Concrete Technology

Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

1.10 Chemical composition of Portland cement

Four compounds are usually regarded as the major constituents of cement:

Table 1.1: Main Compounds of Portland Cement

Where each oxide symbol with one letter:

CaO = C
SiO2 = S
Al2O3 = A
Fe2O3 = F
H2O = H
The rate of cooling affect the degree of crystallization and the amount of amorphous
material present in the cooled clinker.
1.10.1 Bogue Equations

The percentage of the main composition of cement can be calculated according to the
Bogue Equations, based on the assumption that the reactions reached the chemical
equilibrium state:
C3S = 4.07 (CaO) – 7.6 (SiO2) – 6.72 (Al2O3) – 1.43 (Fe2O3) – 2.85 (SO3)
C2S = 2.87(SiO2) – 0.754 (C3S)
C3A = 2.65 (Al2O3) – 1.69 (Fe2O3)
C4AF = 3.04 (Fe2O3)
Where, the terms in brackets represent the percentage of the given oxide in the total
mass of cement. Recently, these compositions are determined by x-ray diffraction.

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Concrete Technology
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Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

 C3S which is normally present in the largest amount, occurs as small

equidimensional colourless grains. On cooling below 1250 °C, it decomposes
slowly but, if cooling is not too slow, C3S remains unchanged and is relatively
stable at ordinary temperatures.
 C2S is known to have three forms.
o α-C2S, which exists at high temperatures, inverts to the β-form at about
1450 °C.
o β-C2S undergoes further inversion to γ-C2S at about 670 °C but, at the
rates of cooling of commercial cements, β-C2S is preserved in the clinker.
β-C2S forms rounded grains, usually showing twinning.
 C3A forms rectangular crystals, but C3A in frozen glass forms an amorphous
interstitial phase.
 C4AF is really a solid solution ranging from C2F to C6A2F, but the description
C4AF is a convenient simplification.

1.10.2 Minor compounds

In addition to the main compounds mentioned above, there exist minor compounds,
such as MgO, TiO2, Mn2O3, K2O and Na2O. Two of the minor compounds are of particular
interest: K2O and Na2O, known as the alkalis (about 0.4-1.3% by weight of cement). They
have been found to react with the reactive silica found in some aggregates, the products of
the reaction causing increase in volume leading to disintegration of the concrete. The
increase in the alkalis percentage has been observed to affect the setting time and the rate of
the gain of strength of cement.
SO3 form low percentage of cement weight. SO3 comes from the gypsum added (2-
6% by weight) during grinding of the clinker, and from the impurities in the raw materials,
also from the fuel used through firing process.

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Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

Iraqi specification no. 5 limited max. SO3 by 2.5% when C3A ≤ 7%, and by 3% when
C3A> 7%.
MgO, present in the cement by 1-4%, which comes from the magnesia compounds
present in the raw materials. Iraqi specification no. 5 limited max. MgO by 5%, to control
the expansion resulted from the hydration of this compound in the hardened concrete. When
the magnesia is in amorphous form, it has no harmful effect on the concrete.
Other minor compounds such as TiO2, Mn2O3, P2O5 represent < 1%, and they have
little importance.
Table 1.3 gives the oxide composition of a typical cement of the 1960s and the
calculated compound composition, obtained by means of Bogue's equations.

Table 1.3. Oxide and Compound Compositions of a Typical Portland Cement of the 1960s

1.10.3: Loss on Ignition (L.O.I)

It is the loss of the cement sample weight when it expose to the red temperature (at
1000 o C). It shows the extent of carbonation and hydration of free lime and free magnesia
P P

due to the exposure of cement to the atmosphere. Also, part of the loss in weight comes from
losing water from the gypsum composition. The maximum loss on ignition permitted by
Iraqi specification No. 5 is 4% by weight.

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Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

1.10.4: Insoluble residue

It is that part of cement sample that is insoluble in HCl. It comes from the unreacted
silica, to form soluble cement compounds diluting in this acid, largely arising from
impurities in gypsum. The maximum insoluble residue permitted by Iraqi specification No. 5
is 1.5% by weight.
1.10.5: Influence of a change in the oxide composition
Table 1.4; column (1) shows the composition of a fairly typical rapid hardening
cement. If the lime content is decreased by 3 per cent, with corresponding increases in the
other oxides (column (2)), a considerable change in the C3S : C2S ratio results. Column (3)
shows a change of per cent in the alumina and iron contents compared with the cement of
column (1). The lime and silica contents are unaltered and yet the ratio of the two silicates,
as well as the contents of C3A and C4AF, is greatly affected. Within the usual range of
ordinary and rapid-hardening Portland cements the sum of the contents of the two silicates
varies only within narrow limits, so that the variation in composition depends largely on
the ratio of CaO to SiO2 in the raw materials.
Table 1.4. Influence of Change in Oxide Composition on the Compound Composition

4
Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

It may be convenient at this stage to summarize the pattern of formation and hydration
of cement; this is shown schematically in Fig. 1.6.

Fig. 1.6. Schematic representation of the formation and hydration of Portland cement
1.10.3: Worked example of a Bogue calculation:

Clinker Analysis
SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O SO3 LOI IR Total
21.5 5.2 2.8 66.6 1.0 0.6 0.2 1.0 1.5 0.5 98.9
Free lime = 1.0% CaO

5
Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

Using the above analysis, the calculation is as follows:

Combined CaO = (66.6% - 1.0% free lime) = 65.6%
This is the figure we use for CaO in the calculation.
From the analysis, we have:
CaO= 65.6%; SiO2=21.5%; Al2O3=5.2% and Fe2O3=2.8%
The Bogue calculation is therefore:
C3S = 4.0710CaO -7.6024SiO2-1.4297Fe2O3-6.7187Al2O3
C2S = 8.6024SiO2+1.1Fe2O3+5.0683Al2O3-3.0710CaO
C3A = 2.6504Al2O3-1.6920Fe2O3
C4AF = 3.0432Fe2O3
Therefore:
C3S = (4.0710 x 65.6)-(7.6024 x 21.5)-(1.4297 x 2.8)-(6.718 x 5.2)
C2S = (8.6024 x 21.5)+(1.0785 x 2.8)+(5.0683 x 5.2)-(3.0710 x 65.6)
C3A = (2.6504 x 5.2)-(1.6920 x 2.8)
C4AF = 3.0432 x 2.8
So:
C3S = 64.67%
C2S = 13.17%
C3A = 9.04%
C4AF = 8.52%

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Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

Hydration of Cement: ‫اماهة السمنت‬

The reaction by virtue of which Portland Cement becomes a bonding agent take
place in a water – cement paste. In order words in the presence of water the
silicate and aluminates form products of hydration which in time produce affirm
.and hard mass called the hydration cement paste or product of hydration
‫ة‬J‫ام في عجين‬J‫امال لاللتح‬J‫ا ع‬J‫ة له‬J‫منت نتيج‬J‫بح الس‬J‫تي يص‬J‫ة ال‬J‫اعالت الفعال‬J‫ك التف‬J‫ان االماهه عبارة عن تل‬
‫تي‬JJ‫ة وال‬JJ‫ة االماه‬JJ‫وبتعبير أخر فانه بوجود الماء تشكل السيليكات وااللومينات نواتج لعملي‬. ‫االسمنت – الماء‬
. ) ‫بدورها وبمرور الزمن تنتج كتلة قوية وصلبه ( عجينة السمنت المتصلبة‬
There are two ways in which compounds of the type present in cement can react
with water. In the first, a direct addition of some molecules of water takes place,
this being a true reaction of hydration. The second type of reaction with water is
hydrolysis. It is convenient and usual, however, to apply the term hydration to all
.reactions of cement with water, i.e. to both true hydration and hydrolysis
‫اء‬JJ‫ع الم‬JJ‫ل م‬JJ‫منت من التفاع‬JJ‫هناك طريقتان قد تتمكن بموجبها المركبات من ذلك النوع والموجودة في االس‬
.‫ة‬JJ‫ة لالماه‬JJ‫ل الحقيقي‬JJ‫األولى تتمثل بحدوث إضافة بعض جزيئات الماء بشكل مباشر وتلك هي عملية التفاع‬.
‫أما الطريقة الثانية من التفاعل مع الماء فهو التحليل المائي ومن الناحية األخرى من المالئم والمعتاد إطالق‬
.‫ إي لكال من االماهة الحقيقة والتحلل بالماء‬,‫تعبير االماهة على كل تفاعالت السمنت مع الماء‬
:Determinations progress of hydration of cement
The progress of hydration of cement can be determined by different methods
:such as
1- Measurement of the a mount of Ca(OH)2 in the paste.
2- The measurement of heat of hydration.
3- The specific gravity of the paste
4- The amount of chemically combined water
5- The amount of un hydrated cement present
6- Strength of the hydrated paste

7
Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

: Calcium Silicate hydrate

The rates of hydration of C3S and C2S in a pure state differ considerably , as
shown in Fig. below . when the various compounds are present all together in
cement, their rates of hydration are affected by compound interaction. In
commercial cement, the calcium silicates contain small impurities of some of the
oxides present in the clinker. The impure C3S is known as alite and the impure
C2S is known as belite. These impurities have a strong effect on the properties of
.the calcium silicate hydrates
‫كل‬JJ‫ح بالش‬JJ‫ا موض‬JJ‫ة وكم‬JJ‫ا النقي‬JJ‫يرا في حالتهم‬JJ‫ اختالف كب‬C3S ‫ و‬, C2S ‫بين‬JJ‫تختلف سرعة االماهة للمرك‬
‫ات‬JJ‫ذه المركب‬JJ‫ل ه‬JJ‫ة لتفاع‬JJ‫ وعند وجود مركبات مختلفة في السمنت فان معدل االماهة سوف يتأثر نتيج‬.‫أدناه‬
‫ه من بعض‬JJ‫ات قليل‬JJ‫ع على كمي‬JJ‫ه في الواق‬JJ‫يوم حاوي‬JJ‫وفي حالة أنواع السمنت التجارية تكون سيليكات الكالس‬
‫رف‬JJ‫ا ويع‬JJ‫ ) كم‬Alite( ‫االليت‬JJ‫ير النقي ب‬JJ‫ ) غ‬C3S ( ‫رف الـ‬JJ‫ ويع‬.‫شوائب االكاسيد المتواجدة في الكلنكر‬
‫درات‬JJ‫واص هي‬JJ‫ير على خ‬JJ‫أثير كب‬JJ‫وائب ت‬JJ‫ك الش‬JJ‫ون لتل‬JJ‫ا ويك‬JJ‫ ) كم‬Belite ( ‫الباليت‬JJ‫ير النقي ب‬JJ‫ ) غ‬C2S (
. ‫سيليكات الكالسيوم‬

2C3S + 6 H = C3S2H3 + 3Ca(OH)2

2C2S + 4 H = C3S2H3 +3Ca(OH)2
The product of hydration is called is called Tobermorrite (CSH) and C3S produce
.more than twice as much Ca(OH)2 as formed by the hydration C2S

8
Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

‫ وذلك بسبب‬J‫ تقريبا ويشار إليه أحيانا بالتوبرمورايت‬C3S2H3 ‫التركيب اإلجمالي لهيدرات الكالسيوم هو‬
Ca(OH)2 ‫ ضعف الكمية من‬C3S ‫وينتج المركب‬. ‫التشابه بينه وبين معدن طبيعي يحمل ذلك االسم‬
. C2S ‫مقارنة بالمركب‬
:Tricalcium aluminate hydrate and the action of gypsum
‫هيدرات ثالث الومينات الكالسيوم وفعل الجبس‬
The amount of C3A present in most cement is comparatively small but its
behavior and structural relationship with the other phases in cement make it of
.interest
The Tricalcium aluminate hydrate forms a prismatic dark interstitial material,
possibly with other substances in solid solution, and is often in the form of flat
.plates individually surrounded by the calcium silicate hydrates
The reaction of pure C3A with water is very violent and leads to immediate
stiffening of the paste, known as Flash Set. To prevent this from happening
gypsum (CaSO4.2H2O) is added to cement clinker
‫) المتواجدة في غالبية أنواع السمنت تكون قليلة نسبيا ولكن سلوكها وعالقة بنيتها مع‬C3A( ‫إن كمية‬
‫األطوار األخرى لالسمنت تجعل منها مادة ذات أهمية حيث تشكل هيدرات ثالث الومينات الكالسيوم مادة‬
‫موشورية خاللية داكنة مع احتمال إن يكون ذلك التشكل مع مواد أخرى من المحلول الجامد وهي غالبا‬
C ‫هذا ويكون تفاعل إل‬. ‫ماتكون على هيئة ألواح مسطحة محاطة بشكل منفرد بهيدرات سيليكات الكالسيوم‬
‫ النقي مع الماء شديد جدا كما يؤدي ذلك التفاعل إلى تصلب مباشر للعجينة وهو ما يعرف بالتجمد‬3A
C3A ‫) ولغرض منع حدوث ذلك يضاف الجبس إلى الكلنكر حيث يتفاعل مع‬Flash Set ( ‫الفوري‬
‫) ولكن تتكون‬3CaO.Al2O3.3CaSO431H2O ( ‫لتكوين السلفو الومينات الكالسيوم غير قابله للذوبان‬
.‫في أخر األمر هيدرات ثالث الومينات الكالسيوم‬
C3A6H2O
C3A + H2O C3A8H2O Un Stable
C3A10H2O
C4AF + H2O C3A6H2O

9
Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

Main characteristics of the major compounds of Portland cement

Property C3S C2S C3A C4AF

Rate of reaction Medium Slow Fast Slow
Heat liberated per unit compound Medium Small Large Small
At early age strength Good Poor Good Poor
At later age strength Good Good Poor Poor

Setting ‫التجمد‬
This is the term used to describe the stiffening of the cement paste, although
the definition of the stiffness of the paste which is considered set is somewhat
arbitrary. Broadly speaking, setting refers to a change from a fluid to a rigid
stage. Although, during setting the paste acquires some strength, for practical
purposes it is important to distinguish setting from hardening, which refers to the
.gain of strength of a set cement paste
It seems that setting is caused by a selective hydration of cement compounds:
the two first to react are C3A and C3S.

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Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

‫ عجينة السمنت على الرغم من إن تعريف صالبة‬Stiffening ‫يستعمل هذا التعبير لوصف تصلب‬
‫ وبتعبير أوسع فان التجمد يشير إلى‬. ‫العجينة والذي يعتبر تماسكا" ليس إال تعريف اختياري إلى حد ما‬
. ‫التغيير من حالة السيولة إلى حالة الصالبة‬
‫وعلى الرغم من إن ألعجينه إثناء تصلبها تحصل على بعض المقاومة فانه ولألغراض العملية من المالئم‬
. ‫إن نميز بين التجمد والتصلب الذي يشير إلى اكتساب المقاومة للعجينة اإلسمنتية المتجمدة‬
‫ لمركبات السمنت حيث إن‬Selective hydration ‫ويبدو إن التجمد يحصل بفعل االماهة االنتقائية‬
.‫يكونان أول المواد المتفاعلة‬C3S ‫ و‬C3A ‫المركبين‬

Flash setting ‫التجمد الفوري‬

The rapid development of rigidity in a freshly mixed Portland cement paste, mortar, or

,concrete, usually with the evolution of considerable heat. This rigidity cannot be dispelled

.nor can the plasticity be regained, by further mixing without addition of water

The reaction of C3A with water is very rapid and the presence at gypsum is retarding this
reaction. The flash – setting properties of C3A is delayed by the addition of gypsum ( which
lays the formation of calcium Aluminate hydrate) thus C3S that sets first .Pure C3S mixed
.with water also exhibit an initial set C2S stiffens in a more gradual manner

‫ مما يسبب تطور سريع في تصلب عجينة‬J‫ بالتجمد الفوري‬J‫ مع الماء يحصل مايسمى‬C3A ‫بسبب التفاعل السريع للمركب‬
‫ هذا التفاعل انبعاث حرارة اليمكن اعادة لدونة الخليط عن طريق‬J‫السمنت البورتالندي أو المونه أو الخرسانة ويصاحب‬
.‫اعادة الخلط بدون إضافة الماء‬

‫ومن ثم يبدا‬.‫ هو الذي يتجمد أوال‬C3S ‫ المائية ولذلك فان المركب‬J‫إضافة الجبس يؤخر عملية تكوين الومينات الكالسيوم‬
."‫ بالتجمد تدريجيا‬C2S ‫المركب‬

 The setting time of cement decreases with rise in temperature .

 A low temperature setting is retarded.

11
Concrete Technology
Undergraduate studies
Al Mustansiryah University / Engineering College / Civil Engineering Department
Asst. Prof. Dr. Layth A. Al- Jaberi & Asst. Lect. Salwa R. Al Taee
Lect. 2

False Setting : ‫التجمد الكاذب‬

False setting is the name given to the abnormal premature stiffening of cement within a few
minutes of mixing with water. It differs from flash set in that no appreciable heat is evolved,
and remixing the cement paste without addition of water restores plasticity of the paste until
.it sets in the normal manner and without a loss of strength

‫تطلق تسمية التجمد الكاذب على عملية التصلب التي تحدث قبل األوان وخالل دقائق قليله من خلط السمنت بالماء وهي‬
) ‫ كما إن اعادة خلط العجينة ( المادة اإلسمنتية‬. ‫عملية تختلف عن التجمد الفوري بعدم انبعاث الحرارة بمقدار ملحوظ‬
.‫ ولحين تجمدها باألسلوب االعتيادي وبدون أية خسارة في مقاومتها‬J‫بدون إضافة الماء يعيد إليها لدونتها‬

: Some of the causes of false set are to be found in the

 dehydration of gypsum when interground with too hot a clinker ; hemihydrates

( CaSO4.1/2H2O) or anhydrite (CaSO4) are formed and when the cement is mixed with
water these hydrate gypsum. Thus Plaster set takes place with resulting stiffening of
the paste.
 False set may be associated with the alkalis in cement , so that during storage they may
carbonate and alkali Carbonates react with Ca(OH)2 liberated of C3S to form (CaCO3).
This induct rigidity of the paste.
 False set can be due to the activation of C3S by aeration at moderately high humidity.

: ‫بعض أسباب حصول التجمد الكاذب تكمن في‬

‫ طحنه مع الكلنكر الحار جدا حيث يتكون جبس نصف مائي وجبس إلمائي‬J‫إزالة ماء الجبس وذلك عن طريق‬ 
‫ يحدث تجمدا للجص‬J‫كما لوحظ انه عند خلط السمنت والماء فان تلك الهيدرات تكون الجبس وبذلك‬. ‫نتيجة لذلك‬
.‫مؤديا إلى تصلب العجينة‬
‫ القلويات المتواجدة في السمنت حيث إن تلك القلويات تتكربن إثناء الخزن وبالتالي فان‬J‫السبب األخر يرتبط بوجود‬ 
J‫ والتي بدورها‬.)CaCO3( ‫ليكون‬C3S ‫ المتحرر من التحليل المائي لـ‬Ca(OH)2 ‫الكربونات القلوية تتفاعل مع‬
.‫تترسب مؤدية إلى تصلب العجينة‬
. ‫ عالية‬J‫ عن طريق التهوية برطوبات‬C3S ‫يمكن إن ينتج التجمد الكاذب نتيجة لتحفيز‬ 

12