Yonsei University Civil. CMME Lab.

Multi-component Hydration Model

Civil and Env. Eng.
Yonsei Univ.
Ha-Won Song
Behavior of Concrete
Yonsei CMME Lab.
Hydration Heat Process of Cement
Hydration Heat Process of Cement
Exothermic Hydration Process of Cement
STEP 1
STEP 2
STEP 3 STEP 4
STEP 5
Initial stage Intermediate stage Latter stage
Elapsed time
H
y
d
r
a
t
i
o
n

h
e
a
t

r
a
t
e
General stages in the hydration process in OPC
(Nagashima, M. 1992)
Step 1 (the first peak)
Ettringite formation reaction
Step 2 Dormant period
The rate of heat generation is too small and the
hydration seems to be stagnant.
Step 3
Rate of heat generation increases
Beginning of the crystallization of the CSH.
Step 4
Rate of heat generation becomes gradually
slower.
Surface area of the unhydratedparts are reduced
according to the progress of hydration.
Step 5
Rate of hydration is remarkably reduced by the
thicker layer of hydrates around particles
Space filled by liquid water is almost occupied by
cement hydrates.
Yonsei CMME Lab.
Conventional Thermal Analysis using Adiabatic Temperature Rise
C : kg/m
3
The weight replacement of ggbs and fly ash in the binding power are 40% and
20%, respectively.
0.059 0.0030 11.0 0.11 30
-0.143 0.0028 8.0 0.12 20
0.141 0.0007 -3.0 0.15 10
Fly ash
0.332 0.0035 15.0 0.10 30
0.207 0.0025 15.0 0.10 20
0.723 0.0014 14.0 0.11 10
ggbs
0.299 0.0021 9.0 0.11 30
0.279 0.0015 9.0 0.10 20
0.303 0.0003 6.0 0.11 10
MC
0.337 0.0040 12.0 0.11 30
-0.036 0.0038 13.0 0.11 20
0.135 0.0015 11.0 0.12 10
OPC
h g b a
casting
temperature
cement
Hydration Heat Process of Cement
Hydration Heat Process of Cement
Yonsei CMME Lab.
0
1
2
3
4
5
6
0 50 100 150 200
Accumulated Heat (kcal/kg) Qi
H
e
a
t ra
te
(k
c
a
l/k
g
/h
r)
H
i
SLAG
FLY ASH
SILICA FUME
-10000
-7500
-5000
-2500
0
0 50 100 150 200
Accumulated Heat (kcal/kg) Qi
T
h
e
rm
a
l A
c
tiv
ity
-
E
/
R
(K
)
SLAG
FLY ASH
SILICA FUME
Cement mineral composition
Amount of gypsum Type of admixture
Unit cement content Unit water content
Replacement ratio Dosage of SP
Initial temp. t
int
Materials to use
Mix proportion
Initial condition
Input data
Basic equation of minerals heat rate
Multi component heat of hydration model
Exothermic characteristics of minerals
Formation of ettringite
Secondary cementitious powders
Retarding effect of SP and fly ash
i
Effect of difference of mineral composition
i
Effect of shortage of Ca(OH)
2

i
Effect of free water reduction
i
Effect of powder fineness
Heat of hydration rate of cement
Input data
Thermal conductivity Specific heat
Environmental temp. Heat trans. coeff.
Temperature history Hydration degree
Temperature distribution Accumulated heat
Output data
Temperature
analysis
Temperature T
0
/
i i i
s S S =
3 3 3 4 4 4
( ) ( )
C C A C AET C A C AET C AFET C AF
H p H H p H H = + + +
3 3 2 2 4
C S C S C S C S SG C AF FA FA SF SF
p H p H p H p H p H + + + + +
C
H CH =
Multi-component Model Computation
0
1
2
3
4
5
6
0 50 100 150 200
Accumulated Heat (kcal) Qi
H
e
a
t ra
te
(
k
c
a
l/
k
g
/
h
r)
H
i
C3A
C4AF
C3S
C2S
0
20
40
60
80
0 100 200 300 400
Accumulated Heat (kcal) Qi
H
e
a
t ra
te
(k
c
a
l/k
g
/h
r) H
i
C3AET
C4AFET
-10000
-7500
-5000
-2500
0
0 50 100 150 200 250
Accumulated Heat (kcal/kg) Qi
T
h
e
rm
a
l A
c
tiv
ity
-
E
/
R
(
K
)
C3A
C4AF
C3S
C2S
-10000
-7500
-5000
-2500
0
0 100 200 300 400
Accumulated Heat (kcal/kg) Qi
T
h
e
rm
a
l A
c
tiv
ity
-
E
/
R
(K
)
C3AET
C4AFET
Yonsei CMME Lab.
Concept of Multi-component Heating Model
3 3 3 4 4 4
( ) ( )
C A C AET C A C AET C AFET C AF
p H H p H H = + + +
C
H CH =
Arrehenius law
3 3 2 2 4
C S C S C S C S SG C AF FA FA SF SF
p H p H p H p H p H + + + + +
Yonsei CMME Lab.
Change of heat rate by difference of mineral composition
Reduction of hydration heat rate by reduction of free water
Delaying Effect of Secondary Cementitious Powders on Hydration
Yonsei CMME Lab.
Evaluation of Reaction Rate Dependent on Calcium Hydroxide
XRD patterns by Ren-Bin Lin et al., 2003
9/1
7/3
5/5
3/7
1/9
Ca(OH)2/silica fume
0 10 20 30 40 50 60
2 (degree)
0 10 20 30 40 50 60
2 (degree)
R
e
l
a
t
i
v
e

i
n
t
e
n
s
i
t
y

(
c
p
s
)
R
e
l
a
t
i
v
e

i
n
t
e
n
s
i
t
y

(
c
p
s
)
16h
8h
25 min
h : Ca(OH)2
s : silica fume
t : CSHs
h
h
h h
h : Ca(OH)2
s : silica fume
t : CSHs
h
h s t
h
h
h h
h
h s
t
Slurrying time
Yonsei CMME Lab.
Quantification of the Hydration Process
Adiabatic temperature
rises
T
e
m
p
e
r
a
t
u
r
e

(
K
)
Time
High
Low
Initial temp.
H
y
d
r
a
t
i
o
n

h
e
a
t

r
a
t
e

H
Accumulated heat Q
Qa Qb Qc
Hydration heat rate
at different temp.
H=dQ/dt
Accumulated heat Q
H
y
d
r
a
t
i
o
n

h
e
a
t

r
a
t
e

H
Qa Qb Qc
Reference heat rate
at constant temp. Ts
Thermal activity
Qa Qb Qc
-
E
/
R
0
A
c
c
u
m
u
l
a
t
e
d

h
e
a
t

(
c
a
l
/
g
)
Gradient
= dQ/dt = H
Qa
Qb
Qc
Time
1/T
1/Ts
0
Q
a
Q
b
Q
c
l
o
g

H
Arrhenius plots
Gradient:
-E/R
Procedures to derive thermal properties of cement hydration
(Suzuki model, 1990)
Yonsei CMME Lab.
Heat generation rates
0
1
2
3
4
5
6
0 50 100 150 200
Accumulated Heat (kcal) Qi
H
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)

H
i
C3A
C4AF
C3S
C2S
Temperature dependency
-10000
-7500
-5000
-2500
0
0 50 100 150 200 250
Accumulated Heat (kcal/kg) Qi
T
h
e
r
m
a
l

A
c
t
i
v
i
t
y

-
E
/
R

(
K
)
C3A
C4AF
C3S
C2S
0
20
40
60
80
0 100 200 300 400
Accumulated Heat (kcal) Qi
H
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)

H
i
C3AET
C4AFET
-10000
-7500
-5000
-2500
0
0 100 200 300 400
Accumulated Heat (kcal/kg) Qi
T
h
e
r
m
a
l

A
c
t
i
v
i
t
y

-
E
/
R

(
K
)
C3AET
C4AFET
0
1
2
3
4
5
6
0 50 100 150 200
Accumulated Heat (kcal/kg) Qi
H
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)

H
i
SLAG
FLY ASH
SILICA FUME
-10000
-7500
-5000
-2500
0
0 50 100 150 200
Accumulated Heat (kcal/kg) Qi
T
h
e
r
m
a
l

A
c
t
i
v
i
t
y

-
E
/
R

(
K
SLAG
FLY ASH
SILICA FUME
SCPs
Ettringite formation
Cement components
Yonsei CMME Lab.
Heat rate as functions at temperatures (Weiping Ma, et al., 1994)
(a) ordinary Portland cement (b) fly ash blended cement (17%)
(c) silica fume blended cement (7.5%) (d) GGBS slag blended cement (65%)
0
4
8
12
16
20
0 20 40 60 80
Accumulated heat Q
H
y
d
r
a
t
i
o
n

h
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)

H
i
10C
15C
20C
25C
30C
35C
40C
45C
50C
55C
0
4
8
12
16
20
0 20 40 60 80
Accumulated heat Q
H
y
d
r
a
t
i
o
n

h
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)

H
i
10C
15C
20C
25C
30C
35C
40C
45C
50C
55C
0
4
8
12
16
20
0 20 40 60 80
Accumulated heat Q
H
y
d
r
a
t
i
o
n

h
e
a
t

r
a
t
e

(
k
a
c
l
/
k
g
/
h
r
)

H
i
10C
15C
20C
25C
30C
35C
40C
45C
50C
55C
0
4
8
12
16
20
0 20 40 60 80
Accumulated heat Q
H
y
d
r
a
t
i
o
n

h
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)

H
i
10C
15C
20C
25C
30C
35C
40C
45C
50C
55C
Converted results of calorimeteric tests
Yonsei CMME Lab.
Comparison heat rate of ordinary Portland cement with
heat rate of silica fume blended cement
-1
0
1
2
3
4
5
0 6 12 18 24
hour
H
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)OPC
SF-blended
Hiopc-Hisf
-1
0
1
2
3
4
5
0 6 12 18 24
hour
H
e
a
t

r
a
t
e
(
k
c
a
l
/
k
g
/
h
r
)
OPC
SF-blended
Hiopc-Hisf
-4
-2
0
2
4
6
8
0 6 12 18 24
hour
H
e
a
t

r
a
t
e
(
k
c
a
l
/
k
g
/
h
r
)
OPC
SF-blended
Hiopc-Hisf
-4
-2
0
2
4
6
8
0 6 12 18 24
hour
H
e
a
t

r
a
t
e
(
k
c
a
l
/
k
g
/
h
r
)OPC
SF-blended
Hiopc-Hisf
10 15
20 25
-4
-2
0
2
4
6
8
0 6 12 18 24
hour
H
e
a
t

r
a
t
e
(
k
c
a
l
/
k
g
/
h
r
)OPC
SF-blended
Hiopc-Hisf
-4
-2
0
2
4
6
8
0 6 12 18 24
hour
H
e
a
t

r
a
t
e
(
k
c
a
l
/
k
g
/
h
r
)OPC
SF-blended
Hiopc-Hisf
-6
0
6
12
18
0 6 12 18 24
hour
H
e
a
t

r
a
t
e
(
k
c
a
l
/
k
g
/
h
r
)OPC
SF-blended
Hiopc-Hisf
-6
0
6
12
18
0 6 12 18 24
hour
H
e
a
t

r
a
t
e
(
k
c
a
l
/
k
g
/
h
r
)OPC
SF-blended
Hiopc-Hisf
30 35
40
45
-4
-2
0
2
4
6
0 10 20 30 40 50
Accumulated heat (kcal/kg)
H
e
a
t

r
a
t
e

(
k
c
a
l/
k
g
/
h
r
)
OPC
SF
Hsf-Hopc
-4
-2
0
2
4
6
0 10 20 30 40 50
Accumulated heat (kcal/kg)
H
e
a
t

r
a
t
e

(
k
c
a
l/
k
g
/
h
r
)
OPC
SF
Hsf-Hopc
-4
-2
0
2
4
6
0 10 20 30 40 50
Accumulated heat (kcal/kg)
H
e
a
t

r
a
t
e

(
k
c
a
l/
k
g
/
h
r
)
OPC
SF
Hsf-Hopc
-4
-2
0
2
4
6
0 10 20 30 40 50
Accumulated heat (kcal/kg)
H
e
a
t

r
a
t
e

(
k
c
a
l/
k
g
/
h
r
)
OPC
SF
Hsf-Hopc
-8
-4
0
4
8
12
0 10 20 30 40 50 60
Accumulated heat (kcal/kg)
H
e
a
t

r
a
t
e

(
k
c
a
l/
k
g
/
h
r
)
OPC
SF
Hsf-Hopc
-8
-4
0
4
8
12
0 10 20 30 40 50 60
Accumulated heat (kcal/kg)
H
e
a
t

r
a
t
e

(
k
c
a
l/
k
g
/
h
r
)
OPC
SF
Hsf-Hopc
-8
-4
0
4
8
12
0 10 20 30 40 50 60
Accumulated heat (kcal/kg)
H
e
a
t

r
a
t
e

(
k
c
a
l/
k
g
/
h
r
)
OPC
SF
Hsf-Hopc
-8
-4
0
4
8
12
0 10 20 30 40 50 60
Accumulated heat (kcal/kg)
H
e
a
t

r
a
t
e

(
k
c
a
l/
k
g
/
h
r
)
OPC
SF
Hsf-Hopc
Yonsei CMME Lab.
Arrhennious Plots
y = -3810.5x + 13.649
y = -4055.2x + 14.712
y = -4331.5x + 15.784
0
0.5
1
1.5
2
2.5
3
0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
1/ T
l
o
g

H
10kcal/kg
15kcal/kg
20kcal/kg
(10kcal/kg)
(15kcal/kg)
(20kcal/kg)
y = -3836.4x + 13.923
y = -4149.7x + 15.196
y = -4271.9x + 15.722
0
0.5
1
1.5
2
2.5
3
0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
1/ T
l
o
g

H
10kcal/kg
15kcal/kg
20kcal/kg
(10kcal/kg)
(15kcal/kg)
(20kcal/kg)
y = -3184.3x + 11.062
y = -3637.6x + 12.379
y = -3968.1x + 13.339
-1
-0.5
0
0.5
1
1.5
2
2.5
3
0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
1/T
l
o
g

H
10kcal/kg
15kcal/kg
20kcal/kg
(10kcal/kg)
(15kcal/kg)
(20kcal/kg)
y = -3821.3x + 13.498
y = -4199.4x + 14.966
y = -4122.1x + 14.807
0
0.5
1
1.5
2
2.5
3
0.003 0.0031 0.0032 0.0033 0.0034 0.0035 0.0036
1/T
l
o
g

H
10kcal/kg
15kcal/kg
20kcal/kg
(10kcal/kg)
(15kcal/kg)
(20kcal/kg)
Ordinary Portland cement
Fly ash blended cement
GGBF Slag blended cement Silica fume blended cement
Yonsei CMME Lab.
Verification
Calculated heat rates of concrete in the multi- component model
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
0 6 12 18 24
Hour
H
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)
OPC
O9G1
O8G2
O7G3
O6G4
O5G5
O4G6
GGBF slag blended cement
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
0 6 12 18 24
Hour
H
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)
OPC
C9F1
C8F2
C7F3
C6F4
0.0
1.0
2.0
3.0
4.0
5.0
0 6 12 18 24
Hour
H
e
a
t

r
a
t
e

(
k
c
a
l
/
k
g
/
h
r
)
OPC
C9SF1
C8SF2
C7SF3
Silica fume blended cement
Fly ash blended cement
Yonsei CMME Lab.
Temperature Analysis results
0
10
20
30
40
50
60
70
80
0 10 20 30 40 50 60 70
Time (Hour)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
Silica fume concrete1
normal concrete 1
Silica fume concrete 2
normal concrete 2
Experimental results
0
10
20
30
40
50
60
70
0 10 20 30 40 50 60 70
TIME (hour)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
analysis
experiment1
experiment2
0
10
20
30
40
50
60
70
80
0 10 20 30 40 50 60 70
TIME (hour)
T
e
m
p
e
r
a
t
u
r
e

(
C
)
analysis
experiment1
experiment2
8
0
c
m 9
0
c
m
1
1
0
c
m
Normal concrete Silica fume concrete
Verification
Yonsei CMME Lab.
0
10
20
30
40
50
60
70
80
0 20 40 60 80 100 120 140 160
Time (hours) .
T
e
m
p
e
r
a
t
u
r
e

(

)
surface-opc
center-opc
surface-si li ca fume 5
center-si li ca fume 5
surface-si li ca fume 10
center-si li ca fume 10
surface-si li ca fume 15
center-si li ca fume 15
0
10
20
30
40
50
60
70
0 20 40 60 80 100 120 140 160
time (hour)
t
e
m
p
e
r
a
t
u
r
e

(

)
cneter (experiment)
center (analysis)
surface (experiment)
surface (analysis)
ambient temperature
0
10
20
30
40
50
60
0 40 80 120 160 200 240
time (hour)
t
e
m
p
e
r
a
t
u
r
e

(

)
center (experiment)
center (analysis)
surface (experiment)
surface (analysis)
ambient temperature
0
10
20
30
40
50
60
70
0 20 40 60 80 100 120 140 160
Time ( hours) .
T
e
m
p
e
r
a
t
u
r
e

(

)
surface-opc
center-opc
surface-si l i ca fume 5
center-si l i ca fume 5
surface-si l i ca fume 10
center-si l i ca fume 10
surface-si l i ca fume 15
center-si l i ca fume 15
Verification
Temperature Analysis results in wall structure
80cm thick wall 60cm thick wall
80cm thick wall 60cm thick wall
Temperature ()
Yonsei CMME Lab.
Remark
The hydration heat model for blended cement
can be developed by incorporating reactions of
blast furnace slag, fly ash and silica fume in the
system.
The reactions of blast furnace slag, fly ash and
silica fume can be modeled to be dependent on
the amount of calcium hydroxide produced by
cement hydration.
The applicability of the proposed model can be
verified by analyzing the results of existing
adiabatic temperature rise tests and
temperature histories.