Portland Cement

Portland Cement
A hydraulic cement capable of setting, hardening and
remaining stable under water. It consists essentially of
hydraulic calcium silicates, usually containing calcium
sulfate.
 Manufacture

Raw Materials:
2/3 calcareous materials (lime bearing) - limestone
1/3
/ argillaceous
g materials ((silica,, alumina,, iron)-
) clay
y
Raw Material
Crushing
g
Blending
Old Method
Kiln
Grinding
 Oooops, Problem Production Process
Production of cement
Is reponsible for 8%
CO2 production in the
world
 Cement grains

Courtesy from Prof. Karen Scrivener, EPFL

 Early Hydration

3 hours 10 hours
C t
Courtesy: Prof.
P f Karen
K S
Scrivener
i
Hydration Products
Hadley Grain
Cli k
Clinker
Based on the following notation:
C C O
CaO
S SiO2
A Al2O3
F Fe3O4
H H2O
Cement Composites

C3S : 3CaOSiO2
C2S : 2CaOSiO2
C3A : 3CaOAl2O3
C4AF : 4CaOAl2O3Fe3O4
See video 1
 CHEMICAL REACTIONS

2C3S + 6H -->
> C3S2H3 + 3CH + 120 cal / g
2C2S + 4H --> C3S2H3 + CH + 62 cal / g
C3A + CSH2 --> Ettringite + 300 cal / g
See video 2
Hydration Products
Hadley Grain
H d t dP
Hydrated Paste
t
 SOLIDS IN CEMENT PASTE
-Calcium Silicate Hydrate

Notation: C-S-H
C/S
/ Ratio: 1.5 to 2.0
Main Characteristics: High Surface (100 to 700 m2/ g) ---->
Hi h Van
High V der d Walls
W ll F Force -----> > Strength.
St th
Volume % : 50 a 60
CSH
C-S-H
SOLIDS IN CEMENT PASTE
-Calcium
C l i H
Hydroxide
d id ( portlandite)
l di )

Ca(OH)2
Volume % : 20 to 25
low Van der Walls force
problems with durability and strength
Calcium Hydroxide
SOLIDS IN CEMENT PASTE

-Calcium Sulfoaluminate Hydrates

Volume % : 15 to 20
first : ettringite
after : monosulfate hydrated.
Ettringite
Review
Review 2
Review 3
 ASTM Portland Cements
Type I- General Purpose
Type II- moderate heat of hydration and sulfate resistance (C
(
8%) : general construction, sea water, mass concrete
Type III-
T III hi h early
high l strengthh (C3A < 15%) : emergency rep
precast, winter construction.
Type IV-
T IV l
low h t
heat ( C3S < 35%,
35% C3A < 7%,
7% C2S > 40%) :
concrete
T
Type V sulfate
V- lf t resistant
i t t ( C3A < 5%) : sulfate
lf t in
i soil,
il se
Advanced Light Source at Berkeley
Imaging at High Spatial Resolution:
Soft X-Ray Microscopy to 15 nm
Two Common Soft X-Ray Microscopes
Early hydrates forming during the pre-
induction period
Early hydrates
(Sheaf of
wheat)

Cement
g
grain

C3S hydrated for 34

min. in saturated lime
and calcium sulfate at
w/c=5, 1s exposure
time, 516eV, scale bar
1
 Early hydrates
(Sheaf of
wheat)

Cement
g
grain

C3S hydrated for 56

min. in saturated lime
and calcium sulfate at
w/c=5, 1s exposure
time, 516eV, scale bar
1
 In-situ Massive precipitation

8h 30min.
 In-situ Massive precipitation

8h 36min.
9h 16min.
Spot
 Summary

• “Sheaf of wheat” hydrates are forming on the

cement g
grains duringg the first minutes

• The induction period is ended by the massive

precipitation of C-S-H (needles)

• The early hydrate layer covering the cement grains

transforms
f dduring
i the
h acceleration
l i period i d
Admixtures: Accelerators (CaCl2)
 Summary
• CaCl2 increases the rate of formation of
inner product C
C-S-H
S H.

• This C-S-H is less dense than in a control

p
sample.

• Th
The accelerative
l i power off CaCl2 C Cl2 may come
from its ability to flocculate hydrophilic
 Retarders: Sucrose

31 minutes 68 minutes 100 minutes

Sucrose has delayed the early formation of C-S-H.

Sucrose has often been referred to as a “delayed
delayed accelerator
accelerator,”
Once the retardation is over, hydration proceeds very rapidly
 Hydration process – Initial
Condition
Let’s study a cement paste with w/c= 0.63
Start with 100 cm3 of cement.
Compute the mass of cement: Mc = 3.14* 100 = 314 g
Compute the mass of water: Mw = 0.63 * 314 = 200 g

Vw= 200 cm3

Vc= 100 cm3

 Hydration Process
Miracle of hydration: Vp = 2 Vc

Vw= 200 cm3 50% Vw= 150 cm3

Vp = 100 cm3
Vc= 100 cm3 Vc=50
Vc 50 cm3
 Once More…

Vw= 200 cm3 75% Vw= 125 cm3

Vp = 150 cm3
Vc= 100 cm3 Vc=25
Vc 25 cm3
 Finally

Vw= 100 cm3

Vw= 200 cm3 100%

Vp = 200 cm3
Vc= 100 cm3
 Exam question
• Calculate the water/cement ratio needed to
obtain zero porosity in a fully hydrated
cement paste.
W/c = 100/100*3
100/100*3.14
14

100 cm3 100% W/c= 0.32

200 cm33

100 cm3
V id iin th
Voids the H Hydrated
d t dC Cementt
-Interlayer
I t l iPaste
space in CSH (HCP)
* size = 5 to 25 Å
* no adverse effect on strength and permeability
* some effect on drying shrinkage and creep
-Capillary
Capillary Voids
> 50 nm : detrimental to strength and impermeability
< 50 nm
nm: important to drying shrinkage and creep.
-Air Voids
* entrapped air: ~ 3 mm
* entrained air: 50 to 200 mm
Water inside the pores
Orders of magnitude
Orders of Magnitude
More Advanced Material