CIVL 529

Sustainable and High

Performance Repair Materials
1. High performance concrete
2. Shotcrete
3. Concrete with polymers
4. Fiber reinforced concrete
5. Geopolymers
6. Ultra High Performance Fiber Reinforced
Concrete
 Course CIVL 529

Concrete: Review of Hydration and

Development of Microstructure

2
 Cementitious
Repairs/Strengthening
Concrete is a $10 Billion Market
ANNUAL PRODUCTION OF
CONCRETE (2019)
~8.3 Billion Cubic Meters
~20 Billion Tons
Aggregate : 3.8 and 4.6 GT

FOR COMPARISON:
SALT ~200 MILLION TONNES
SUGAR ~135 MILLION TONNES
OIL~5.2 BILLION TONNES
 Carbon Foot Print
◼ Cement is the source of about 8% of the world's carbon
dioxide (CO2) emissions, according to think tank Chatham
House.
◼ If the cement industry were a country, it would be the third
largest emitter in the world - behind China and the US.

◼ It contributes more CO2 than aviation fuel (2.5%) and is not far
behind the global agriculture business (12%).
 Paris Agreement on climate change: Annual emissions from
cement will need to fall by at least 16% by 2030.

2.4 Billion Tons

1.728 Billion Tons

China makes more cement than the rest of the world

 Ancient Cements
You always need a binder
SIMPLE SLAKING (Galilee 7000 BC)
CaCO3 + HEAT → CaO + CO2
CaO is unstable in the presence of moisture and CO2.
CaO + H2O → Ca(OH)2 + HEAT
SLAKING AND CARBONATION
Ca(OH)2 + CO2 (gas-> aq) → CaCO3 Egyptian Cements (3000 BC)
CaO + CaS04 → Some Ettringite Formation

SLAKING AND POZZALANICITY

(ROMANS 300 BC)
Cao + Silica (amorphous alumino-silicates) → Some
form of Calcium Silicates that resist leaching and can
be cast in water (hydraulic cements)
Roman Aqueduct
Portland, Blended and Other
Hydraulic Cements
cement industry
 1 ton of cement
Cement Production generates 1 ton of
CO2
CO2

CaCO3 SiO2

(GYPSUM)

Dry Process Preferred: The

(Gypsum) DRY PROCESS is faster, less
energy consuming and clinker
calcinated in the kiln has better
(Clinker) quality.
 Dry Process Preferred: The
The Different Between Dry Process And Wet DRY PROCESS is faster, less
energy consuming and clinker
Dry process: Water content is generally less than calcinated in the kiln has better
1%. So, the dry process can `reduces heat loss quality.
needed by heating and autoclaving water. But the
dry process has its own flaw that is the bad fluidity
of materials grain in a kiln. It will cause an uneven
mix.

Wet process: Slurry with 32%-40% water content.

Wet process method’s advantage is that its good
fluidity of raw materials slurry makes more even
mixed materials and produces high-quality clinker.
But it requires more heat consumption, so it is
environment-unfriendly.
Energy Consumption
 CO2 Production (Clinker)
(Gypsum)

Quarrying and
Transportation
(32%)

CO2 produced by the combustion of

fossil and alternative fuels used in
the burning process (responsible for
35–40% of the CO2 emissions).
Chemical Composition of Cement
Cement production is a fusion process where CaCO3 (chalk)
and SiO2 (shale) react at high a temperature (1300oC). The
high temperature oxidation produces stable oxides of various
elements
Typical Cement
CaO - 63%, SiO2 - 21%,
Al2O3 - 4.5%
Fe2O3 - 3%
In the cement chemistry notation,
C = CaO, S = SiO2, F = Fe2O3 and A = Al2O3
Typical Oxide Composition Cement
(Type 1)
Oxide Shorthand Common Name Mass (%)

CaO C lime 63
SiO2 S silica 22
Al2O3 A alumina 6
Fe2O3 F ferric oxide 2.5
MgO M magnesia 2.6
K2O K 0.6
alkalis
Na2O N 0.3
SO3 S sulfur trioxide 2

CO2 C carbon dioxide -

H 2O H water -
 Typical Mineral Composition of Portland
Cement
Compound Formula Shortha Mass
nd (%)

Tricalcium Ca3SiO5 C3S 55

silicate
Dicalcium Ca2SiO4 C2S 20
silicate
Tricalcium Ca3Al2O6 C3A 10
Aluminate
Tetracalcium Ca4Al2Fe2O10 C4AF 8
aluminoferrite

Gypsum CaSO4•2H2O CSH2 5

Cement Hydration
 Hydration of C3S and C2S
C3S
2C3S + 11H = C3S2H8 + 3CH
Tricalcium Silicate + Water = Calcium Silicate Hydrate (C-S-H) + Calcium Hydroxide

C2S
2C2S + 9H = C3S2H8 + CH
Dicalcium Silicate + Water = Calcium Silicate Hydrate (C-S-H) + Calcium Hydroxide

C3S or C2S + water = CSH + CH

CSH – Calcium Silicate Hydrate, amorphous and

colloidal in nature and main strength imparting
compound

CH – Calcium Hydroxide, portlandite, large crystals,

 Hydration of C3A and Role of Gypsum

Ettringite
C3A + H2O = reacts very fast (false set)
C3A + H2O + CSH2 = reacts much slower
C3A + 3CSH2 + 26H = C6AS3H32 H = -1350 J/g
Tricalcium Aluminate + Gypsum + Water = Ettringite

Monosulfoaluminate
Once CSH2 is depleted:
C 3A
C6AS3H32 + 2C3A + 4H = 3C4ASH12

Ettringite + Tricalcium Aluminate + Water =

Monosulfoaluminate
Ettringite
 Ettringite : An Expansive Reaction

Microcracks induced by ettringite

crystallizing in pore spaces

C3A + 3CSH2 + 26H = C6AS3H32

Tricalcium Aluminate + Gypsum + Water = Ettringite

Sulphate attack on concrete

 Hydration of C4AF

•Forms same reaction as C3A but to a lesser degree

•Uses small amounts of gypsum

C4AF + 2CH + 14H = C4(A,F)H13 + (A,F)H3

Tetracalcium aluminoferrite + Calcium hydroxide + Water

= Tetracalcium aluminoferrite hydrate + Ferric/Aluminum
Hydroxide
Hydration Characteristics

 Reactivity (how rapidly the four

cementing compounds react
with water)
 Fineness (how fineness controls
the rate of reaction)
 Heat Evolved (how much heat is
evolved in the process)
Fineness of Cement

 ↑ fineness, ↑ rate of reaction and thus

strength gain
 as the concrete gets older, the difference
between fine and coarse grain cement
disappears
 finer cements give off more heat early in
the hydration
 common measure is “blaine” fineness
 Heat Evolution

With Gypsum

Dormant Period
Reactivity of Cement Compounds

C3A C3S

C4AF

C2S
Cement Type and Use
ASTM C 150 (AASHTO M 85)
I General purpose cement, when there are no
extenuating conditions
II Aids in providing moderate resistance to sulfate
attack (Reduced C3A)
III When high-early strength is required
(Reduced C2S, Increased C3S, Increased fineness)
IV When a low heat of hydration is desired (in massive
structures) (Reduced C3S, Increased C2S)
V When high sulfate resistance is required
(Further Reduced C3A)
 Potential compound
composition,%
Type of Blaine
portland fineness Type
cement C3S C2S C3A C4AF m2/kg

I (mean) 54 18 10 8 369 Normal

Sulphate
II (mean) 55 19 6 11 377 Resistant

High early
III (mean) 55 17 9 8 548 strength

Low heat
IV (mean) 42 32 4 15 340 of
hydration
High
sulfate
V (mean) 54 22 4 13 373 resistance
 Types of Portland Cement (CANADA)

CSA A5 Description
Designation
Type 10 Normal Portland (used for most types of
construction)
Type 20 Moderate Portland (not common but used
for moderate sulphate resistance or
moderate heat of hydration
Type 30 High-early-strength (not common but used
for occasionally for rapid strength gain)
Type 40 Low-heat (not common now but historically
common for mass concrete projects)
Type 50 Sulphate-resistant (common in areas
where required by soil conditions)
 Heat of Hydration at 7 Days

Type I Type II Type II Type III Type IV Type V

cement cement Moderate cement cement cement
heat cement
% of
100 99 75 106 67 89
Type I

I Normal
II Moderate sulfate resistance
III High early strength
IV Low heat of hydration
V High sulfate resistance
Blended Hydraulic Cements
 Blended Hydraulic Cement
CSA A362 (ASTM C595)
 a mixture of portland cement and
one of:
 fly ash (or other pozzolans in ASTM)
 slag

 silica fume

 ternary blend (CSA)

 or calcined clay (ASTM)

 can be interground or blended after

grinding
 Hydraulic Cements - ASTM C 1157
“Performance Cement”
 cement specifications have historically been
prescriptive
⚫ e.g.: specify on types of ingredients and
chemistry

 modern plants want to use a variety of

material and develop their own secret
blends

 ASTM C1157 cements must meet physical

performance test requirements
⚫ e.g. strength, durability etc
Hydraulic Cement ASTM C1157
Performance Based Specifications

Type GU General use

Type HE High early strength
Type MS Moderate sulfate resistance
Type HS High sulfate resistance
Type MH Moderate heat of hydration
Type LH Low heat of hydration
 Other Types of Cements
Commercial Products
 Masonry cements
 Micro-fine or ultrafine of finely-
ground
 Expansive cement (e.g. Type K)
 Oil-well cements
 Calcium Aluminate Cements
 others
Development of Microstructure
Chemical Compounds of Portland
Cement

Tricalcium silicate Alite C3S 55

Dicalcium silicate Belite C2S 20

SEMs of Hardened Cement
Paste

500 X 1000X
 2C3S + 11H = C3S2H8 + 3CH
2C2S + 9H = C3S2H8 + CH

Calcium Silicate Hydrate (C3S2H8) Calcium Hydroxide (CH)

High W/C with Large
Capillary Porosity
Properties of the Hydration Products (Mindess 2003)
Development of Microstructure
a b

Schematic Outline of
Microstructural
Development in Portland
Cement Pastes (Calcium
Sulfoaluminates are
c d included in C-S-H here)
a) Initial Mix
b) 7 days
c) 28 days
d) 90 days
Pore Size Distribution in
Hydrated Cement Pastes

w/c =0.90

w/c =0.30
Age 28 Days
 Increasing
 Dimensional Range of Solids and
Pores in a Hydrating Cement Paste
 Unhydrated Cement and Pores

◼ Unhydrated residue of cement grains may persist even in

well hydrated cements
◼ Enormous range of pore sizes
◼ Water that occupies the pores plays many different roles
Simplified Model of Paste
Structure

C=Capillary
Porosity
(Depends on
w/c)

Gel
(Fixed
Porosity of
28%)
 Role of Water

Capillary
pores 
(Medium capillary pores)

Gel pores  (small capillary pores)

(Mindess 2003)
Classification of Water Held in
Hydrating Cement Paste
Volume Relationships among Constituents
of Hydrating Cement Paste

A Fixed Water/Cement Ratio= 0.5

Degree of Hydration = 1
Mineral and Chemical Admixtures

48
 Mineral Admixtures:
Supplementary
Cementing Materials

Nearly 85% of concrete in Canada has one or the other

Supplementary Cementing Material (SCM) in it. Almost
100% of repair materials have some SCM in them.

CSA A23.5 - A material that, when used in conjunction with

Portland cement, contributes to the properties of the hardened
concrete through cementitious or pozzolanic activity, or both.
 What are Pozzolans?
◼ CSA A23.5 - a Siliceous or alumino-siliceous
material that, in finely divided form and in the
presence of moisture, chemically reacts at
ordinary room temperatures with calcium
hydroxide released by the hydration of Portland
cement to form compounds possessing
cementing properties
 Pozzolans in Ancient Cements
SIMPLE SLAKING (Galilee 7000 BC)
CaCO3 + HEAT → CaO + CO2
CaO is unstable in the presence of moisture and CO2.
CaO + H2O → Ca(OH)2 + HEAT
SLAKING AND CARBONATION
Ca(OH)2 + CO2 (gas-> aq) → CaCO3 Egyptian Cements (3000 BC)
CaO + CaS04 → Some Ettringite Formation

SLAKING AND POZZALANICITY

(ROMANS 300 BC)
Cao + Silica (amorphous alumino-silicates) → Some
form of Calcium Silicates that resist leaching and can
be cast in water (hydraulic cements)
Roman Aqueduct
 The First Known Pozzolans

Coliseum: A Structure Using Early Pozzolanic

Cement

Volcanic Ash
Italian town of
Pozzouli
 Supplementary Cementing Materials

Silica Fume
Fly Ash (F)

Slag

Metakaolin

Fly Ash (C)

Calcined Shale
How Do Pozzolans Work?

◼ Approx. 20% - 25% of Hardened Paste

◼ Water Soluble
◼ Readily Reacts with CO2
◼ Weak Crystal Structure
◼ Very High pH

Calcium Hydroxide
Advantages of Pozzolans
◼ Better Workability
◼ Increased Long term Strength
◼ Reduced Efflorescence
◼ Reduced Heat of Hydration
◼ Increased Resistance to Chemical Attack
◼ Economy
◼ Increased Set Time in Hot Weather
◼ Reduction in Mix Water

Disadvantages of Pozzolans
◼ Increased Set Times especially in Cold Weather
◼ Lower Early Strength
◼ Some interference with air entrainment
 Types of Supplementary
Cementing Materials
◼ Natural Pozzolans (Diatomaceous Earth,
Calcined Shale, Pumicite, Quesnel Pozzolan,
Lassenite)
◼ Metakaolin
◼ Fly Ash
◼ Granulated Slag
◼ Silica Fume

Replacement of Cement from 5% to 50%

 Industrial By-Products
AS SUPPLEMENTARY CEMENTING MATERIALS

CaO SiO2 Al2O3 Fe2O3

Ordinary Highly
63% 22 6 3 Cementitious
Portland
Cement
SLAG Latent-
40 35 8 0 Cementitious

FLYASH Pozzolanic &

20 35 20 5 Cementitious
(High Lime)
FLYASH Pozzolanic
1 50 25 10
(Low Lime)
Highly
Silica 0 90 2 2 Pozzolanic
Fume
 Industrial By-Products
AS SUPPLEMENTARY CEMENTING MATERIALS

CaO SiO2 Al2O3 Fe2O3

Ordinary Highly
63% 22 6 3 Cementitious
Portland
Cement
SLAG Latent-
40 35 8 0 Cementitious

FLYASH Pozzolanic &

20 35 20 5 Cementitious
(High Lime)
FLYASH Pozzolanic
1 50 25 10
(Low Lime)
Highly
Silica 0 90 2 2 Pozzolanic
Fume
Fly-Ash

cenosphere A cenosphere is a
lightweight, inert,
hollow sphere made
largely of silica and
alumina and filled with
air or inert gas,
typically produced as a
coal combustion
byproduct at thermal
power plants.
Fly Ash and Bottom Ash
Fly Ash

Typical Coal
Fired Generating
Station

Si, Al, Fe, Ca, Mg, K, Na, Sr, V,

Zn, Mn, Cr, Cu, Pb, Ni, Co, As
and Cd

Bottom Ash
Cement Fly Ash

Irregular
Spherical
Cement
FA Grain
Grain

Average Size of Cement Grains = Average Sized of Fly Ash Grain

Particle Size Distribution

Cement and Fly Ash

 Carbon Content
Two Sources of Carbon:
1. Un-burnt coal
2. Activated carbon used to control the heavy metal content of flue exhaust
Result:
1. Increase in water requirement
2. Interference with surface active admixtures such as super-plasticizers and
air-entraining agents.

(a) Fly ash

(b) unburned carbon in fly

ash.
 Effects of Fly Ash on Fresh Concrete:
Reduced Water Demand
◼ Less Bleed
◼ Less Segregation

segregation in concrete

Bleeding in fresh concrete refers to the

process where free water in the mix is
pushed upward to the surface due to the
settlement of heavier solid particles such
as cement and water.
Improves Pumpability
Better workability due to spherical
particles and the “Ball Bearing”
Effect

Entrained Air
Increases Air Entraining
Admixture Dosage Requirement
Fly Ash Stabilizes Air Through
Pump
 Lengthens (Setting) Workability
Time
Without Fly Ash
Final Set
With Fly A

Initial Set

ASTM C191 - 19

Standard Test Methods for Time of Setting of

Hydraulic Cement by Vicat Needle
Effects of Fly Ash on
Hardened Concrete
 Compressive Strength
◼ Reduced Early Age Strength
in the same “28- Day Cross-Over Point
Strength” Concrete
◼ Higher Long Term Strength
◼ Better Safety Factor
◼ High Strength Mixes
 Lower Heat of Hydration
◼ Important in Mass Footings and
Large Members
◼ Important in Hot Weather
◼ Important in High Strength
Concrete
 Blast Furnace Slag
◼ CSA A23.5 - the non-metallic product,
consisting essentially of silicates and alumino-
silicates of calcium and other bases, that is
developed in a molten condition
simultaneously with iron in a blast furnace.
◼ Granulated Blast Furnace Slag : CSA A23.5
- the glassy granular material formed when
molten blast-furnace slag is rapidly cooled.
 Industrial By-Products
AS SUPPLEMENTARY CEMENTING MATERIALS

CaO SiO2 Al2O3 Fe2O3

Ordinary Highly
63% 22 6 3 Cementitious
Portland
Cement
SLAG Latent-
40 35 8 0 Cementitious

FLYASH Pozzolanic &

20 35 20 5 Cementitious
(High Lime)
FLYASH Pozzolanic
1 50 25 10
(Low Lime)
Highly
Silica 0 90 2 2 Pozzolanic
Fume
 Where Does Slag Come From
◼ Steel Making Industry: Slag is the glass-like by-product left over after a desired
metal has been separated (i.e., smelted) from its raw ore. Slag is usually a
mixture of metal oxides and silicon dioxide. However, slags can contain
metal sulfides and elemental metals.

Steel

Slag
Granulated Slag with
Pelletization

Rapid Cooling

Slag
 Grind into Finished Product
◼ Typically Interground with Clinker
◼ Clinker Replacements as High as 60%
 Other Types of Slags
◼ Lead-Zinc Slag (Cominco)
◼ Copper Slag
Not Covered by CSA A3000

copper slag

LEAD SLAG
Use of Slag
Strength Development
High Reactivity Slag

Cement Alone)

Low Reactivity Slag

Silica Fume (A Super Pozzolan)

◼ CSA A23.5 - the finely divided residue

resulting from the production of silicon, ferro-
silicon, or other silicon-containing alloys that is
carried from the burning surface area of a
furnace by exhaust gases.
 Industrial By-Products
AS SUPPLEMENTARY CEMENTING MATERIALS

CaO SiO2 Al2O3 Fe2O3

Ordinary Highly
63% 22 6 3 Cementitious
Portland
Cement
SLAG Latent-
40 35 8 0 Cementitious

FLYASH Pozzolanic &

20 35 20 5 Cementitious
(High Lime)
FLYASH Pozzolanic
1 50 25 10
(Low Lime)
Highly
Silica 0 90 2 2 Pozzolanic
Fume
Where Does Silica Fume Come
From
◼ By-Product of the Silicon Metal Industry
◼ Silicon Metal from Smelting Quartz
 Silica Fume Chemistry
Typical Silica Fume Typical Cement
◼ SiO2 - 90% ◼ SiO2 - 21%

◼ LOI - 3% ◼ Al2O3 - 4.5%

◼ Fe2O3 - 3%

◼ CaO - 63%

Size Comparison
Irregular Cement
Grain Regular Silica Fume Grain

1 Cement Grain = 100 to 150 Silica Fume Grains

Particle Size Distribution

Cement and Fly Ash

Silica Fume
Densification by Silica Fume
 Why a Super Pozzolan?
(Extreme Reactivity)
Without Silica Fume

10%

20%

With Silica Fume

Solution pH

30%
Determination of Pore Size Distribution
of Cement Paste by Thermoporometry

Densification by Silica Fume

Thermoporometry
◼ Thermoporometry is a method of
evaluation of the pore size distribution
and the pore structure of cement paste by
a calorimetric method (involving heat). In
this method, a probe liquid (water) is
entered in the pore structure of cement
and the pore size distribution is evaluated
based on the heat involved in melting or
freezing the probe.

◼ Significance of the investigation: cement

is a porous material. Porosity plays an
important role in physical and mechanical
properties; strength. Also, it greatly
affects durability and vulnerability to
deleterious materials.
 Thermoporometry
◼ Pore size distribution is obtained “based on the
melting or crystallization point depression of a
liquid confined in a pore” (Landry, 2005).

◼ The effective pore radius calculated based on

the magnitude of the depression in the freezing
point of water when samples are cooled; the
finer the pore structure, the greater the
depression that shall be observed.
 Thermoporometry
Heat Flow Rate (mW)

Endothermic
Temperature
(Degree Celcius)
or Time (sec) 0oC
0

Exothermic
(Supercooling)

DS Calorimeter
Depression of Freezing Point with
Reduction in Pore Radius
1.E+04
Freezing Stage (Brun et al.)
Freezing Stage (Ishikiriyama et al.)
Freezing Stage (Landry)
1.E+03 Melting Stage (Brun et al.)
Melting Stage (Ishikiriyama et al.)
Pore Radius, rp (nm)

Melting Stage (Landry)

1.E+02

1.E+01

1.E+00
0.01 0.1 1 10
Freezing or Melting Point Depression, -∆T (K)
 Pore Size Distribution (PSD)
Thermoporometry (TP) using Differential
Scanning Calorimeter
dV fp  dQ dt dT  1
= 
drp  dt dT drp  md H f (T )  fp (T )

The above equation determines a pore volume at a given

pore size (rp) from a heat flow, heating rate, the freezing
point of water confined in the pore, the mass of dry sample,
an enthalpy of fusion, and a density of freezable pore water.
Vfp : the volume of freezable pore water
r p : effective pore radius
Notation
ΔT : melting and freezing point depression
rp : effective pore radius
δf : thickness of non-freezable layers in the freezing process
δm : thickness of non-freezable layers in the melting process
T : temperature
To : the triple point of bulk water
vl : molar volume
γsl : surface tension
Δhf : molar heat of fusion
rsl : radius of curvature
ΔHf (T) : enthalpy of fusion
mfp (T) : mass of the freezable pore water
Q(T) : heat resulted from a calorimeter
dQ/dt : heat flow rates from a calorimeter
dt/dT : scanning rate in a calorimeter
Vfp(T) : the volume of freezable pore water,
ρfp(T) : the density of supercooled water or the density of ice
md : the mass of dried porous materials,
dVfp / drp : the distribution of pore size
P : the applied pressure
γ : the air-mercury surface tension
θ : the contact angle of mercury on a hardened cement paste
 Thermoporometry with Silica
Fume
◼ Objective: Understand the effect of w/c ratio and silica
fume on pore size distribution

Cement Paste + 5%
Mix# Cement Paste
Silica Fume
1 w/c = 0.4
2 w/c = 0.2
3 w/c = 0.2
4 w/c = 0.4

◼ Thermoporometry carried out at 7 and 28 days after casting.

 Calorimetry and Calculating the Effective Pore Radius
1.E+04
Freezing Stage (Brun et al.)
Freezing Stage (Ishikiriyama et al.)
Freezing Stage (Landry) ◼ Samples placed in DSC , frozen to an initial
Melting Stage (Brun et al.)
1.E+03
Melting Stage (Ishikiriyama et al.) temperature that keeps the free water frozen and the
Pore Radius, rp (nm)

Melting Stage (Landry)

heating and freezing cycles begin. The heating and
1.E+02
freezing is applied to the water within the pores only;
only interested in effective pore radius.
1.E+01
◼ The results from the DSC experiments give two
1.E+00
quantitative data sets: the heat flow and the
0.01 0.1 1 10 temperature. From these data sets, the effective
Freezing or Melting Point Depression, -∆T (K)
pore radii of the various mixes are calculated. The
graph of heat flow vs. temperature is plotted for
‘freezing’ portion of the curve as this portion shows
us the depression of the freezing-point.
◼ Pore size distribution is obtained based on the area
under heat flow vs. temperature curve. Maximum
point on the pore size distribution graph indicates the
range where most radii fall within. The corresponding
radius is considered as the effective pore radius.
Pore Size Distribution Heat Flow Rate (mW)

Endothermic
Temperature
(Degree Celcius)
or Time (sec)
0

Exothermic
(Supercooling)

Effective Pore Radii

7 Day Radius, 28 Day Radius,
Mix Average Value Average Value
(nm) (nm)
W/C = o.4 87 83
W/C = o.2 45 42
W/C = o.4
55 18
+ Silica Fume
W/C = o.2
4 2
+ Silica Fume
 Significance of Silica Fume
◼ At 7 days: there is a
modest reduction in mean
pore size due to silica
fume; the mean pore size
with silica fume is 63.3 %
that of the mix without
silica fume.
◼ At 28 days: the mean pore
size of the silica fume mix
is 21.8% that of the
cement-only mix.
 Thus…
◼ Effect of Water to Cement Ratio:
◼ The mean pore size for the 0.4 water/cement ratio mix is
noticeably greater than that of the 0.2 water/cement ratio mix
both at 7 and at 28 days.
◼ Effect of Silica Fume:
◼ Pore structure refinement due to addition of just 5% silica
fume. This refinement is comparatively greater at 28 days
than at 7 days, indicating a greater refinement over time;
◼ The refinement due to silica fume is proportionally greater at
0.2 water/cement ratio than at 0.4 water/cement ratio. Silica
fume is therefore more effective at lower water/cement ratios.
Benefits of Silica Fume
Very High Strengths
Very Low Permeability
Better Abrasion Resistance
Improved Shotcrete Adhesion
Higher Chemical Resistance
etc...

Applications of Silica Fume

REPAIRS
Bridge Decks
Parking Structures
Marine Applications
Chemical Tanks
Water Tight Structures
High Strength Concrete
Nanotechnology and Supplementary
Cementitious Materials

98
 Nanotechnology - The Tiny Revolution
▪ Nanotechnology n.
The ability to do things—measure, see, predict and make—on the scale of
atoms and molecules and exploit the novel properties found at that scale.

▪ Understanding and manipulation of materials on the nano scale (<100nm)

Watson and Crick-Double Helix

What is so special about the nano-scale?

• Nanotechnology is not just about miniaturizing things

• At the nano-scale:
❑ Different laws of physics come into play (quantum physics) and
substance properties are dictated by quantum mechanics
❑Surface area to volume ratio is higher, so the behavior of surface
atoms starts to dominate the behavior of bulk materials.
❑Surface atoms possess more energy than bulk atoms and are
chemically more reactive, thereby increasing the Chemical
Reactivity of nano-particles.
What is so special about the nano-scale?
❑Improved performance and new functionalities

Size-dependent Properties
Chemical properties reactivity, catalysis

Thermal properties melting temperature

Mechanical properties adhesion, capillary forces, strength

Optical properties absorption and scattering of light

Electrical properties tunneling current

Magnetic properties super-paramagnetic effect

Nanotechnology and the Concrete Industry?

▪ Improving the primary properties of traditional materials

(e.g. mechanical properties, durability and service life)

▪ Potential to reduce the environmental impact and energy

intensity of concrete structures (e.g. CO2 emission)

▪ Structural health monitoring and sensing devices

▪ Add functionalities to existing materials or developing new

materials to fill existing needs (e.g. coatings with antimicrobial,
self cleaning or pollution reducing properties, nano-encapsulated
corrosion inhibitors for concrete corrosion protection)
Nanotechnology in Concrete
Nano-Particles in Strength,
#1 Morphology, Setting and
Mechanics
Nano-tubes in Sensing and
#2 Structural Health Monitoring
Nanotechnology in Concrete
Nano-Particles in Strength,
#1 Morphology, Setting and
Mechanics
Nano-tubes in Sensing and
#2 Structural Health Monitoring
General Principles of Nano Modification
TiO2, Al2O3, Fe3O4, ZrO2, , SiO2, Nanoclays

FILLERS
❑ Densify the microstructure
❑Nanoclays: For Fire
❑ Reduce concrete permeability and corrosive ions Resistance of FRPs
penetration
❑ Enhance the Interfacial Transition Zone (ITZ) resulting ❑ Nanolimestone:
in a better bond between aggregate and paste and
repair
For Processing SCC
REACTANTS
❑ Accelerate cement hydration rate due to their high
reactivity ❑Nanosilica:
❑ Accelerate the pozzolanic reactions and produce Pozzolanic
additional CSH
❑ Act as nucleation site for crystallization of cement
hydrates
❑Nano-Cellulose:
❑ Improve mechanical properties Hydrophilic
❑ Improve durability
Nano-Materials
❑Nanosilica
Nano-silica (n-SiO2)

Metakaolin
Silica Fume 100 nm Nanosilica
400 nm 4 nm
Cement Grain
40000 nm
Nano-silica (n-SiO2)
Mitigate Erosion in Flyash Concrete
0%CNS 7months
❑ 0% CNS paste: fly ash
particles are seriously eroded
and hydrates around them
are uniform
5%CNS 7months
❑ 5% CNS paste: fly ash are less
hydrated and coated with a
compacted layer of low Ca/Si,
which is documented as less
permeable. (Garrault, 2001)
Nano-silica ❑Denser microstructure with less CH crystals
(n-SiO2) ❑Enhanced resistance to chemical attack
❑Reduced porosity and better durability
❑Reduced bleeding and segregation
❑Improved cohesiveness and reduced CH leaching
rate

NS = 2.5%
90-Days
NS = 5%
NS = 0%
7-Days

Increasing NS Reducing time

IN HVFA SYSTEMS: Hydration IN HVFA SYSTEMS: Higher early-age

and setting are accelerated at early compressive strength, Comparable at
the later age
ages
Effects of Nano-silica (n-SiO2)
Influence of nanosilica on the properties of
HVFA-cement systems:

❑ Accelerated rate of hydration

Due to:
1) Seeding effect
❑ Accelerated setting
2) Pozzolanic effect
❑ High early-age (7d) compressive strength gain

❑ Lower later-age (90d) compressive strength 3) Coating effect

Chemical Admixtures for Concrete

111
 Chemical Admixtures
• Definition (ASTM C 125): a material other than water, aggregate,
hydraulic cement, and fiber reinforcement that is used as an
ingredient of concrete or mortar and is added to the batch
immediately before or during its mixing.
• Classification
– Plasticizing admixtures ( ASTM C 494 and C 1017) – are water-
soluble polymers designed to enhance workability or to reduce
water requirements for a desired workability
– Set-controlling admixtures (ASTM C 494) - are added to control
setting and to induce early hardening
– Air-entraining agents (ASTM C 260) – are added primarily to
improve resistance to freezing/thawing cycling
– Miscellaneous admixtures
• E.g. Viscosity modifiers, corrosion inhibitors, shrinkage reducing
admixtures, etc.

Retarders
Plasticizing Admixtures (Water-Reducing
Admixtures)
• Increase slump without increase water and
cement contents
• to facilitate difficult placements
• Achieve desired slump with less water (lower
w/c)
• improve strength, impermeability, and
durability
• Achieve desired slump with lower cement
content without changing w/c
• Economic reason: reduce cost
• Technical reason: reduce heat
• Classification of Plasticizing Admixtures

(Mindess et al 2003)
 Composition
• Regular WRA
– Lignosulphonates
– Hydro-carboxylic acids and their salts
– Hydroxylated polymers derived from
hydrolyzed starch

• High-Range WRA (Superplasticizers)

– Sulphonated naphthalene-formaldehyde
condensates
– Sulphonated melamine-formaldehyde
condensates
– Modified lignosulphonates
– Carboxylated acrylic ester copolymers
(polycarboxylates)
 Mechanism of Water Reduction

Cement
particles
• Electrostatic repulsion
Cement –Negatively charged
Grains in Water
reducing organic molecules
Suspension admixture

Charge
molecules
adsorbed primarily at
Neutral the solid-water interface

- Negative Molecules of
WRA neutralize +ve
surface charges on
cement particles and
thus cause all surface to
Flocculation carry uniform charges of
Deflocculation
like sign (-ve)
Cement
Trapped particles

– Particles repel each

water

other, remain dispersed

 Mechanism of Water Reduction (cont’d)

Cement
Water particles
reducing
admixture
molecules

Freed
water

• Steric Hindrance Effect

–The bulky nature of the adsorbed molecules (superplasticizers
are generally high molecular weight polymers) can cause steric
hindrance effect (bulky particles do not react readily), results in
dispersion and also set-retardation (as in superplasticizers).
Effect on the Properties of Fresh
Concrete
• Flowing concrete
– Increase slump
• Use of SP allows high slumps to be achieved
without excessive segregation and bleeding
• pumping concrete, self-leveling concrete, tremie
placement
• Bleeding
– Overdose of superplasticizer should be
avoided (freed water can cause excessive
bleeding)

• Retardation of Set
– Many regular or mid-range WRA will also act
as retarding agents, some SP at high dosages
have retarding effect
– Beneficial in hot weather concreting so long as
it does not affect setting and strength
development significantly
Effect on the Properties of Hardened Concrete

• Compressive strength
– When WRA is used to lower water requirement,
strength 
–  in the compressive strength is up to 25% greater
than would be anticipated from the  in w/c alone,
attributed to more uniform microstructure

• High-strength concrete
– SPs are used in most concrete with 28-day
compressive strengths of more than 80 MPa
– Lower w/c improve the rate of strength development
at early age, can be used for precast concrete plant

• Other properties
– Reduce permeability and penetration of harmful
substances