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Structure of hydrated cement paste

At any stage of hydration cement paste consist of
1-Calcium silicate hydrate.
The calcium silicate hydrate phase, CS-H, makes up 50 to 60 percent of the
volume of solids in a completely hydrated, the most important phase
determining the properties of the paste.; the C/S ratio varies between 1.5 and
2.0. The morphology of C-SH also varies from poorly crystalline fibers to
reticular network. Due to their colloidal dimensions and a tendency to cluster,
C-S-H crystals could only be resolved by electron microscopy. the material has
a layer structure with a very high surface area100 to 700 m2/g. The size of gel
pores, or the solid-to-solid distance about 18Å.
2-Calcium hydroxide.
Calcium hydroxide crystals (also called portlandite)constitute 20 to 25 percent
of the volume of solids in the hydrated paste.. It tends to form large crystals
with a distinctive hexagonal-prism morphology. The morphology usually and is
affected by the available space, temperature of
hydration, and impurities present in the system. It is has adverse effect on
cement paste durability to acidic solution because of the higher solubility of
Ca(OH)2 than C-S-H.
3-Calcium sulfoaluminates hydrates. Calcium sulfoaluminate hydrates
occupy 15to 20 percent of the solid volume in the hydrated paste and, therefore,
play only a minor role in the microstructure-property relationships. during the
early stages of hydration the sulfate/alumina ionic ratio of the solution phase
generally favors the formation of trisulfate hydrate, , also called ettringite,
which forms needle-shaped prismatic crystals.
In pastes of ordinary Portland cement, ettringite eventually transforms to the
monosulfate hydrate, C4AS−H18, which forms hexagonal-plate crystals. The
presence of the monosulfate hydrate in Portland cement concrete makes the
concrete vulnerable to sulfate attack.
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4-Unhydrated clinker grains. Depending on the particle size distribution of

the
anhydrous cement and the degree of hydration, some unhydrated clinker grains
may be found in the microstructure of hydrated cement pastes, even long after
hydration. As stated earlier, the clinker particles in modern Portland cement
generally conform to the size range 1 to 50 μm. With the progress of the
hydration process, the smaller particles dissolve first and disappear from the
system, then the larger particles become smaller.

Voids in the hydrated cement paste

In addition to solids, the hydrated cement paste contains several types of voids
which have an important influence on its properties.
1-Interlayer space in C-S-H. The width of the interlayer space within the C-S-
H structure to be 18 Å and that it occupy for 28 percent of the volume of solid
C-S-H. water in these small voids can be held by hydrogen bonding, and its
removal under certain conditions may contribute to drying shrinkage and creep.
2-Capillary voids. Capillary voids represent the space not filled by the solid
components of the hydrated cement paste. Capillary pores size about 1.3µm ,
varying in shapes and interconnected to form system randomly distributed
through cement paste, and its responsible on the permeability of hardened
cement paste.
Volume of capillary system reduced with progress of hydration because of the
volume of hydration products occupy more than twice volume of cement alone.
At w/c ratio more than 0.38 the volume of gel not sufficient to fill all voids so
that, capillary porosity depend on w/c ratio of mix and degree of hydration
influenced by type of cement.
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In mature and dense pastes the capillary voids may become blocked and
segmented by gel, and born into capillary pores interconnected by gel pores
only.
Continuous capillaries can be blocked and segmented or removed completely
from cement paste by using suitable w/c ratio and sufficiently long period of
curing.

Structure of aggregate phase

Aggregate properties such as bulk density and strength affected concrete
characteristics such as unit weight, elastic modulus and dimensional stability.
Many concrete properties affected by size, shape, and surface texture of
aggregate. Chemical and mineralogical composition of aggregate are less
important than physical characteristics such as size, volume, surface texture and
pores distribution.
Aggregate phase is stronger than other two phases of concrete and it has no
direct influence on strength of concrete except the case of high porous and
weak aggregate such as pumice, and the case of using aggregate containing the
higher portion of flat and elongated particles that cause a film of water close to
surface of coarse aggregate, this weak transition zone.
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Interfacial Transition Zone in Concrete

Significance of the interfacial transition zone
Have you ever wondered why:
■ Concrete is brittle in tension but relatively tough in compression?
■ The components of concrete when tested separately under uniaxial
compression remain elastic until fracture
■ The compressive strength of a concrete is higher than its tensile strength by
an order of magnitude?
■ At a given cement content, water-cement ratio, and age of hydration, cement
mortar will always be stronger than the corresponding concrete? Also, the
strength of concrete goes down as the coarse aggregate size is increased.
■ The permeability of a concrete containing even a very dense aggregate will
be higher by an order of magnitude than the permeability of the corresponding
cement paste?
■ On exposure to fire, the elastic modulus of a concrete drops more rapidly
than its compressive strength?
Microstructure
The following the sequence of transition zone development from the time
concrete is placed.
First, in freshly compacted concrete, water films form around the large
aggregate particles. This would account for a higher water-cement ratio closer
to the larger aggregate than away from it.
Next, as in the bulk paste, calcium, sulfate, hydroxyl, and aluminate ions,
produced by the dissolution of calcium sulfate and calcium aluminate
compounds, combine to form ettringite and calcium hydroxide. These
crystalline products in the vicinity of the coarse aggregate consist of relatively
larger crystals, and therefore form a more porous framework than in the bulk
cement paste. The platelike calcium hydroxide crystals tend to form
in oriented layers, with the c-axis perpendicular to the aggregate surface.
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Finally, with the progress of hydration, poorly crystalline C-S-H and a second
generation of smaller crystals of ettringite and calcium hydroxide start filling
the empty space that exists between the framework created by the large
ettringite and calcium hydroxide crystals. This helps to improve the density and
strength of the interfacial transition zone.
Strength
the cause of adhesion between hydration products and the aggregate particle is
van der Waals force of attraction; therefore, the strength of the interfacial
transition zone at any point depends on the volume and size of voids present.
Even for low water-cement ratio concrete, at early ages the volume and size of
voids in the interfacial transition zone will be larger than in bulk mortar;
consequently, concrete is weaker in strength. However, with increasing age the
strength of the interfacial transition zone may become equal to or even greater
than the strength of the bulk mortar. This may occur as a result of
crystallization of new products in the voids of the interfacial transition zone.
Such interactions are strength contributing because they also tend to reduce the
concentration of the calcium hydroxide in the interfacial transition zone. Large
calcium hydroxide crystals possess less adhesion capacity, not only because of
the lower surface area and correspondingly weak van der Waals forces of
attraction, but also because they serve as preferred cleavage sites owing to their
tendency to form an oriented structure.
In addition to the large volume of capillary voids and oriented calcium
hydroxide crystals, a major factor responsible for the poor strength of the
interfacial transition zone in concrete is the presence of micro cracks. The
amount of micro cracks depends on numerous parameters, including aggregate
size and grading, cement content, water-cement ratio, degree of consolidation
of fresh concrete, curing conditions, environmental humidity, and thermal
history of concrete.
The interfacial transition zone will be susceptible to cracking when subjected to
the influence of tensile stresses induced by differential movements between the
aggregate and hydrated cement paste. Such differential movements commonly
arise either on drying or on cooling of concrete. In other words, a concrete can
have microcracks in the interfacial transition zone even before a structure is
loaded. Obviously, short-term impact loads, drying shrinkage, and sustained
loads at high stress levels will have the effect of increasing the size and number
of microcracks.
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Strength of concrete
Strength of materials is the ability to resist stresses without failure.
Concrete is most unlike structural materials because it contain fine cracks even
before it subjected to external stresses, therefore concrete strength is related to
the required stress to cause fracture.

Significance of concrete strength

In concrete design and quality control, strength is the property generally
specified because of, testing of strength is easy, and many properties of
concrete such as, elastic modulus, water tightness or impermeability, and
resistance to weathering conditions including water aggressive are directly
related to strength and can be deduced from strength data.
In practice concrete is subjected to a combination of compressive, shearing and
tensile stresses in two or more direction, but uniaxial compression test is the
easiest to perform in the laboratory. 28-day compressive strength of concrete is
accepted as a general index for concrete strength.

Strength-Porosity Relationship
In general, a fundamental inverse relationship between porosity and strength of
solids. For simple homogeneous materials, it can be described
by the expression

where S = strength of the material which has a given porosity p

S0 = intrinsic strength at zero porosity
k = constant
For many materials the ratio S/S0 plotted against porosity follows the same
curve. the data in Fig. below represent normally-cured cements, autoclaved
cements, and a variety of aggregates.
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Powers found that the 28-day compressive strength fc of three different

mortar mixtures was related to the gel/space ratio.

where a is the intrinsic strength of the material at zero porosity p, and x the
solid/space ratio.

In hardened cement paste or mortar the porosity can be related to strength. The
presence of microcracks in the interfacial transition zone between the coarse
aggregate and the matrix makes concrete too complex a material for prediction
of strength by precise strength-porosity relations. The general validity of
strength-porosity relation, must be respected because porosities of the
component phases of concrete, including the interfacial transition zone, indeed
become strength-limiting.
With concrete containing low-porosity or high-strength aggregates, the strength
of the material will be governed both by the strength of the matrix and the
strength of the interfacial transition zone.
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Failure Modes in Concrete

Failure modes under stress are very complex and vary with the type of stress.
Under uniaxial tension, relatively less energy is needed for the initiation and
growth of cracks in the matrix. Rapid propagation and interlinkage of the crack
system, consisting of preexisting cracks at the interfacial transition zone and
newly formed cracks in the matrix, account for the brittle failure.
In compression, the failure mode is less brittle because more energy is needed
to form and to extend cracks in the matrix. It is generally agreed that, in a
uniaxial compression test on medium- or low-strength concrete, no cracks are
initiated in the matrix up to about 50 percent of the failure stress; at this stage a
stable system of cracks, called shear-bond cracks, already exists in the vicinity
of coarse aggregate. At higher stress levels, cracks are initiated within the
matrix; their number and size increases with the increasing stress levels. The
cracks in the matrix and the interfacial transition zone (shear-bond cracks)
eventually join up, and generally a failure surface develops at about 20°
to 30° from the direction of the load.

Compressive strength and factors affecting it:

Response of concrete to applied stresses depend on, type of stress and a
combination of various factors affecting porosity of matrix and transition zone.
These factors are discussed under three categories, materials proportions,
curing conditions and testing parameters.
characteristic and proportion of materials
a- Water-cement ratio
Strength is inversely proportional to w/c ratio according to Abrams w/c
ratio rule.
where k1 &k2 are constants

Figure below represent the relation between w/c ratio and compressive
strength of concrete. From figure, it noticed a typical deceasing of
compressive strength as w/c ration increasing, this reduction of strength
as a result of volume of voids increasing in the matrix and interfacial
transition zone.
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In high strength concrete (low w/c ratio) w/c <0.3, high increase in compressive
strength as a small reduction in w/c ratio, this behavior due to a significant
improvement in the strength of transition zone because Ca (OH)2 become
smaller.

b- Air entrainment
When air voids are incorporated in the system, either as a result of
inadequate compaction or using air entraining admixtures. They have
effect of increasing porosity and decreasing strength, the rate of loss
strength depend on w/c ratio in concrete mixture. Figures below show
effect of air entraining on compressive strength of concrete.
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Cement type:

Degree of cement hydration has a direct effect on porosity and strength. Under
standard curing condition, portland cement type III hydrate more rapidly than
other types, therefore at early age of hydration cement type III will has lower
porosity and higher strength. Compare with cement types I, II, and III the rate
of hydration and strength development of cement types IV, V, Is and Ip are
slower up to 28-days, thereafter diffrences are disappeare when they achieved a
similar degree of hydration. Therefore the effect of cement compositions on
porosity and stength is limited at early age.

Figures below represent effect of w/c ratio and cement type on compressive
strength.
Compressive strength

7-day 28-day
3-day Type I
1-day

w/c ratio
Compressive strength

1-day 3-day Type III

7-day 28-day

w/c ratio
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Aggregate:
In concrete technology, an overemphasis on the relationship between
water-cement ratio and strength has caused some problems. The influence of
aggregate on concrete strength is not generally appreciated in normal strength
concrete because, with the exception of lightweight aggregates, the aggregate
particle is stronger than the matrix and the transition zone in concrete. There are
aggregate characteristics other than strength, such as the size, shape, surface
texture, grading, and mineralogy, which are influence the characteristics of the
interfacial transition zone and therefore affect concrete strength. A change in
the maximum size of well-graded coarse aggregate can have two opposing
effects on the strength of concrete. With the same cement content and
consistency, concrete mixtures containing larger aggregate particles require less
mixing water than those containing smaller aggregate and larger aggregates
tend to form weaker interfacial transition zone containing more microcracks.
The net effect will vary with the water-cement ratio of the concrete and the type
of applied stress.
The effect of increasing maximum aggregate size on compressive strengths was
more pronounced with high and medium strength. This is because at lower
water-cement ratios the reduced porosity of the interfacial transition zone play
an important role in the concrete strength. A change in the aggregate grading
without any change in the maximum size of coarse aggregate, and water-
cement ratio, can influence the concrete strength when this change causes a
corresponding change in the consistency and bleeding characteristics of the
concrete mixture.