Department of Civil Engineering

Indian Institute of Technology Kanpur

LECTURE 4
PORTLAND CEMENT BASED PASTE SYSTEMS
Textbooks or Reference Materials
[1] Sidney, M., Young, J.F., and Darwin, D. Concrete, 2nd Edition, Prentice-Hall,
Pearson Education, Inc., New Jersey, 2003.
[2] Mehta, P.K., and Monteiro P.J.M., Concrete – Microstructure, Properties and
Materials, Third Edition, McGraw Hill Education (India) Private Limited, New
Delhi, Prentice-Hall, Inc., 1993 or 2006.
[3] Neville, A.M., Properties of concrete, 5th Edition, Pitman Publishers, 1996.
[4] Taylor., H.F.W., Cement Chemistry (2nd Edition), Thomas Telford Services,
New York, USA
[5] Indian Standard Specifications (IS 383, IS 456, IS 2386 and others)
[6] Other websites and web based sources
A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

PORTLAND CEMENT BASED PASTE SYSTEMS

OVERVIEW
This lecture will provide details about the characteristics of hydrated compounds
other than the major compounds. An understanding of this lecture will enable
the students to perceive knowledge about some microstructural aspects such as
porosity, permeability and others as a result of cement hydration process.

TOPICS
o Characteristics of hydrated compounds (OTHERS)

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

CHARACTERISTICS OF HYDRATED
COMPOUNDS (OTHERS) IN PCBPS

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Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Components of hydrated PCBPSs (Revisiting)

o C-S-H gel (tobermorite)
o CH (portlandite)
o Ettringite (Aft)
o Monosulfoaluminates (Afm)
o Pores (capillary, gel, entrained & entrapped air)
o Water filled in pores (pore solution)
o Minor compounds
o Unhydrated cement
A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Pores
o The amount or volume of pores in PCBPS is called
its “POROSITY,” a major component of its
microstructure and an important durability property
o PCBPS is highly porous just after adding water.
o The porosity of the system decreases with time due
to reactions of the chemical compounds in cement
o Porosity of PCBPS is determined by
(i) Mercury Intrusion Porosimetry & (ii) Physical adsorption of gases
A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Pores
o Different types of pores or voids include
* Capillary pores
* Gel pores (Using Models)
* Entrained air voids
* Entrapped air voids

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
Capillary Pores
Difference between Capillary and Gel Pores

Description Diameter Description

10000-50 nm Large capillaries
(or 10-0.05mm) (macropores)
Capillary Pores 50-10 nm
Medium capillaries
(large mesopores)
10-2.5 nm Small isolated capillaries
(small mesopores)
Gel Pores 2.5-0.5 nm Micropores
< 0.5 nm Interlayer spaces

Courtesy: Sidney, M.,Young, J.F., and Darwin

 Comparison of different pores or voids in
PCBPS

Gel pores
 Difference between Capillary and Gel Pores

Description Category Role of water Properties Affected

Macropores Behaves as bulk Permeability; Diffusivity
water
Capillary Pores Large mesopores Small surface Permeability in the
tension forces absence of macropores;
generated Shrinkage above 80% RH
Small mesopores Large surface Shrinkage between 80%
tension forces RH and 50%
Gel Pores generated
Micropores Strongly adsorbed Shrinkage at all RH;
water; no menisci Creep
form

Courtesy: Sidney, M.,Young, J.F., and Darwin

Models for understanding gels

Courtesy: Sidney, M.,Young, J.F., and Darwin

C-S-H gel structure [Feldman and Sereda, 1970]
Surface tension and meniscus formation when gets water accumulated

No meniscus
formation

Vander Waal’s
bond/attraction
or ionic/covalent
bonding

Clay structure C-S-H gel structure

Courtesy: Sidney, M.,Young, J.F., and Darwin
C-S-H gel structure [Feldman and Sereda, 1970]
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Entrapped Air Voids

o Air voids in PCBPS is usually in the range of 1%-2.5%
(by volume of concrete)
o All these voids are entrapped
o Entrapped air voids occur due to improper
compaction of PCBPS mixtures
o If improperly compacted, air voids can be as high as
~5%-30%, which may result in porous, permeable
and extremely low strength mixtures
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Dr Sudhir Misra
Dr KV Harish
 Problems with improper consolidation

Honey-combing – (Very big entrapped air voids and continuous)

Bug-holes - (Very big entrapped air voids but discontinuous)

Typical entrapped air void size range: ~0.5 mm to 4 mm (visible)

 Department of Civil Engineering
Indian Institute of Technology Kanpur

Entrapped Air Voids

o Entrapped air voids can be reduced to the desired
level of size and quantity by
- Slightly increasing the w/c (without affecting other properties)
- Using the appropriate type or method of compaction
- Increasing the compaction effort
- Using other quality control measures at site/lab

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Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Methods of Compaction
o Hand compaction:
- Rodding
- Tamping
- Ramming
o Compaction by vibration:
- Internal Vibrators
- Formwork Vibrators
- Table Vibrators
- Platform Vibrators
- Surface Vibrators

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Entrained Air Voids

o Entrained air voids are not present if the mixture
either does not have air-entraining admixture or is
not subjected to any method used to entrain air
o Entrained air voids is important from the standpoint
of FREEZE-THAW condition
o Concrete can resist freeze-thaw damage only if it
has total air voids in the range of 4.5%-7%

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Entrained Air Voids

o An increase in the air voids of PCBPS will result in a
drastic decrease in its compressive strength even
within the levels or limits of voids required for
freeze-thaw resistance
o For highest effectiveness, the size of entrained air
voids shall be in the range of ~60 mm to 1 mm
o Air entraining admixtures are technologically
designed to cater for this requirement
A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Entrained Air Voids

o The dosage of air-entraining admixture used in
PCBPS is ~0.05% to 0.3% (by weight of cement),
rarely a dosage of 0.5% is used

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Comparison of different pores or voids in
PCBPS

Gel pores
 Department of Civil Engineering
Indian Institute of Technology Kanpur

MEASURING PORES INSIDE PORTLAND

CEMENT BASED PASTE SYSTEMS

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Dr Sudhir Misra
Dr KV Harish
Measuring pores using Mercury Intrusion Porosimetry (MIP)

The pressure required for

intrusion is according to the
Washburn-equation is:

D – diameter of pore radius

ϒ - surface tension of mercury
θ - contact angle
P - pressure

Courtesy: http://www.porotec.de/fileadmin/user_upload/PDF/Pascal_Broschure.pdf
http://porotechnology.com/gallery
http://www.particletechlabs.com/index.php/analytical-testing/gas-adsorption-porosimetry-analyses/mercury-intrusion-porosimetry
Measuring pores using Mercury Intrusion Porosimetry (MIP)

The pressure required for

intrusion is according to the
Washburn-equation is:

D – diameter of pore radius

ϒ - surface tension of mercury
θ - contact angle
P - pressure

Courtesy: http://www.porotec.de/fileadmin/user_upload/PDF/Pascal_Broschure.pdf
http://porotechnology.com/gallery
 Typical MIP curves for PCBPS

The pressure required for

intrusion is according to the
Washburn-equation is:

D – diameter of pore radius

ϒ - surface tension of mercury
θ - contact angle
P - pressure
dc – refers to critical pore diameter [mean size of pore entryways that allows max. percolation through the pore system (pt. of steep slope)]
dt – threshold diameter (first inflection point representing the onset of percolation)

Courtesy: http://www.porotec.de/fileadmin/user_upload/PDF/Pascal_Broschure.pdf
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Water-filled Pores (Pore solution)

o Water initially used during concrete mixing goes for
cement hydration and workability
Parts Water Available in Quantity
1 Chemically combined Inside the cement gel or hydrated Large
water compounds [C-S-H, CH, Aft (H36), Afm (H12)]
2 Physically adsorbed water Around or entrapped in the cement gel Significant
and/or interlayer water
3 Some water Evaporated due to heat evolved during Small
hydration
4 Some water Evaporated due to improper curing Small to
Significant
5 Water-filled pores Inside the capillary pores Small to
Significant
A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Water-filled Pores (Pore solution)

o Pore solution is in equilibrium (i.e. the rates of
dissolution and precipitation are equal to one
another) with the hydrated paste
o The pH of pore solution of pastes is ~13-13.5
o Pore solution contains Calcium, hydroxyl, alkali
(sodium and potassium) and sulfate ions

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
Typical changes in pore solution composition in
hydrating cement paste
Solution chemistry dominated Solution chemistry dominated
primarily by sulfate & alkali primarily by alkali

Sulfate is fully consumed by

the formation of ettringite

Courtesy: Sidney Diamond, Purdue University

 Department of Civil Engineering
Indian Institute of Technology Kanpur

Minor compounds
No. Name Hydration Quantity Importance to
Compound concrete
properties
1 Aft and Afm like C4AF Less to Not much
compounds substantial
2 Brucite [Mg(OH)2] MgO Less Cause cracking
3 CH Free lime Less Cause cracking
4 Other forms of calcium C3A Less Cause cracking
aluminate hydrates
5 Others - - -

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Unhydrated Cement Grain (UCG)

o UCG refers to the amount of cement in the PCBPS that
has not hydrated over longer periods of time
o UCG exists primarily because of the inability of the
water used in the PCBPS mixture to completely diffuse
into every individual cement grain
o The amount of UCG can be determined by calculating a
factor called as “degree of hydration (a)” using volume
relationships developed from hydration models

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

Unhydrated cement grain

o Generally for low w/c ratio mixtures, UCG will be
higher and for high w/c mixtures, UCG will be
lower
o UCG remain as unreacted micro-fillers in the PCBPS
o The hydration of UCG after 28 days is usually not
that easy since the system would have already
become very less permeable by this time

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

DEVELOPMENT OF HYDRATION
COMPOUNDS IN PCBPSs

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Understanding the development of hydrated compounds
in PCBPSs with time

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Development of hydrated compounds in PCBPSs
(during the first 30 minutes)

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Development of hydrated compounds in PCBPSs
(during the first 6 hours)

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Development of hydrated compounds in PCBPSs
(during the first 2 days)

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Development of hydrated compounds in PCBPSs
(during the first 90 days)

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Development of hydrated compounds in PCBPSs
(during the first 30 minutes)

Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

SUMMARY
o The types, characteristics and sizes of the
pores, voids, water-filled pores and minor
compounds are discussed

o Determination of porosity and development

of hydrated compounds of PCBPS is also
discussed

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish
 Department of Civil Engineering
Indian Institute of Technology Kanpur

A course on Hydration, porosity and strength of cementitious materials under the Massive Open Online Courses initiative
Dr Sudhir Misra
Dr KV Harish Courtesy: M.S. Shetty