A Numerical Hydration Model of Portland Cement

Ippei Maruyama1, Tetsuro Matsushita2 and Takafumi Noguchi3

ABSTRACT : A computer-based numerical model is presented, with which hydration and

microstructural development in Portland cement-based materials can be simulated. Proposed model
enables the prediction of hydration curves as a function of the particle size distribution, chemical
composition of the cement, water to cement ratio and the actual curing temperature. Mutual
relationship between developing the microstrucure and its effect on hydration process is modeled
explicitly. In this contribution modeling and validation of this model are discussed.

KEYWORDS: Hydration model, particle size distribution, microstructure, cement composition

1. INTRODUCTION

Over the past few decades a number of studies have been made on modeling of cement hydration in
order to grasp the time dependent properties of cement based materials (Kondo 1968). In those recent
studies, simulation of intricate and compound process of cement hydration, especially focused on
micro-mechanics, with the potential of modern computer is attempted (van Breugel 1995, Bentz 1991).
Two points seem to be helpful in attempting to sketch out what makes it complex to simulate process
of cement hydration and why it needs computer power. One is physical aspect. Cement paste structure,
which is composed of cement particles and water, is determined by particle size distribution (Bezjak,
1980) and water to cement ratio. In cement hydration process, cement particles are interconnected and
make structure of cement matrix. This physical aspect affects the rate of cement hydration through
diffusion of ions (Knudsen 1984). Second is chemical aspect. Cement is mainly composed of
tricalcium silicate, but is poly-mineral material at the same time. Reactions of the components interact
with each other. And temperature is much influential on the rate of hydration from the chemical points
of view (Tomosawa 1974). These two aspects have mutual dependent relationship through diffusion of
ions and material formation. This relationship can not be solved with simple equation with regard to
space-time problem in cement-based material. But using computer power with concept of discrete
event system makes it possible to find an answer to this problem.

2. HYDRATION MODEL OF CEMENT PARTICLE

2.1 Basic Assumptions

Proposed hydration model is based on the fundamental kinetic model for Portland cement that is
developed by Tomosawa (Tomosawa 1997). Tomoswa’s model is expressed as a single equation
composed of four rate determining coefficients which determine the rate of formation and destruction
of initial impermeable layer, the activated chemical reaction process and the following relent diffusion
controlled process. This preliminary approach shows high potential of simulating of hydration process.
Four coefficients, however, are just fit parameter in Tomosawa’s model and they are not predictable

1
Research Associate, Graduate School of Engineering, Hiroshima University, Japan
2
Graduate student, Graduate School of Engineering, The University of Tokyo, Japan
3
Associate Prof., Graduate School of Engineering, The University of Tokyo, Japan

1
from any information of cement properties. This can be deduced by the fact that particle size
distribution and interparticle contact, which play important role in hydration process, are not
considered. In order to take into account these and get consistent relationship between cement
properties and coefficients, reconstruction and modification are conducted from the assumptions of
Tomosawa’s model with additional change. The assumptions are listed as follows:
1. The cement particle initiates hydration from the moment that it is brought into contact with
water.
2. The hydrate formed by hydration adheres to the cement particle. And hydrate will be
covering it up spherically until interparticle contact comes up. And unhydrated cement keeps
spherical shape as well. The new gel is formed at the surface with no restriction of
interparticle contacts. If the surface contacts with the surface of another particle, new gel is
no longer produced on it.
3. The hydrate has a vgel times as much as the original cement in volume.
4. The liquid phase, which is assumed to be water, diffuses through the hydrate layer and
reaches the surface of the cement particle (reacting front) and chemically reacts with cement.
This process continues through hydration process. And part of the hydrate produced at the
reacting surface moves out through the layer of hydrate. Hence, equi-molar counter diffusion
of water and hydrate (presumably ions) is assumed to be taking place in the hydrate layer.
5. The diffusion coefficient of hydrate layer for water is not different between outer products
and inner products. This diffusion coefficient is affected by tortuosity of gel as well as radius
of gel pore in hydrate. This phenomenon is expressed as a function of degree of hydration.
6. The particle size distribution of cement can be approximated by Rosin-Rammler function.
And each particle with the same diameter has the same rate of hydration.
7. Dormant period in the initial process of hydration is assumed that there is a process in which
the reaction resistance increases with the increase of degree of hydration in each particle
(film formation) followed by a period in which the reaction resistance decreases with
increasing thickness of outer products.

2.2 Paricle size distribution in space

Cement particle distribution will make a big difference in cement hydration process. Defining degree
of cement hydration as ratio of reacted cement volume to initial cement volume, in this sense, each
particle shows different degree of hydration and degree of hydration of total cement paste should be
accounted for this different degree of hydration of each particle. In the proposed model, it is assumed
that the cement particle distribution can be expressed with Rosin-Ramler function:

(
V ( d p ) = 1 − exp −bd p
n
) (1)

On the other hand, cement particles develop an interparticle contacts as hydration proceeds. This
phenomenon is determined by the reaction rate, initial position and size of each cement particle in
paste matrix. After formation of interparticle contact, cement hydration will be inhibited by decrease
of area to suck available water to hydrate. In regard to this aspect, these exist several models of
location of cement particles. To cite instances,
random distribution model (Kunders 1997) and
flocculation model (Bentz 2000) are proposed so
far. In this proposed model, it is assumed that
each cement particle has the same ratio of
available water volume to its cement volume and
unit cubic cell is determined as centered spherical
cement particle surrounded water in cube. The
size of unite cubic cell is according to entire
water to cement ratio of cement paste. (see
Figure 1) This is one of the methods to arrange Figure 1. Schematic representation of particle size
distribution model in cement paste

2
the cement particles in space homogeneously. In this case, the cement particles are located as pseudo-
6-neighborhood. The 6-neighborhood arrangement is not efficient. If the closest packing is assumed,
the arrangement should be 12-neighborhood among the same size of particles. But when flocculation
is considered (Taylor 1997), the arrangement of spherical cement particles, which assumes
homogenous arrangement with regard to volumetric ratio, must be less efficient and the number of
neighboring particles will be reduced.

2.3 Hydration model of each cement particle

According to the Tomosawa’s model hydration process is expressed as a single equation that is
dominated by three different rate-determining phenomena, i.e. producing initial protective layer,
inward diffusion of external water equivalent to the outward diffusion of reaction products and
chemical reaction on the surface of unhydrated surface (Tomosawa 1997):
drt Cw∞
− ρ c (γ + Wa , g ) rt dRt ( vgel − 1) rt drt
2
= 2

dt 1 1 r − 1 Rt 1 , = ⋅ (2)
2
+ t + 2 dt Rt
2
dt
kd rt De kr rt
where rt is radius of unhydrated cement particle, Rt is total radius including the gel layer, De is
effective diffusion coefficient of water in the cement gel, kr is coefficient of reaction rate per unit area
of reaction front, γ is the stoichiometric ratio by mass of water to cement, Wa , g is the ratio of water
entrapped in the gel pore to cement, ρc is density of unhydrated cement and vgel is volumetric ratio of
hydrated cement paste gel to unhydrated cement.
With Eq.(2), degree of hydration of each particle, α d is calculated:
3
4  4  r 
α d = 1.0 −  π rt 3   π r03  = 1.0 −  t  (3)
3  3   r0 
where α d is degree of hydration of the cement particle whose diameter is d = 2r0 . The total degree of
hydration α is defined as accumulation of each degree of hydration over the cement particles whose
distribution is according to Eq.(1).
The first term of the denominator on the right side of former Eq.(2) relates to the initial reaction,
indicating its reaction resistance. This affects only a very early stage when total degree of hydration
almost equals to 0, and in this case, the reaction rate is determined by kd . Here kd is assumed to be
expressed as the sum of the term of increase of mass transfer resistance as increase of total degree of
hydration and the term of degrease of mass transfer resistance as increase of thickness between
original boundary and reaction front ( r0 − rt ) of each hydrating cement particle:
B
+ C ⋅ ( r0 − rt )
4.0
kd = (4)
α 1.5
As the hydration process progresses the gel density has been found to increase (Relis 1977). The
effective diffusion coefficient De is assumed to be decrease with increase of the gel density:
1.5
 1 
De = DE  ln  (5)
 αd 
where DE is initial diffusion coefficient that is dependent on the composite of cement particle.

2.4 Structural limitation by interparticle contact

Cement particles are expanding with hydration process by a factor vgel . Available space is occupied
on a first come and each particles are interconnected with hardening of cement paste matrix. This
formed cement paste matrix structure has effects on physical aspect of matrix as well as hydration
process of cement with feedback from it. In this regard, the structural limitation is modeled explicitly.

3
Cement particle is assumed be spherical
and each particle has cubic space in
accordance with water to cement ratio. This
assumption means that the each particle is
even in terms of available space for
expanding. There are three type of mode
with degree of expanding (Figure 2). Mode 1 Mode 2 Mode 3
Figure 2. 3-dimensional expression of structural
“Mode 1” is the state that the cement
limitation of expanding hydrate gel
particle does not make contact with
surfaces of cell, “mode 2” is the state that the cement particle starts to make contact with surfaces of
cell and the contacted parts have circular shape and “mode 3” is the state that the cement particle
makes contact with surfaces of cell widely and the contacted parts are connected each other.
(i) Initial state of cement particle and cell
Volume of cement particle in the cell whose size is 1 in a side is determined with the cement density
ρc , the water density ρ w and water to cement ratio W / C :
1
Vc = (6)
ρ
W /C ⋅ c +1
ρw
Ratio of radius of cement particle to the length of cubic side r0 holds:
1/ 3
 3V 
r0 =  c  (7)
 4π 
(ii) Surface and volume
In “mode 1”, “mode 2” and “mode 3”, the ratio of radius of hydrated cement particle to the length of
cubic side r satisfies r0 ≤ r < 0.5 , 0.5 ≤ r < 2 / 2 and 2 / 2 ≤ r < 3 / 2 respectively. The surface that
is in contiguity with water is represented by a function of r :
1/ 2 1/ 2
 0.5  r
S (r ) = 4π r 2 , S (r ) = 4π r 2 − 12π 1 −

 , S (r ) = 8
r  2
∫ 2
∫ 2 r − x2 − y 2
2
dxdy (8)
r −1/ 2 r −1/ 4 − x

And the volume of hydrated cement is represented by a function of r :

4 4 2 1 1 
V ( r ) = π r 3 , V (r ) = π r 3 − 6π  r 3 − r 2 + 
3 3 3 2 24 

1
V (r ) = 2 ⋅ r 2 − +
2
1 
⋅ 0.5 ⋅ r 2 − x 2 − 1/ 4 (9)
0.5  2 
16 ∫  2  dx
 r − x2 π  0.5  
r 2 −1/ 2  + ⋅  − Arc cos   
 2  4  r −x
2 2
  

Each three equation is shown according to an order of “mode 1”, “mode 2” and “mode 3”.
The structural limitation of hydration process is introduced to Eq.(2) by using the reduction factor Cst :

drt Cw∞
− ρ c (γ + Wa , g )rt
2
= Cst ⋅
dt 1 1 r − 1 Rt 1
2
+ t +
kd rt De kr rt 2

4
 dRt 4π ( vgel − 1) rt drt
2

= ⋅ (10)
dt S ( Rt ) dt

where Cst is defined as:

S ( Rt )
Cst = (11)
4π Rt
2

where Cst means the effect of reduction of water through gel surface that is contacted with water and
S ( Rt ) is the same function of Eq.(8).

2.5 Temperature effect on hydration process

Curing temperature effect on the rate of chemical reaction, i.e. hydration process. Temperature effect
is introduced to each mass transfer coefficient and reaction factor in this proposed model (Tomosawa
1997). It is assumed that B in Eq.(4), kr and De in Eq.(2) follow Arrheniu’s law. Hence, with the
values of B293 , kr 293 and De 293 that are given for 293 K, the coefficients at T K are expressed as
follows:
B = B293 exp  − β1 (1/ T − 1/ 293) 

De = De 293 exp  − β 2 (1/ T − 1/ 293)  (12)

kr = kr , 293 exp  − E / R ⋅ (1/ T − 1/ 293) 

3. MODEL PARAMETERS

For the determination of the model parameters kr 293 , DE 293 (in Eq.(5)), B293 , C293 , β1 , β 2 and E / R an
evaluation was conducted. Degree of hydration is determined by the ratio of amount of heat liberation
to maximum heat liberation predicted by Woods equation (Woods 1932). In this evaluation more than
20 hydration tests (i.e. Tomosawa 1997-2) were involved, comprising 9 different types of Portland
cement with C3S contents ranging from 20% to 70%. Curing temperatures varied from 10 °C to 60 °C,
particle size distribution with blaine value ranging from 200 m2/kg to 550 m2/kg.
The kr 293 is expressed as a function of the C3S and C3A contents:

( )
0.975
kr 293 = 8.05 ⋅ 10−10 × rwC3 S + rwC3 A (13)

where rwC3 S and rwC3 A are mass contents of C3S and C3A respectively.
This parameter indicates the reaction rate per unit area of reaction front and this value dominates the
initial rate of hydration process. It seems reasonable to suppose that the kr 293 is associated with C3S
and C3A contents showing high reaction speed before dormant period. In this evaluation the value of
kr 293 is ranging from 1.8 ·10-8mm/h to 5.6·10-8mm/h.
The DE 293 is expressed as a function of the C3S contents:
2.024
DE 293 = 3.2 ⋅ 10−14 × rwC3 S (14)

The DE 293 value represents effective diffusion coefficient of cement gel in initial stage. This rate-
determining value may be affected by the C3S contents. This DE 293 is found from 20·10-12mm2/h to
180 ·10-12mm2/h. For the factors B293 , C293 , β1 , β 2 and E / R with constant value is applicable in
Table 1. Model parameters in proposed model
Coefficient B293 [x10 mm/h] C293 [x10-7/mm3·h]
-0
β1 [K-1] β 2 [K-1] E / R [K-1]
Value 0.3 5.0 1231 7579 5364

5
majority cases (See Table 1). The B293 , C293 and 500
E / R are rather sensitive to the behavior before
dormant period. 20%-variation of there value may 400

Simulation result [J/g]

cause 5% of degree of hydration at 72 hours. The β1
and β 2 are insensitive. 20% -variation of these values 300
may leads 2% of difference in degree of hydration at
72 hours. 200
In Figure 3 Comparison of simulation result with
experimental data of heat liberation is shown. The
100
experimental heat liberation is value of the end of
each experiment. Simulation results are good
0
agreement with experimental results. 0 100 200 300 400 500

Expeimental Heat liberation [j/g]

4. CONCLUSION Figure 3. Predictive accuracy of heat liberation
by proposed model (Comparison is made at
Entire hydration process of each cement particle is the end of experiment.)
modeled by a single kinetic equation with assuming
that particle size distribution, interparticle contact with cell concept and that each cement particle has
the same ratio of available water volume to its cement volume. Entire system of cement paste is
presented as accumulation of them. Simulation results shows good agreement with experimental data
and its accuracy is better than 10% before 72 hours from mixing.

5. REFERENCES
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Bentz, D. P. (2000). “CHEMHYD3D: A Three-Dimensional Cement Hydration and Microstructure
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Technology
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