CSE 224: ENGINEERING MATERIALS II.

2nd Semester 2017/2018.

Lecturer: Dr. Bruce. Kandie Week 2

Cement Hydration:

The reaction of cement with water is termed hydration: ettringites (rod-like crystals) are formed filling the pore in mature
concrete or mortar.
Cement + water C-S-H + CH + other phases
Calcium-silicate hydrate:
The “glue” that holds things Calcium hydroxide: Alumino-ferrite phases:
together and is mainly Little cementitious properties – easily Ultimate fate of sulfates –
responsible for strength and leached – involved in some deterioration impact on durability (esp.
impermeability. processes – represents approx 25% of sulfate attack) – dealt with in
hydration products and impermeability CE5503

The equation for the hydration of dicalcium silicate and tricalcium silicate are given by:
Tricalcium silicate + Water Calcium silicate hydrate+Calcium hydroxide + heat
2Ca3SiO5 + 7H2O 3CaO.2SiO2.4H2O + 3Ca(OH)2 + 173.6kJ
Dicalcium silicate + Water Calcium silicate hydrate + Calcium hydroxide +heat
2Ca2SiO4 + 5H2O 3CaO.2SiO2.4H2O + 3Ca(OH)2 + 58.6 kJ
In general, the rates of hydration during the first few days ranked from fastest to slowest are:
tricalcium aluminate > tricalcium silicate > tetracalcium aluminoferrite > dicalcium silicate.
There are typically four hydration produces:
1. Calcium silicate hydrate: this is the main reaction product and is the main source of concrete strength. It is often
abbreviated, using cement chemists' notation, to "C-S-H," the dashes indicating that no strict ratio of SiO2 to CaO
is inferred. The Si/Ca ratio is somewhat variable but typically approximately 0.45-0.50 in hydrated Portland
cement but up to perhaps about 0.6 if slag or fly ash or microsilica is present, depending on the proportions.
2. Calcium hydroxide - Ca(OH)2: often abbreviated to 'CH.' CH is formed mainly from alite hydration. Alite has a
Ca:Si ratio of 3:1 and C-S-H has a Ca/Si ratio of approximately 2:1, so excess lime is available to produce CH.
3. AFm and AFt phases: these are two groups of minerals that occur in cement, and elsewhere. One of the most
common AFm phases in hydrated cement is monosulfate. By far the most common AFt phase in hydrated cement
is ettringite. The general definitions of these phases are somewhat technical, but for example, ettringite is an AFt
phase because it contains three (t-tri) molecules of anhydrite when written as C3A.3CaSO4.32H2O and
monosulfate is an AFm phase because it contains one (m-mono) molecule of anhydrite when written as
C3A.CaSO4.12H2O.
When water is added, the reactions which occur are mostly exothermic, that is, the reactions generate heat. We can get an
indication of the rate at which the minerals are reacting by monitoring the rate at which heat is evolved using a technique
called conduction calorimetry. An illustrative example of the heat evolution curve produced is shown below.

Three principal reactions occur:

Almost immediately on adding water some of the clinker sulphates and gypsum dissolve producing an alkaline, sulfate-
rich, solution.

© Dr. Bruce Kandie 2017/2018 Academic year Page 1 of 3

CSE 224: ENGINEERING MATERIALS II.
2nd Semester 2017/2018.
Lecturer: Dr. Bruce. Kandie Week 2

Soon after mixing, the (C3A) phase (the most reactive of the four main clinker minerals) reacts with the water to form an
aluminate-rich gel (Stage I on the heat evolution curve above). The gel reacts with sulfate in solution to form small rod-like
crystals of ettringite. (C3A) reaction is with water is strongly exothermic but does not last long, typically only a few
minutes, and is followed by a period of a few hours of relatively low heat evolution. This is called the dormant, or
induction period (Stage II).
The first part of the dormant period, up to perhaps half-way through, corresponds to when concrete can be placed. As the
dormant period progresses, the paste becomes too stiff to be workable.
At the end of the dormant period, the alite and belite in the cement start to react, with the formation of calcium silicate
hydrate and calcium hydroxide. This corresponds to the main period of hydration (Stage III), during which time concrete
strengths increase. The individual grains react from the surface inwards, and the anhydrous particles become smaller.
(C3A) hydration also continues, as fresh crystals become accessible to water.
The period of maximum heat evolution occurs typically between about 10 and 20 hours after mixing and then gradually
tails off. In a mix containing PC only, most of the strength gain has occurred within about a month. Where PC has been
partly-replaced by other materials, such as fly ash, strength growth may occur more slowly and continue for several months
or even a year.
Ferrite reaction also starts quickly as water is added, but then slows down, probably because a layer of iron hydroxide gel
forms, coating the ferrite and acting as a barrier, preventing further reaction.
Voids in hydrated cement:
Concrete strength, durability, and volume stability is greatly influenced by voids in the hydrated cement paste
Two types of voids are formed in hydrated cement paste
Gel pores
Gel pores are needle-plate or foil shaped
Space between layers in C-S-H with thickness between 0.5 and 2.5 nm
Includes interlayer spaces, micropores, and small isolated capillary pores
Can contribute 28% of paste porosity
Little impact on strength and permeability
Can influence shrinkage and creep
Capillary pores
Capillary Voids are those pores not filled with hydration products
Depend on initial separation of cement particles, which is controlled by the w/c
It is estimated that 1 cm3 of anhydrous Portland cement requires 2 cm3 of space to accommodate
the hydration products
Space not taken up by cement or hydration products is capillary porosity
On the order of 10 to 50 nm, although larger for higher w/c (3 to 5 mm)
Larger voids affect strength and permeability, whereas smaller voids impact shrinkage
Concrete also commonly contains entrained air and entrapped air
Dimensional Range of Solids and Voids in Hydrated Cement Paste

© Dr. Bruce Kandie 2017/2018 Academic year Page 2 of 3

CSE 224: ENGINEERING MATERIALS II.
2nd Semester 2017/2018.
Lecturer: Dr. Bruce. Kandie Week 2

AGGREGATES:
Aggregates are normally used for concrete are natural deposits of sand and gravel, where available. In some localities, the
deposits are hard to obtain and large rocks must be crushed to form the aggregate. Up to 85% of concrete is aggregates.
TYPES OF AGGREGATE.
Aggregates are divided into two types as follows:
FINE AGGREGATE. These are aggregates material that will pass a No. 4 sieve and will, for the most part, be retained on
a No. 200 sieve. For increased workability and for economy as reflected by use of less cement, the fine aggregate should
have a rounded shape. The purpose of the fine aggregate is to fill the voids in the coarse aggregate and to act as a
workability agent.
COARSE AGGREGATE. Coarse aggregate is a material that will pass the 3-inch screen and will be retained on the No. 4
sieve. The application of coarser aggregate, the more economical the mix. Larger pieces offer less surface area of the
particles than an equivalent volume of small pieces. Use of the largest permissible maximum size of coarse aggregate
permits a reduction in cement and water requirements.
Aggregates is classified in to:
1. Roundness – fully water-worn or completely shaped by attrition
2. Irregular – naturally irregular, or partly shaped by attrition and having round edges
3. Flaky – material of which the thickness is small relative to the other two dimension
4. Angular – possessing well defined edges formed at the intersection of roughly planar face
5. Elongated – material, usually angular in which the length is considerably large than the other two dimension
6. Flaky and Elongated – material have the length considerably larger than the width and the width considerably
larger than the thickness
Grading of Fine and Coarse Aggregates
Percent age by mass passing sieves
Sieve size BS 882: 1992 AST M
C 33-93
AST M Overall Coarse Medium Fine
BS No. grading grading grading grading
10.0 mm 3/18 in. 100 100
5.0 mm 3/16 in. 89 - 100 95 - 100
2.36 mm 8 60 - 100 60 - 100 65 - 100 80 - 100 80 - 100
1.18 mm 19 30 - 100 30 - 90 45 - 100 70 - 100 50 - 85
600 µm 30 15 - 100 15 - 54 25 - 80 55 - 100 25 - 60
300 µm 50 5 - 70 5 - 40 26 - 80 5 - 70 5 - 70
150 µm 100 0 - 15 17 - 54 27 - 80

© Dr. Bruce Kandie 2017/2018 Academic year Page 3 of 3