KAR-NAJAF Cement Plant

Training Course
Aug 2018

ACIS@NAJAF O&M TEAM

Training for Lab Test Staff- Cement
Basic Knowledge

Trainer：Song Tinghua

Date：2018.08
 Cementitious material

 Cementitous material：
 Under the action of physical chemistry, substances that can change from slurry to solid
stone body and can bond other materials and have a certain mechanical strength are
collectively referred to as gelling material. It is divided into two major categories,
inorganic and organic. Inorganic cementitious materials are classified into two types:
hydraulic and gas hardening.
 1） Hydraulic cementitious materials refer to materials that can harden in
air and in water after mixing. These materials are collectively referred to as
cement, such as Portland cement, sulfate-resistant cement, etc.
 2）Gas-hardening cementitious materials can not be hardened in water, but
can only be hardened in air, so it is called gas-hardening cementitious
materials, such as lime, gypsum, magnesium cementitious materials etc.
 Classification of Cementitious
Materials
Asphalt&Res
Organic in
 胶凝材料的分类
Cementiti
ous- Non-hydraulic Gypsum, lime,
hard water glass,
material magnesia
Inorgan
ic
Hydraulic
cement
hard

After mixing with water, it can After mixing with water, it can
only harden in the air and harden in the air and harden
cannot harden in water in water
 Portland Cement Production

Two Mills & One Kiln

 水泥生产工艺
Siliceous(cl
ay, sand)
1450℃

Burnin
Clinkd
Calcium Raw meal

er
(Limestone)

g
Corrective RM Fuel
material Clinker
(iron ore)
Corrective
Cement Gypsum
material
(bauxite) CM
Grinding Mixed
aids material
 Portland Cement Production
 Cement production
 The production of Portland cement mainly goes through three
stages: raw material preparation, clinker calcination and cement
grinding, referred to as two grinding and one burning;
 Raw material preparation: mainly to crush the calcareous raw
materials, clay raw materials and a small amount of corrected
raw materials, mix them in a certain proportion, grind them, and
mix them into raw materials with suitable ingredients and
uniform quality;
 Clinker calcination: a Portland cement clinker with calcium
silicate as a main component obtained by calcining the prepared
raw material in a cement kiln to partial melting;
 Cement grinding: the cement clinker is added with appropriate
amount of gypsum, and sometimes mixed with appropriate
amount of mixed materials to make cement;
 The key to the above process is the ingredients and calcination.
The purpose is to calcine the calcium-containing limestone and
the silicon-containing, aluminum-containing clay and iron ore
fines in a desired ratio to form the desired silicate minerals.
 Mixed Material Classification
Material that has volcanic ash property Mixed material Have no potential
or potential water hardening property water hardening
classification property

Active mixed material Inactive mixed material

 混合材料分类：
Activity indicator does not meet the
requirements

Sand,limestone,
block blast furnace
slag
Granulated Volcanic
blast ash Coal ash
furnace slag mixture
 Mixed Material Classification

Granulated The cement mortar 28d compressive

Volcanic strength ratio is greater than or equal to
blast Coal
ash mixed 75% of active mixed material; less than
furnace ash
material 75% is inactive mixed material.
slag
 Active Materials and Inactive
Materials
 1.Active mixed material: Under normal temperature conditions, a
mixed material capable of hydration with Ca(OH) 2 or cement
and producing a corresponding hydraulic hydration product is
called an active mixed material. In addition to the action of the
inactive mixed material, the active mixed material can also
produce a certain strength and can significantly improve the
performance of the cement.
 2.Inactive mixed materials: Mixed materials that cannot undergo
hydration reaction with Ca(OH)2 or cement under normal
temperature conditions are called inactive mixed materials.
Incorporating inactive mixed materials into cement can increase
cement production, reduce cement costs, adjust cement strength
grades, reduce hydration heat, and improve corrosion resistance.
 Modulus for Raw Meal & Clinker
* Limestone LSF
Limestone saturation factor is the ratio of the CaO content
required for the formation of calcium silicate (C2S and C3S) in all
SiO2 in cement clinker to the CaO content required for the total
SiO2 to form CaS. i.e.
CaO*100
LSF＝ ----------------------------------------------
2.81 SiO2 +1.18 Al2O3+0.65 Fe2O3
The LSF value of clinker reflects the amount of C3S produced by
clinker during calcination. High LSF value, difficult calcination,
easy to produce free calcium oxide, but high LSF value, good
calcined clinker, low free calcium oxide, high content of
tricalcium silicate, high clinker strength, fast hardening
characteristics; LSF The value is low, the content of dicalcium
silicate in clinker increases, the hardening rate of clinker slows
down, and the early strength is low.
 Modulus for Raw Meal & Clinker
* Silicic acid modulus
The silicic acid mojulus is the ratio of the SiO2 content in the
cement clinker to the sum of the contents of Al2O3 and Fe2O3.
SiO2
SM＝——————————
Al2O3＋Fe2O3
The magnitude of silicic acid ratio indicates the relative amount of
clinker-forming minerals and flux minerals produced during the
calcination process. The rate of silicic acid is too high, the silicate
minerals in the clinker are many, the flux minerals are less, the
calcination is difficult, the clinker hardening rate is slowed down;
the silicic acid rate is too low, the flux minerals are increased, the
silicate minerals are reduced, and the liquid phase is excessive.
When calcined, it is prone to blockage, ringing, etc., and the
clinker strength is lowered.
 Modulus for Raw Meal & Clinker
* Aluminum oxide modulus
The aluminum oxide ratio is the ratio of Al2O3 content to Fe2O3
content in cement clinker, i.e.
Al2O3
AM＝——————
Fe2O3
The aluminum oxide modulusreflects the relative content of C3A
and C4AF in the flux minerals, which is related to the speed of
clinker hydration and the difficulty of clinker calcination. When
the flux mineral content is constant, the aluminum oxygen rate is
high: the C3A content in the clinker increases, the C4AF content
decreases, the liquidus viscosity increases, and the C3S rate is slow.
Clinker calcination is difficult. On the contrary, the viscosity of the
liquid phase is lowered, and the clinker is easy to form, but the
sintering range of the material is narrow, and it is easy to form a
large block, which is disadvantageous for operation.
 Other Control Conditions in Raw
Meal
Due to poor adaptability of precalcining kiln to raw materials,
in order to avoid skinning and clogging, the alkali content
(K2O+Na2O) in the raw material is required to be less than 1,
and when the alkali content is greater than 1%, the sulfur in
the raw material is required. The molar ratio is 0.5 to 1.
Sulfur base molar ratio = MSO3 / (MK2O + 1/2MNa2O) In
order to control crust and blockage, the chloride ion in the
raw meal should be less than 0.150% (with bypass system).
Clinker
The clinker is mainly composed of four oxides of CaO, SiO2,
Al2O3 and Fe2O3. The sum of its contents is usually above 95%.
The fluctuation range of these four oxides is as follows:
CaO 62%～67% ;SiO2 20%～24% ;Al2O3 4%～7% ;Fe2O3 2.5%～6%
 Portland Cement Composition
 Mineral composition of Portland cement clinker
 Cement clinker is a collection of various minerals with fine
crystals.
Compound Abrr.
Oxide component Content% Remark
name symbol

Tricalcium
3CaO.SiO2 C3S 42～60
silicate
72~ Silicate
78 mineral
Dicalcium
2CaO.SiO2 C2S 15～32
silicate

Tricalcium
3CaO.Al2O3 C3A 4～11
aluminate
20~
Flux mineral
24
Tetracalcium
4CaO.Al2O3.Fe2O3 C4AF 10～18
ferric acid
 Main mineral composition in Portland cement
clinker

 There are four main minerals in clinker: C3S, C2S, C3A, C4AF, and a
small amount of f-CaO, periclase, alkali-containing minerals, and
vitreous. Generally, C3S+C2S content in clinker is about 75%, and
C3A+C4AF content is about 22%.
 1.Tricalcium silicate C3S: The content of C3S is usually more than
50% of clinker. It is quicker in hydration and higher in early
strength. It plays a major role in promoting cement hardening,
especially in early strength and late strength of cement. The
formation of C3S requires a high firing temperature and a long
firing time. The content is too high, and the firing is difficult,
which tends to cause an increase in f-CaO and a decrease in the
quality of the clinker.
 Main mineral composition in
Portland cement clinker

 2.Dicalcium silicate C2S (β-C2S): The content usually

accounts for about 20% of clinker, the hydration is
slow, the early strength is low, the hydration heat is
low, the volume is dry, the sulfate attack resistance is
strong, and the coagulation hardening is slow. It
plays a major role in the late strength of cement.
 Main mineral composition in Portland cement
clinker
 3.Tricalcium aluminate C3A: The content usually accounts for 4-11%
of clinker. The hydration speed, coagulation hardening is fast, the
exotherm is much, and the hardening is fast, which mainly
contributes to the early strength of the cement. In the later stage,
it almost no longer grows, even shrinks. C3A has large shrinkage
deformation, poor resistance to sulfate, high brittleness and poor
wear resistance.
 4.Tetracalcium tetracalcium C4AF: usually accounts for 10-18% of
clinker. The hydration rate is between C3A and C3S in the early
stage. The early strength is similar to C3A but can be continuously
increased in the later stage. The hydration heat is low. The
compressive strength contributes little, and the main contribution
to the flexural strength is greater. The shrinkage deformation is
small, and the wear resistance, impact resistance and sulfate
resistance are strong.
 Effect of mineral composition on
cement properties
 Cement is a mixture of several clinker minerals. By changing
the proportion of clinker minerals, the nature of the cement
changes accordingly.
 For example, increasing the content of tricalcium silicate can
produce high-strength cement; reducing the content of
tricalcium alluminate and tricalcium silicate, increasing the
content of dicalcium silicate, and producing cement with low
hydration heat, such as cement for dam Increase the content
of tetracalcium iron alluminate to obtain cement with higher
flexural strength, such as road cement.
 The influence of various minerals in
Portland cement on strength

 The hydration rate of each mineral of Portland

cement clinker is: C3A＞C4AF ＞C3S＞C2S
 C3S mainly make strength effect
 C2S mainly make late strength effect
 C3A mainly make early strength effect
 C4AF mainly make durability effect
 The main influencing factor of cement stability is
free CaO、MgO。
 Portland Cement Composition
 Effect of clinker minerals on cement properties

Characteristic
Nam Strength Corrosio
Hydra Dry
e Hydration development Setting n
tion shrin
speed time resistanc
Early Late heat k
e
mediu medi
C3S Faster high high normal medium
m um

C2S Slower low high slow low high low

C3A Rapid high low quick high low high

<C3A slow in mediu

C4AF low normal low high low
late period m
 Harmful cement clinker mineral
 In addition to the above four main clinker minerals, cement
clinker also contains a small amount of free CaO, MgO, K2O,
Na2O and SO3 harmful components.
 （1） Free CaO, excessive MgO will lead to poor cement
volume stability;
 （2） K2O, Na2O can react with some rocks as concrete
aggregates to cause "alkali-aggregate reaction", which
causes the cement slurry to burst and is extremely harmful;
 （3） Excessive SO3 content may cause false condensation,
decrease in strength or cause cracking of cement stone,
and even lead to poor cement volume stability.
 Magnesium Oxide
 MgO in the clinker is mainly brought in by limestone raw
material. Developed into a coarse, structurally dense
periclsite at a high temperature of 1400 °C.
 Calcification rate of periclase is slower and is generally
hydrated after 10 months. Therefore, it takes a long time to
reveal its harmfulness. When it hydrates to form Mg(OH)2,
the volume expands by 148%.
 In the test, the 100 ° C boiling method can not make a
large amount of hydration, so the autoclave method under
high temperature and high pressure conditions.
 Magnesium Oxide
* Magnesium oxide (MgO) in clinker can cause cement to swell
and affect the stability of cement.
 An appropriate amount (about 2%) of MgO is present, which
can increase the amount of liquid in the clinker and lower the
viscosity of the liquid phase. Promote the formation of
silicate minerals and reduce the content of f-CaO, which is the
lowering of the firing temperature of cement clinker and
significantly improve the quality of clinker.
 MgO has a significant sulfur-fixing effect, and in a certain
content range (1%~2.29%), as its content increases, SO3
content in clinker also increases.
 Appropriate amount of MgO make the color of cement
clinker turn dark green. Excessive MgO make the color of
cement clinker turn grayish green and exists in the form of
periclase, which can destroy the stability of cement and
reduce the strength performance.
 The effect of chemical
substances on concrete

Calcium chloride 15%

Ammonium sulfate 20%

 The effect of chemical
substances on concrete

Sodium sulfate 25%

Sodium sulfate 25%

 The effect of chemical
substances on concrete

Sodium sulfate 10%

Sodium sulfate 40%

 Alkali content
 Alkali aggregation reaction: the alkali reacts with the active
silica in the aggregation to form an alkali silicate gel,
volume of which is larger than silica before the reaction, and
the gel swells and causes the concrete to crack.
 May cause rapid condensation and false condensation. The
gypsum will react with the alkali to consume a part, which
will destroy the retardation of gypsum.
 White spot on concrete surface
 The cement is not matched with some admixtures: it is
generally believed that as the soluble alkali content in
cement increases, adaptability of water reducing agent to
cement becomes worse, the plasticizing effect of water
reducing agent decreases, and concrete slump loss increases
with time.
 The effect of chemical
substances on concrete

Typical alkali
aggregation
reaction

Sodium hydroxide 10% Sodium hydroxide 10%

 Hydration and condensation
hardening of Portland cement
The substance changes from a non-aqueous state to a
Hydration watery state, from low water content to high water
content, collectively referred to as hydration.

The process of forming a malleable slurry in the initial

Condensation stage of cement and water mixing, and then gradually
thickening and losing plasticity is called coagulation.

Thereafter, the strength of the slurry gradually increases

Hardening and becomes a hard stone-like solid (cement stone), a
process called hardening.

Cement + water (fluid) → Plasticity slurry (plastic body) → solid

Hydration is the premise of cement toughening, and condensation
hardening is the result of cement hydration.
 Hydration and condensation
hardening of Portland cement
Initial
Incubation Condensati Hardening
reaction
period period on period period

 硅酸盐水泥熟料矿物的硬化
Initial 5～10min
Approx. 1～2h After hydration
Osmosis
for 24h

The rate of heat release has Continue to increase

increased dramatically and Hydration hydration and heat Heat release rate
then dropped to a very low is very slow is minimized
level release

Hydrated cement is Gradually lose Generate

only a very small part Basic plasticity
plasticity strength
 Hydration and condensation
hardening of Portland cement
 Condensation hardening process of Portland
cement

⑴ Initial coagulation: loss of

plasticity, no strength.

Condensation
⑵ Final setting: When
hardening
starting to have strength.
process

⑶ Hardening: Strength
develops to form cement
stone.