusing a mixture of limestone and
bauxite (containing iron oxide, silica, magnesia
and other impurities)
Characterized by very rapid rate of
development of strength and superior
resistance to seawater and sulfate-bearing
water
38. OTHER CEMENTS
Silicate Cements
-
Possess low coefficients of expansion
It withstand all concentrations of inorganic
acids except hydrofluoric.
Not suitable at pH values above 7 or in
presence of crystal-forming systems
Joining of bricks in chromic acid reaction
tanks and in alum tanks
39. OTHER CEMENTS
Sulfur Cements
-
Resistant to non-oxidizing acids and salts
Should not be used in the presence of alkalis,
oils, grease or solvents
Generally accepted as a standard material
for joining bricks, tile and cast iron pipe
40. OTHER CEMENTS
Polymer Concrete
-
Polymer bonded concretes
Consist of aggregate plus resins such as
epoxy, methyl methacrylate or polyester
Rapid curing, corrosion resistance or high
corrosive strength
More expensive than regular portland
cement concrete
41. OTHER CEMENTS
Magnesium
Oxychloride Cement
Sorel’s cement
3MgO + MgCl2 + 11H2O 3MgO· MgCl2 ·11H2O
- Crystalline oxychloride contributes the
cementing action to the commercial cements
- Flooring cement with an inert filler and coloring
pigment
- Strongly corrosive to iron pipes in contact with it
-
43. CALCIUM COMPOUNDS
Limestone
Sedimentary
rock which is relatively inert,
except in the presence of a strong acid.
With the proper purity the rock deposit can
be used to produce lime, a manmade
chemical.
45. CALCIUM COMPOUNDS
Uses
Medical
purposes
Insecticides
Animal food
Gas absorption, precipitation, dehydration
Paper-making, soap, rubber, varnish
Manufacture of high grade steel and cement
46. CALCIUM COMPOUNDS
Quicklime (Burnt lime)
Calcium
oxide (CaO)
It is a white, caustic, alkaline crystalline solid at
room temperature.
Dangerous form of lime
47. CALCIUM COMPOUNDS
Slaked lime (Hydrated lime)
Calcium
hydroxide, Ca(OH)2
It is a colorless crystal or white powder and is
obtained when calcium oxide (quicklime) is
mixed, or slaked with water.
Used in many applications, including food
preparation.
48. CALCIUM COMPOUNDS
Hydraulic lime
Slaked
lime, used to make lime mortar (paste
used to bind construction blocks together and
fill the gaps between them)
Obtained from burning of limestone
containing clay and other impurities
Hydraulicity is the ability of lime to set under
water or wet conditions
50. CALCIUM COMPOUNDS
Manufacture
Lime has always been a cheap commodity because
limestone deposits are prevalent anywhere.
The lumps sometimes found in overburned or deadburned lime result from changes in the calcium oxide
itself, as well as from certain impurities acted upon by
excess heat, recognized as masses of relatively inert,
semi-vitrified material.
On the other hand, it is underburned lime if it often
happens that rather pure limestone is calcined
insufficiently and lumps of calcium carbonate are left
in the lime.
52. CALCIUM COMPOUNDS
Manufacture
The
total heat required for calcining per ton of
lime produced may be divided into two parts,
sensible heat to raise the rock to decomposition
temperature and latent heat of dissociation.
53. CALCIUM COMPOUNDS
Rotary kilns
Capacity
of up to 1600t/day. Almost all lime
produced in the country is calcined through this
one. The exterior of a rotary kiln is heavy steel and
the interior is lined with refractory brick.
Have the highest capacity and produce lime of
the most uniform quality but require the greatest
capital investment, have a high energy
consumption and need very expensive dustcollecting systems.
54. CALCIUM COMPOUNDS
Vertical kilns
Have
a hundreds of design
Four imaginary zonal sections in common:
- storage
- preheating
- calcining
- cooling
Limestone is charged into the top of the kiln and
the cooled lime is discharged at the bottom
55. CALCIUM COMPOUNDS
Dorrco FluoSolids system for producing lime from pulverized limestone or
calcium carbonate sludge. This is a five compartment reactor.
56. CALCIUM COMPOUNDS
Gypsum
very
soft sulfate mineral composed
of calcium sulfate, CaSO4·2H2O
component of Portland cement used to
prevent the flash settling of concrete
added about 4- 5% during the final grinding
57. CALCIUM COMPOUNDS
Gypsum
CaSO4·2H2O CaSO2· ½H2O + 1½H2O
ΔH25ºC = +69 kJ
If the heating is at a higher temperature, gypsum
loses all its water and becomes anhydrous
calcium sulfate, anhydrite
Calcined gypsum (the half water salt) can be
made into wall plaster by addition of a filler
material (eg. asbestos, wood pulp or sand)
Plaster of paris (without addition) can be used
for making sculptures and craft projects
58. CALCIUM COMPOUNDS
Calcination of Gypsum
Grinding
the mineral and placing it in large
calciners holding 9 to 22 tons
Temperature is raised to 120 to 150ºC, with
constant agitation to maintain uniform temp
The material in the kettle, plaster of paris or
first-settle plaster, may be withdrawn and
sold at this point, or it can heated further to
190ºC to make a second-settle plaster
59. CALCIUM COMPOUNDS
Calcination of Gypsum
First-settle
plaster is approximately the half
hydrate, CaSO4· ½H2O
Second-settle plaster is anhydrous
Practically all gypsum plaster sold in the form
of first-settle plaster mixed with sand or pulp
Second form is used in manufacture of
plasterboard and other gypsum products
Gypsum may be calcined in rotary kilns
similar to those used for limestone
60. CALCIUM COMPOUNDS
Hardening of Plaster
Hydration
chemical conversion
CaSO4· ½H2O + 1½H2O CaSO4· 2H2O
ΔH = - 2.9 kJ
Plaster sets and hardens because the liquid
water reacts to form a solid crystalline hydrate
Hydration with liquid water takes place at
temp below about 99ºC and thus gypsum
must be heated above 99ºC for practical
dehydration
61. CALCIUM COMPOUNDS
Miscellaneous
Calcium Compounds
Calcium
carbonate [CaCO3]
Whiting – pure, finely divided CaCO3 prepared
by wet grinding and levigating natural chalk
Putty – produced when whiting is mixed with
18% boiled linseed oil
62. CALCIUM COMPOUNDS
Miscellaneous
Calcium Compounds
Calcium
sulfide [CaS]
- Made by reducing calcium sulfate with coke
- Main use is as depilatory in the tanning
industry and in cosmetics
- Employed in luminous paints (finely dived
form)
63. CALCIUM COMPOUNDS
Miscellaneous
Calcium Compounds
Halide
salts [CaCl2, Ca(OCl)2]
- Main applications are to lay dust on highways,
to melt ice and snow on highways in winter, to
thaw cool in oil and gas as well fluids and as an
antifreeze in concrete
64. CALCIUM COMPOUNDS
Miscellaneous
Calcium Compounds
Calcium
arsenate [Ca3(AsO4)2]
- Produced by the reaction of CaCl2, Ca(OH)2,
NaH2AsO4· H2O (lime) , H3AsO4
- Used extensively as an insecticide and as a
fungicide
65. CALCIUM COMPOUNDS
Miscellaneous
Calcium Compounds
Calcium
organic compounds
Calcium acetate – employed largely in dying of
textiles
Calcium lactate – used in medicines and in foods
as source of calcium
Calcium soaps (stearate, palmitate and abietate)
are made by the action of the sodium salts of
acids on a calcium salt such as chloride. These are
insoluble in water but soluble In hydrocarbons.
Mainly used as waterproofing agents
67. MAGNESIUM COMPOUNDS
Magnesium
One
of the most widely distributed elements,
occupying 1.9% of the earth’s crust.
Occurs usually in the chloride, silicate,
hydrated oxide, sulfate or carbonate, in either
a complex or in simple salts.
68. MAGNESIUM COMPOUNDS
Uses
Extensively
in refractories and insulating
compounds
Manufacture of rubber, printing inks,
pharmaceutical and toilet goods
Air pollution control systems (removal of
sulfur dioxide from stack gases)
69. MAGNESIUM COMPOUNDS
Manufacture
Production of magnesium compounds by
separation from aqueous solutions may be
divided into four processes:
1.
Manufacture
from
seawater
without
evaporation, using seawater and lime as the
main raw materials
2. Manufacture from bitterns and mother liquors
from the solar evaporation of seawater for salt
3. Manufacture from dolomite and seawater
4. Manufacture from deep-well brines
70. MAGNESIUM COMPOUNDS
MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2
ΔH = +9.46 kJ
MgSO4 + Ca(OH)2 + 2H2O Mg(OH)2 + CaSO4· 2H2O
ΔH = - 13.3 kJ
The production of magnesium compounds from
seawater is made possible by the almost complete
insolubility of magnesium compounds by such a process
depends upon the following:
1. Means to soften the seawater cheaply, generally with
lime or calcined dolomite
2. Preparation of a purified lime or calcined dolomite
slurry of proper characteristics
3. Economical removal of the precipitated hydroxide
from the large volume of water
4. Inexpensive purification of the hydrous precipitates
5. Development of means to filter the slimes
74. MAGNESIUM COMPOUNDS
Magnesium Carbonates
These
vary from dense MgCO3 used in
magnesite bricks to the very low density 4MgCO3
· Mg(OH)2· 5H2O and 3MgCO3 · Mg(OH)2· 3H2O
once employed for insulation
Most of these of employed as fillers in inks, paints
and varnishes
75. MAGNESIUM COMPOUNDS
Oxides and
Hydroxides of Magnesium
On
heating magnesium carbonate or hydroxide,
magnesium oxide (MgO) is formed. It is used in
vulcanization of rubber, insulating material,
refractory material, for making other magnesium
compounds and as an abrasive
Magnesium peroxide is available from the
reaction of magnesium sulfate and barium
peroxide. It is employed as an antiseptic and a
bleaching agent.
76. MAGNESIUM COMPOUNDS
Magnesium Sulfate
Prepared by the action of sulfuric acid on
magnesium carbonate or hydroxite. It is sold on
many forms, eg. Hydrate MgSO4 · 7H2O, Epsom
salts. The less pure material is used extensively
as sizing and as a fireproofing agent.
77. MAGNESIUM COMPOUNDS
Magnesium Chloride
The
compound resembles calcium chloride and
has many of the same uses.
Application on ceramics, in the sizing of paper
and manufacture of oxychloride cement
Main use is in the making of metallic magnesium
78. MAGNESIUM COMPOUNDS
Magnesium Silicates
Asbestos
– mixed with varying qualities of
silicates of calcium and iron. Used in the
making of many fireproof and insulating
materials but its fibers have cancer causing
characteristics.
Talc – pure magnesium silicate in the form of
3MgO· 4SiO2·H2O, found naturally in scapstone
Its is employed as filler in paper, plastics,
cosmetics and toilet preparations.
80. MANUFACTURERS
CEMAP
Cement Manufacturers’ Association of the Philippines
Formerly known as Cement Institute of the
Philippines until 1965.
The association enjoyed the support of the
Philippine government which recognized its importance
in ensuring economic growth.
The early industry association’s goals were to pool
the resources of the cement industry and to undertake
various endeavors that would enhance its orderly
growth and share in the development of the nation’s
economy.
81. MANUFACTURERS
Cemex Philippines
Group of Companies
APO Cement Corporation
CEMEX is the only eco-labeled cement company in the
Philippines. The APO Cement Plant is in Naga City, Cebu
Solid Cement Corporation
Located at Barangay San Jose, Antipolo City
82. MANUFACTURERS
Holcim
Philippines, Inc.
Bulacan, La Union, Lugait and Davao Plants
Currently the biggest cement company in the Philippines.
It was created by the merger in 2000 of the three cement
companies carrying the Union Cement brand; Bacnotan
Cement Corporation (BCC), Davao Union Cement
Corporation (DUCC) and Hi Cement Corporation (HCC).
83. MANUFACTURERS
Lafarge Associated
Companies
Lafarge
Republic, Inc. (LRI) - Bulacan Plant
Lafarge Republic, Inc. (LRI) - Norzagaray Plant
Lafarge Republic, Inc. (LRI) - Batangas Plant
Lafarge Republic, Inc. (LRI) - Teresa Plant
Lafarge Iligan, Inc.
Lafarge Mindanao, Inc.
85. MANUFACTURERS
Pacific Cement
Philippines, Inc.
It was organized and incorporated in 1964 to
manufacture ordinary Portland cement. The plant
comprises a Wet Process Single Production Line
with an original rated capacity of 600 TPD. It is
located at Surigao City.
89. POLLUTION PROBLEMS
Environmental Impacts
These
include emissions of airborne pollution in
the form of dust, gases, noise and vibration
when operating machinery and during blasting
in quarries, and damage to countryside from
quarrying.
Equipment to reduce dust emissions during
quarrying and manufacture of cement is
widely used, and equipment to trap and
separate exhaust gases are coming into
increased use.
90. POLLUTION PROBLEMS
Carbon Dioxide
Emissions
The
cement industry is one of two primary
industrial producers of carbon dioxide (CO2),
creating up to 5% of worldwide man-made
emissions of this gas, of which 50% is from the
chemical process and 40% from burning fuel.
The amount of CO2 emitted by the cement
industry is nearly 900 kg of CO2 for every 1000 kg
of cement produced.
91. POLLUTION PROBLEMS
Heavy Metal
Emissions in the Air
The
high-temperature calcination process of
limestone and clay minerals can release in the
atmosphere gases and dust rich in volatile
heavy metals; thallium, cadmium and mercury
are the most toxic.
92. POLLUTION PROBLEMS
Heavy Metals
Present in the Clinker
The
presence of heavy metals in the clinker
arises both from the natural raw materials and
from the use of recycled by-products or
alternative fuels.
Nickel, zinc and lead are commonly found in
cement in non-negligible concentrations.
94. SUPPLY AND DEMAND
World
sales for cement are forecast to expand
more than five percent annually through 2017 to
over 4.7 billion metric tons. Demand will rebound
sharply in North America and Western Europe,
while growth in China will decelerate yet still
achieve impressive gains. Blended cement will
account for over three-fourths of all new demand.
96. SUPPLY & DEMAND
The Southeast Asian cement market can be categorized under
three distinct clusters, namely: the large producers (Indonesia,
Thailand and Vietnam), the midsized producers (Malaysia and
Philippines), and the rest (Singapore, Cambodia, Laos, Myanmar,
Brunei and East Timor).
97. SUPPLY & DEMAND
The Philippines: Cementing growth
The Department of Budget and Management released its
economic growth forecasts. GDP is expected to expand
by between 6.6% and 7.6% in 2013 and by 7.4% and 8.6% in
2014, with industry – including construction, leading the
charge.
One of the biggest economic growth in 2012 was the
Philippines’ cement sector. According to the CEMAP,
demand for cement rose by 18% in 2012, the sharpest
increase in 15 years.
In 2013, Mr. Ernesto Ordoñez, president of the CEMAP, said
higher spending from the government on infrastructure
developments and increased investments in building
developments would boost turnover.