MCSS2008_1.

ppt
Concrete
Concrete
An Example for Complex Porosity
An Example for Complex Porosity
Wolfgang Brameshuber
Institute of Building Materials Research (ibac),
RWTH Aachen University, Germany
Marie Curie Summer School
19-29 August 2008, Tet
Porosity Definition
2
MCSS2008_1.ppt
=
V
pores
V
tot
Importance of Porosity in Building Materials
3
MCSS2008_1.ppt
mechanical properties: compressive and tensile strength
e.g. f
c
= f
c
0
(1 - v)
n
Youngs modulus
hygric properties: moisture transport
moisture storage
thermal properties: heat conduction
thermal capacity
durability: frost resistance
chemical attack
Pore Sizes in Concrete
4
MCSS2008_1.ppt
meso
gel pores
characteristic dimension
1 nm 30 nm 1

m 30

m 1 mm
m
a
t
e
r
i
a
l
p
o
r
e
s
Prof. Dr. M. Setzer, UGE - IBPM
m
i
c
r
o

g
e
l

p
o
r
e
s
1 cm
micro
capillary
pores
meso
capillary
pores
macro
capillary
pores
coarse
pores
Kies
gravel
Pore Sizes in Concrete
4
MCSS2008_1.ppt
meso
gel pores
characteristic dimension
1 nm 30 nm 1

m 30

m 1 mm
m
a
t
e
r
i
a
l
p
o
r
e
s
Prof. Dr. M. Setzer, UGE - IBPM
m
i
c
r
o

g
e
l

p
o
r
e
s
1 cm
micro
capillary
pores
meso
capillary
pores
macro
capillary
pores
coarse
pores
Kies
gravel
sand
gravel
aggregates
Pore Sizes in Concrete
4
MCSS2008_1.ppt
meso
gel pores
characteristic dimension
1 nm 30 nm 1

m 30

m 1 mm
m
a
t
e
r
i
a
l
p
o
r
e
s
Prof. Dr. M. Setzer, UGE - IBPM
m
i
c
r
o

g
e
l

p
o
r
e
s
1 cm
micro
capillary
pores
meso
capillary
pores
macro
capillary
pores
coarse
pores
Kies
gravel
sand
gravel
aggregates
cement
sand
gravel
fresh concrete
Pore Sizes in Concrete
4
MCSS2008_1.ppt
meso
gel pores
characteristic dimension
1 nm 30 nm 1

m 30

m 1 mm
m
a
t
e
r
i
a
l
p
o
r
e
s
Prof. Dr. M. Setzer, UGE - IBPM
m
i
c
r
o

g
e
l

p
o
r
e
s
1 cm
micro
capillary
pores
meso
capillary
pores
macro
capillary
pores
coarse
pores
Kies
gravel
sand
gravel
aggregates
cement
sand
gravel
fresh concrete
cement
hydrates
hardened
concrete
sand
gravel
Pore Sizes in Concrete
4
MCSS2008_1.ppt
meso
gel pores
characteristic dimension
1 nm 30 nm 1

m 30

m 1 mm
m
a
t
e
r
i
a
l
p
o
r
e
s
Prof. Dr. M. Setzer, UGE - IBPM
m
i
c
r
o

g
e
l

p
o
r
e
s
1 cm
micro
capillary
pores
meso
capillary
pores
macro
capillary
pores
coarse
pores
cement
hydrates
hardened
concrete
sand
gravel
directly visible
SEM
microscope
s
p
e
c
i
a
l
m
e
t
h
o
d
s
sorption
MIP
Where Do the Pores Come From?
5
MCSS2008_1.ppt
compaction voids
air voids
capillary pores
gel pores
caused by production
Powers model (1958)
Hydration of Hardened Cement Paste
6
MCSS2008_1.ppt
water
unhydrated
cement particles
10 m
cement paste
= cement + water
immediately after mixing
Hydration of Hardened Cement Paste
7
MCSS2008_1.ppt
cp
cp
cp
cp
cp
hardened cement paste
= cement + water
in hardened condition
= cement clinker
(unhydrated, c)
+ gel
(hydrated, h)
+ capillary pores
(cp)
Hydration of Hardened Cement Paste
8
MCSS2008_1.ppt
cp
CH CH
CH
CH
g
c
c
c
c
gp
CSH
hardened cement paste
= cement clinker
(unhydrated, c)
+ gel g
(CSH + gel pores gp)
+ calcium hydroxide
(CH)
+ capillary pores
(cp)
Raw Materials of Cement and
Reaction Products with Water
9
MCSS2008_1.ppt
burn at
1400 to
1500 C
addition
of water
CaO
SiO
2
Al
2
O
3
Fe
2
O
3
H
2
O
C
S
A
F
H
abbreviation
limestone
hydraulic
factors
CaCO
3
+ Al
2
O
3
+ SiO
2
+ Fe
2
O
3
raw materials
C
2
S
C
3
S
C
3
A
C
4
AF
clinker-
minerals
CSH
CSH
CAH
CAFH
CH
reaction products
Products of Hydration
10
MCSS2008_1.ppt
responsible for
strength
C S: alit C S: belit
3 2
C S C S
2 3
CSH
C S
2
C S
3
: 2 (2CaO
.
SiO ) + 4 H O
2 2
: 2 (3CaO
.
SiO ) + 6 H O
2 2
3 CaO
.
2 SiO
.
3 H O +
2 2
Ca(OH)
2
3 CaO
.
2 SiO + 3 H O +
2 2
3 Ca(OH)
2
responsible for
early age strength and
chemical properties
C A
3
CAH
2
.
(3 CaO
.
Al O ) + 2 Ca(OH) + 11 H O
2 3 2 2
2 (4 CaO
.
Al O
.
13 H O)
2 3 2
responsible for
colour of cement and
chemical properties
C AF
4
CAFH
2
.
(2 CaO
.
(Al O ; Fe O )) + 4 Ca(OH)
2 3 2 3 2
2 (4 CaO (Al O ; Fe O )
.
13 H O)
2 3 2 3 2
SEM Pictures of Hardened Cement Paste (hcp)
11
MCSS2008_1.ppt
hcp with CSH phases magnification
Water Balance during Hydration of Cement
(Powers Model)
12
MCSS2008_1.ppt
w/c = 0.42
100 %
per mass
cement
+
gel water =
100 % gel
CSH
(with w
n
= 0.24
.
m
.
c water chemically bonded)
w
g
= 0.18
.
m
.
c (physically bonded)
example:
42 %
per mass
water
m: degree of hydration
c: cement content
C
3
S = 2
.
(3 CaO
.
SiO
2
) + 6 H
2
O
3 CaO
.
2 SiO
2
.
3 H
2
O + 3 Ca(OH)
2
ca. 28 % chemically bonded
Pores and Water
13
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partially empty
partially filled with free water
evaporable at T < 105 C
capillary pores
always water-filled
(physically bonded )
evaporable at T > 105 C
gel pores
water chemically bonded
(not evaporable)
CSH
Bulk Density of Water in Hardened Cement Paste
14
MCSS2008_1.ppt
consequences: volume of cement + water larger than
volume of hardened cement paste
hardened cement paste shrinks during hydration
free water (capillary pores)
gel water (gel pores)
water chemically bonded
: = 1000 kg/m
3
: = 1001 kg/m
3
: = 1333 kg/m
3
> 1000 kg/m
3
!
Degree of Hydration
15
MCSS2008_1.ppt
1 365
concrete age in days
0
1.0
degree of hydration, m
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
90 28 7 3
T = 20 C
32.5 R
32.5 N
dependent on:
= measure for completeness
of chemical reaction of cement
0
<
_
m
<
_
1.0
temperature
cement fineness
age
Volume of Cement Gel
16
MCSS2008_1.ppt
V
g
volume of
cement gel
m
.
c

c
initial volume
of already
hydrated cement
w
n
wn

volume of
chemically
bonded water
CS H
w
g
wg

volume of
gel water
(= volume of
gel pores)
= + +
Volume of Cement Gel
17
MCSS2008_1.ppt
initial volume of
already hydrated cement
m = 1.0 , w/c
>
_
0.42 V = 2.13
.
g
c

c
{
V = 0.68
.
m
.
c [dm ] = 2.13
.
g
3
m
.
c

c
V
g

c
3
wn
3
wg
3
= 3.15 kg/dm , = 1.33 kg/dm , = 1.00 kg/dm
m
.
c

c
0.24
.
m
.
c

wn
0.18
.
m
.
c

wg
= + +
Volume of Cement Gel
18
MCSS2008_1.ppt
volume of cement
!
V = 2.13 with m = 1.0 < V = 2.32
g go
c

c
c

c
hardened cement paste reduces its volume
(chemical shrinkage)
initial volume of cement paste for cement gel:
{
V = 0.74
.
m
.
c [dm ] = 2.32
.
go
3

c
3
w
3
= 3.15 kg/dm , = 1.00 kg/dm
m
.
c

c
V
go
m
.
c

c
0.24
.
m
.
c

w
0.18
.
m
.
c

w
= + +
Volume of Capillary Porosity
19
MCSS2008_1.ppt
V
o
c

c
w
o
w

= +
V
g
=
2.13
.
m
.
c

c
V
nhc
= V - V = - = (1 - m)
.
c hc
c

c
c

c
m
.
c

c
water
unhydrated cement
particle
initial volume of cement paste:
volume of cement gel:
volume of unhydrated cement:
Volume of Capillary Porosity
20
MCSS2008_1.ppt
V
cap
= V - V - V
o g nhc
V = + - - (1 - m)
c

c
c

c
w
o
w

2.13
.
m
.
c

c
= (
.
- 1.13
.
m)
c

c
w
w
c
o
V
V
o
cap

c w
/ = 3.15 =
w /c
.
/ - 1.13
.
m
w /c
.
/ + 1
o z w
o c w


cp
cp
cp
cp
cp
V
V
o
cap
w /c - 0.36
.
m
w /c + 0.32
o
o
=
fraction of empty capillary pores within the capillary pore volume:
V (empty)
V
cap
o
V - V
V
go g
o
(2.32 - 2.13)
.
m
.
c/
c/ + w /


c
c o w
0.06 m
w /c + 0.32
o
= = =
Volume Fractions in Hardened Cement Paste
21
MCSS2008_1.ppt
V
V
cap
0
V
V
g
0
w /c - 0.36
.
m
w /c + 0.32
0
0
0.68
.
m
w /c + 0.32
0
= = ;
V (empty)
V
cap
0
V
V
nhc
0
0,06
.
m
w /c + 0.32
0
0.32 (1 - m)
w /c + 0.32
0
= = ;
0 1.0
w/c ratio
0.8 0.6 0.4 0.2
0
100
1.0
0.5
volume in %
m
80
V
cap
60
40
20
V
nhc
evaluation
c
e
m
e
n
t

p
a
s
t
e

i
m
m
e
d
i
a
t
e
l
y

a
f
t
e
r

m
i
x
i
n
g
Volume Fractions in Hardened Cement Paste
22
MCSS2008_1.ppt
V
V
cap
0
V
V
g
0
w /c - 0.36
.
m
w /c + 0.32
0
0
0.68
.
m
w /c + 0.32
0
= = ;
V (empty)
V
cap
0
V
V
nhc
0
0,06
.
m
w /c + 0.32
0
0.32 (1 - m)
w /c + 0.32
0
= = ;
evaluation
0 1.0
w/c ratio
0.8 0.6 0.4 0.2
0
100
1.0
0.5
volume in %
m
80
V
cap
V
g
V
nhc
60
40
20
V
cap
(empty)
h
a
r
d
e
n
e
d


c
e
m
e
n
t

p
a
s
t
e

a
f
t
e
r

"
c
o
m
p
l
e
t
e
"
h
y
d
r
a
t
i
o
n
"complete" hydration
w/c = 0.25
< 0.42 !
m
max
= 0.6
6 %
6 %
72 %
22 %
V
cap
(empty)
V
cap
V
V
nhc
w/c = 0.5
> 0.42
m = 1.0
7 %
17 %
83 %
0 %
w/c = 0.75
> 0.42
m = 1.0
6 %
36 %
64 %
0 %
Measurement Techniques
23
MCSS2008_1.ppt
microscope (air voids)
water absorption at 150 bar (total porosity)
gas adsorption techniques (gel pores)
mercury intrusion porosimetry (capillary pores)
Mercury Intrusion Porosimetry (MIP)
24
MCSS2008_1.ppt
very fast
covers a wide range of pores from 3 nm to 100 m
with one theoretical model
calculates pore size distribution, medium pore diameter
and critical pore size
Basics of MIP 1
25
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capillary ascension
(wetting fluid)
capillary depression
(non-wetting fluid)
Basics of MIP 2
26
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sin( d ) tan( d )
1 1

1
2
1
2
ds
2R
1
1
sin( d ) tan( d )
2 2

1
2
1
2
ds
2R
2
2
(Washburn equation)
(p - p) ds ds = 2 ds sin( d ) + ds sin
g l 1 2 lg 2 1 1
2 ( d )
lg 2
1
2
1
2
d , d
1 2
infinitesimal
p p - p = -
l g

lg
( + ) = - =
1
R
1
1
R
2
2
R

lg
-2 cos
r

lg

1/R = (1/R + 1/R )

1 2
1
2
R = r/cos
MIP Conclusions
27
MCSS2008_1.ppt
non-wetting liquid is used (i.e. mercury)
device applies pressure to intrude sample
device measures volume intruded
pressure is related to pore size with the Washburn Equation
which idealizes pore as cylinder:
p =
-2
lg
cos
r
thus, a pore size vs. volume relationship can be derived
Interpretation of MIP-Results
28
MCSS2008_1.ppt
P
1
P
2
P
3
bottleneck pores lead to
misinterpretation:
comparison of similar
materials
absolute values
example:
m
e
r
c
u
r
y
i
n
t
r
u
s
i
o
n
pore radius
MIP
reality
Typical Result of a MIP-Measurement
29
MCSS2008_1.ppt
1E-3 0.01 0.1 1 10 100
0
2
4
6
8
10
12
14
1E-3 1 10 100
0
10
20
30
40
50
60
70
80
90
100
incremental intrusion
pore radius r in m
i
n
c
r
e
m
e
n
t
a
l

i
n
t
r
u
s
i
o
n

i
n

%
cumulative intrusion
c
u
m
u
l
a
t
i
v
e

i
n
t
r
u
s
i
o
n

i
n

%
pore radius distribution of a hardened cement paste with w/c = 0.45
Change of Porosity with Increasing Hydration
30
MCSS2008_1.ppt
1 day 7 days 28 days
Micrographs by Paul Stutzman, NIST
0.075mm full width
Time Dependent Change of Pore Radius Distribution
in Concretes
31
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PhD thesis Thomas Bier, Karlsruhe University, Germany
Influence of Carbonation on Pore Radius Distribution
32
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PhD thesis Thomas Bier, Karlsruhe University, Germany
Summary and Conclusion
33
MCSS2008_1.ppt
Porosity of cementitious materials covers a range of to mm
Durability and strength are mainly influenced by capillary
pores in the range of 0.1 to 100 m
Mercury intrusion porosimetry is very effective, but has some
drawbacks
Porosity of cementitious material is changing with time