Research progress in modelling of ageing

viscoelastic properties cement paste

Poornima Patil

Kansas state university

+17853177017
ppatil@ksu.edu
Abstract

Keywords cement Viscoelastic Ageing Modelling

Abstract

Studying cement paste with respect to different geometry and properties such as creep and aging
effects will more precisely explain the long term behavior of concrete. Hydration of cement paste
essentially influences the microstructure and some phase properties prominently at early age.
Hence, recently researches are focusing on studying the aging viscoelastic properties of cement in
order to understand the behavior of concrete at later age. This review paper discuss the different
approaches available to model the ageing viscoelastic properties of cement paste and also try to
throw some light on limitations associated with each approach. It can be observed from the
literature review that the solidification theory is fundamental theory to model ageing viscoelastic
properties but cannot be used effectively alone. A model that accounts for both aging due to
solidification and inherent aging of the cement paste gel (modeled using the time–shift approach)
more precisely predicts the aging viscoelastic behavior of portland cement paste. Combination of
different approaches leads to reliable results compared to individual approach.

1 Introduction

The materials which exhibit both viscous and elastic responses are known as
viscoelastic; the strength and deformation under stress of viscoelastic materials
are dependent on load duration. Hence, in order to envisage the performance and
anticipate the useful life of a material, modeling and testing the material
properties including time as independent variable is must. The test for creep is to
predict deformation. The strength and the related stress relaxation tests are to
measure the loss of stress at constant strain. In the context of effective mechanical
properties of heterogeneous materials derived by scale transition, viscoelasticity
has a special place and still represents a challenging problem.

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1.1 Concrete viscoelastic behavior

Concrete structures are known to age with time which can sometimes significantly
degrade and eventually eliminate their functionality. It is very well known that
concrete is a viscoelastic material which exhibits the creep and stress relaxation
characteristics with ageing. To understand the long term behavior of prestressed
and conventional concrete members subjected to changing load histories, it is
necessary to study the ageing properties of concrete. As ageing can be defined
with different variables it becomes difficult to model these properties and in turn
results in ambiguous predictions of long term performance. These predictions
with uncertainties may lead to serviceability issues and structural failures at the
later stage of service life of concrete. The viscoelastic behavior of concrete is a
complex subject. It is almost entirely attributable to changes in the properties of
cement paste.
Continuous hydration of cement, combined with the accumulation of cracking and
dissolution of hydration products, results in the development of properties that are
dependent on mix design, time, stress, temperature and humidity.[5]
Since the rate of change in cement paste is very significant at an early age (less
than 28 days), a study of this period of the evolution of the paste should give the
greatest insight into the mechanisms responsible for behavior. [5]. Thus, studying
cement paste with respect to different geometry and properties such as creep and
aging effects will more precisely explains long term behavior of concrete.

1.2 Ageing viscoelasticity of cement paste

The viscoelastic behavior of concrete is dictated by the behavior of the cement

paste as aggregate inclusions are typically non-aging elastic. Stress development
and time dependent deformations of concrete structures are believed to be mostly
affected by the viscoelastic behavior of cement paste.
Creep is usually modeled using viscoelastic constitutive equations and in order to
have a reliable prediction of possible early age cracking because of shrinkage and
thermal stress or long term performance comes with proper understanding of
ageing viscoelastic behavior. Cement paste is subjected to ageing and is directly
related to changes in the microstructure of the material. These changes can be
attributed to hydration process in addition to relaxation of hygro-chemically
induced self equilibrated prestress of the microstructure [11,12]. Degradations
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processes (e.g. leaching), which can be coupled with the viscoelastic behaviour of
the material itself, can be also a source of the ageing behavior [6]
Ageing creep is difficult to predict because the microstructure evolves after the
application of the initial load and creeps non uniformly [3]. In spite of its practical
significance, there are very limited experimental data on the creep properties of
cement paste at ages less than 72 h in literature.
Presently there are various theories that try to explain the viscoelastic behavior of
cement based materials, but most of them cannot adequately describe the
viscoelastic behavior. One of the reasons for this is that cement-based materials
are composite materials with random matrix arrangements that are difficult to
model; and the other reasons is that the internal chemical components of cement-
based materials change during the hydration process, including the dissolution of
existing components and the formation of new component materials which is also
referred to as ageing process [3].

1.3 Modeling of ageing viscoelastic properties of cement paste

Modeling of ageing viscoelastic behavior of cement paste is important so that

simulated computational experiments can be conducted and hence analysis of
these modeling results can help in understanding the mechanisms responsible for
viscoelastic behavior of cement paste. To effectively model the aging viscoelastic
properties of cement paste, a microstructure dependent dependent analytical
constitutive model of cement paste can be constructed and then the characteristic,
aging viscoelastic behavior of the micrometric cement paste phases can be
integrated to anticipate the viscoelastic macroscale responses of cement paste.
Basic knowledge of the time dependent behavior of concrete is attained through
modeling of aging viscoelastic properties of cement paste and such models may
be believed to be useful in anticipating the behavior of concrete by engineers and
to help improve the design of damage-resistant structures. It may also assist in
overcoming the current limitations of concrete and developing new advanced
materials [3].

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2 Constitutive theories for aging viscoelastic
materials

A considerable amount of research has been conducted to develop reliable mathe-

matical models for the viscoelastic behavior of viscoelastic materials, and many
simple constitutive models have been effectivelyexploited, such as the Maxwell
model, the Kelvin-Voigt model, and the Standard Linear Solid Model [4]. All
these models prove to generate effective simulations for a linear viscoelastic
material under different forms of stresses, but fail to consider the effect of
hydration reaction on creep of concrete. A standard theory which chains linear
viscoelasticity and the formation effect is the solidification theory [14, 15], The
advantages and limitations of different theories for ageing viscoelastic materials is
discussed in this paper. [3]

2.1 General Constitutive Theory

The general form of the constitutive equation for a linear viscoelastic material is

𝑡 𝜕𝜎𝑘𝑙 (𝑡 ′ )
𝜀𝑖𝑗 (𝑡) = ∫0 𝑆𝑖𝑗𝑘𝑙 (𝑡 − 𝑡 ′ ) 𝑑𝑡 ′ + 𝜀 𝑓 (𝑡)𝛿𝑖𝑗 (1)
𝜕𝑡 ′

where 𝑆𝑖𝑗𝑘𝑙 is the viscoelastic compliance tensor, 𝜎𝑘𝑙 (𝑡) is the stress function,

𝜀𝑓 (𝑡) is the free strain, 𝜀𝑖𝑗 (𝑡) is the overall time-dependent strain, and 𝛿𝑖𝑗 is

Kronecker‟s delta. In this equation, 𝑆𝑖jkl (𝑡) is a function of single variable (𝑡−𝑡′).

For aging linear viscoelastic materials, the most general form is

𝑡 𝜕𝜎𝑘𝑙 (𝑡 ′ )
𝜀𝑖𝑗 (𝑡) = ∫0 𝑆𝑖𝑗𝑘𝑙 (𝑡, 𝑡 ′ ) 𝑑𝑡 ′ + 𝜀 𝑓 (𝑡)𝛿𝑖𝑗 (2)
𝜕𝑡 ′

Here 𝑆𝑖𝑗𝑘𝑙 (𝑡) is a function of both t and 𝑡′.

The above equation complicates the viscoelastic analysis. Meanwhile many

theories have been developed trying to modify this equation so that the analysis is

simple and also takes into account the viscoelasticity and aging effect.

2.2 Solidification Theory

The solidification theory was initially derived by Bazant (1977) to explain the
aging effect concrete creep. The main concept of the model is that “hydration
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products are non-aging viscoelastic materials and that aging effects are present on
the bulk scale as a result of the gradual solidification of new hydration products”.
According to the model individual layer of the hydration products must solidify
independent of stress which shows that the layers which are formed at the age t’
are only stressed by loads which are applied after t’ The solidification theory is
demonstrated in Fig. 6.

Fig. 6. Conceptual diagram of solidifying material subjected to applied stress, σ.

Carol and Bazant (1993).

The ultimate form of the constitutive equation for uniaxial loading and
deformation is as shown in the below equation.[7]

𝜕𝜀(𝑡) 𝐽0 𝜕𝜎(𝑡) 1 𝑡 𝜕𝐽𝑡 (𝑡−𝑡 ′ ) 𝜕𝜎(𝑡 ′ ) 𝜕𝜀 𝑓 (𝑡)

= + ∫ 𝑑𝑡 ′ +
𝜕𝑡 𝑣(𝑡) 𝜕𝑡 𝑣(𝑡) 0 𝜕𝑡 ′ 𝜕𝑡 ′ 𝜕𝑡

(3)

J0 denotes instantaneous elastic uniaxial compliance, v(t) denotes aging function

for the material (representing the volume fraction of solidified material), Jg(t –t’)

denotes non-aging viscoelastic uniaxial compliance of the cement gel which is

dependent on a single variable (t – t’), and εf (t) denotes free strain. Since Jgis

dependent on a single variable, it can beexpressed by models such as a Kelvin

chain. Another form of the constitutive equation for a solidifying, linear

viscoelastic material is expressed as:

𝑡 𝜕𝜀(𝑡 ′ )
𝜎(𝑡) = ∫0 𝑣(𝑡 ′ ) 𝐸𝑔 (𝑡 − 𝑡 ′ )𝑑𝑡 ′
𝜕𝑡 ′

(4)
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where 𝜈(𝑡) is the aging function, 𝐸𝑔(𝑡 − 𝑡′ ) is the non-aging viscoelastic uniaxial

moduli of the solidifying phases [18].

From the equation (13) the elastic component may be written as

𝜕𝜀(𝑡) 𝐽0 𝜕𝜎(𝑡)
= (5)
𝜕𝑡 𝑣(𝑡) 𝜕𝑡

The equation explains that the instant strain in the material is reliant on the age

when the load was initially applied. The main advantage of the solidification

theory is that it can be effectively used to model the aging viscoelastic properties

of both concrete and cement paste. Solidification theory is not physically

represented by a simple change in the rate of viscoelastic response.

2.3 Time–shift approach

A characteristic of thermorheologically simple materials is that the shape of the

functions on the log time scale does not change with loading age. By measuring

the viscoelastic compliance or modulus at multiple ages and selecting one age to

be the ‘master’, the retardation or relaxation times for the other ages are simply

shifted by a constant factor until they fall in line with the master curve on a log–

log plot [7]

The time–shift approach used for modeling aging viscoelasticity is corresponding

to the time– temperature superposition principle. The principle states that the

change in the temperature leads to increase or decrease in the relaxation times.

The outcome is basically a shift in the compliance or moduli functions along the

log time axis without changing the shape of the curves. The aging of viscoelastic

materials may be explained using temperature superposition principle.

The shift coefficients for each age can be determined and fit to a function Atusing

the following equation.

𝑡𝑟𝑒𝑓 𝜇
𝐴𝑡 = ( ) (6)
𝑡
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Here trefis the reference master age, t is the current age, and μ is a fitting parameter

(Struik 1978). The constitutive equation for an aging material is given as

(Morland and Lee 1960)

𝑡 𝜕𝜎𝑘𝑙 (𝑡 ′ )
𝜀𝑖𝑗 (𝑡) = ∫0 𝑆𝑖𝑗𝑘𝑙 (𝜉(𝑡) − 𝜉(𝑡 ′ )) 𝑑𝑡 ′ + 𝜀 𝑓 (𝑡)𝛿𝑖𝑗 (7)
𝜕𝑡 ′

where ξ is a pseudo-time and ξ(t) −ξ(t’) is expressed as

𝑡 𝑑𝑡 ′′
𝜉(𝑡) − 𝜉(𝑡 ′ ) = ∫𝑡 ′ 𝐴 ′′
𝑡 (𝑡 )

(8)

Vichit-Vadakan and Scherer (2003) proved that the shape of the relaxation

function was conserved during aging, and utilized this technique to cement paste

to explain aging effect on short-term early age stress relaxation.

[7] noted that the time–shift approach is phenomenological and is not linked to
any specific proposed aging mechanism, per se. The ability of the time–shift
approach to accurately model the aging of a viscoelastic material simply implies
that the aging manifests itself as nothing more than a change in the retardation or
relaxation rate with age, with no change in ultimate magnitudes of viscoelastic
behavior. For example, for a material characterized by a Kelvin chain, aging
according to the time–shift approach would simply be represented by age-
dependent viscosities or age dependent retardation times in a Dirichlet or Prony
series expansion.[7]

2.4 Dissolution–precipitation approach

The Dissolution–precipitation method is based on the concept that creep of

concrete occurs basically because of dissolution and consequent precipitation of
new products. In the dissolution–precipitation approach, aging is accounted for by
the time-dependent deviation of the elastic modulus and viscosity with the degree
of reaction. This approach considers the solidifying material as elastic because the
creep or stress relaxation can be explained by the reduction in the bulk elastic
modulus caused by dissolution process. The major advantages of the dissolution–
precipitation approach are the connection between the chemical processes and

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deformation which permit the effect of degradation mechanisms to be quantified,
and the aging rate effect can be physically explained.
[10] The theory presented here is capable of predicting the observed aging
‘viscoelastic’ behavior of hydrating and reacting concrete. The theory explains
that aging is due to the temporal variation of the elastic modulus and viscosity
with the reaction rate. The validity of the superposition principle reveals the
inherent linear character of material response. Basically, the proposed theory fits
in the group of linear aging viscoelasticity theories. the proposed theory is capable
of predicting creep, recovery,relaxation, dissipation and divergence of reacting
solids

2.5 Combined solidification –time-shift constitutive model[7]

Grasley and lamge (2007) found that both the time–shift approach and the
solidification theory were unable to explain the ageing viscoelastic properties of
cement paste samples tested in their study.
It is likely to expect that progress in degree of hydration should effect both elastic
modulus and viscoelastic properties of cement paste. Hence, realistic constitutive
model should account for the solidification effects. It is observed that there are
additional mechanisms which affect the creep/relaxation behavior without
affecting the instantaneous elastic properties.in contrast to solidification theory
Combined solidification–time-shift constitutive approach accounts for direct
ageing of cement paste gel.
This approach, considers a solidifying material which on the microscale or
nanoscale is an aging, linear elastic material. The direct aging of the gel is
considered to be a rate-type effect modeled using the time–shift approach. The
derivation of this model follows that of Bazant’s solidification theory (Bazant
1977; Carol and Bazant 1993), except that the real time is replaced by a pseudo-
time such that the linear viscoelastic compliance of the solidifying gel (Jg)
becomes[7]

(𝑡 − 𝑡 ′ ) = 𝐽𝑔 {𝜉(𝑡) − 𝜉(𝑡 ′ )} (9)

The two basic governing equations for a solidifying material become

𝑡
𝜎(𝑡) = ∫0 𝜎𝑔 [𝑣(𝜃), 𝑡] 𝑑𝑣(𝜃) (10)

𝜉
𝜀(𝜉) − 𝜀(𝜃) = ∫𝜃 𝐽𝑔 {𝜉(𝑡) − 𝜉(𝑡 ′ )}𝑑𝜎𝑔 (𝜉 ′ ) (11)
8
where σg is the microscopic stress acting on the infinitesimal layers at any time t,
and v(t) is the effective volume of solidified material. Equation (12) is the
constitutive equation for the solidifying material where (10) has been utilized
Following the derivations in Bazant (1977) or Carol and Bazant (1993), one finds
the final constitutive equations as

𝜕𝜀(𝑡) 1 𝜕𝜎(𝑡) 𝑡 𝜕𝐽𝑔 {𝜉(𝑡)−𝜉(𝑡 ′ )} 𝜕𝜎(𝑡 ′ )

= [𝐽 + ∫0 . 𝑑𝑡 ′ ] (11)
𝜕𝑡 𝑣(𝑡) 0 𝜕𝑡 𝜕𝑡 𝜕𝑡 ′

J0 is the instantaneous elastic compliance at the reference age.

𝑡 1 𝜕𝐽𝑔 {(𝜏1+𝜇 −𝜏′1+𝜇 )/(1+𝜇)}

𝐽(𝑡, 𝑡 ′ ) = ∫𝑡 ′ 𝑣(𝜏) 𝑑𝜏 (12)
𝜕𝜏

Above Equation (18) expresses the compliance function of a solidifying material

consisting of an aging, viscoelastic gel. It is obvious that the combined approach
produces improved overall predictions than each method separately.
This is probably due to the fact that the inclusion of both models accounts for
multiple aging mechanisms simultaneously. The It was observed that the fit
quality in the combined constitutive model depends on the function chosen to
represent the aging time-shift.

2.6 Microstructural modeling[8]

Models to predict the long-term creep of cement pastes are usually established
based on mathematical functions that fit empirical data (Bažant and Baweja 2000;
Grasley and Lange 2007) or based on micromeChanical models (Pichler and
Lackner 2008; Scheiner and Hellmich 2009). [8] presented a new numerical
approach for prediction the ageing creep in early-age cement paste. They
simulated creep behavior by applying a time-varying generalized Maxwell model
on the individual elements of a finite-element mesh of a simulated three-
dimensional microstructure and compared obtained results with the literature.
The results demonstrated how numerical models can be used to upscale phase
characteristics to macroscopic properties of composites. Similar to the contact
creep compliance the uniaxial creep compliance was defined as below
1 1 𝑡−𝑡0
𝐽(𝑡, 𝑡0 ) = 𝐸 + 𝐶 ln (1 + ) (13)
𝑢𝑛𝑖 𝜏

where Jðt; t0 Þ (GPa−1) = uniaxial creep compliance a certain time t of the

material loaded from time t0; E (GPa) = elastic module of C-S-H; and Cuni (GPa)
= uniaxial creep modulus
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This paper demonstrates the strength of microstructural models in simulating the
effect of the spatial distribution of cement particles and the hydration products on
the development of mechanical properties of cement pastes. The authors
successfully managed to simulate the combined effect of microstructural
development process and creep (which occur parallel) in the models. The model
also proves to be efficient in capturing the effect of age of loading observed in
cementitious materials. [8] Suggests that the assumption of densification of C-S-H
in the simulations provides significantly better predictions of ageing creep for
early-age loading on cement pastes. The model fails to predict the realistic
absolute values of creep due to the observed relative errors of approximately 20%.
Another source of weakness in the approach could arise from the necessity to
discretize the microstructure into a mesh, where the size of the mesh elements
may affect convergence and accuracy.[8]

2.7 combining analytical and numerical homogenization tools [9]

[9] proposed a study combining numerical and analytical tools to evaluate the
ageing viscoelastic properties of cement-based materials within a multiscale
framework. In this study With analytical homogenization the properties at the
cement paste and mortar scales were estimated by a combining Generalized Self-
Consistent (GSC) and Mori-Tanaka (MT) schemes. Numerical homogenization
10
has the advantage of allowing assessing local information and to study more
complex geometries. This combined strategy establishes a reliable tool to study
how different mechanisms leading to ageing at the hydrated products scale, as
well as other features of cement-based materials such as the ITZ affect the
viscoelastic behavior at larger scales.
Homogenization was applied at cement paste, mortar and concrete scales. The
creep and relaxation tensors were obtained by numerical inversion of Laplace
transforms. Then, the resulting ageing behaviour of the material was obtained by
integration over the changes in the volume fraction of the constituents in time

Fig.3 Multiscale strategy with combined analytical and numerical homogenization

The study does not account for the mechanisms acting in long term and also
assumes that percolated structure exists at the different levels which are not true at
very early ages.

3 Conclusions

Each approach used to model the ageing viscoelastic properties of cement has got
its own limitation. It is evident from the literature that Microstructural modeling
approach fails to predict the realistic absolute values of creep as the results shows
an error of 20% and also the size of the mesh elements effect the accuracy and
convergence.[] The combined analytical and numerical homozenigation approach
fails to account for the mechanisms acting in long term and also assumes that

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percolated structure exists at the different levels which is not true at very early
ages.
Solidification approach is the fundamental approach to assess the ageing
viscoelastic properties of cement paste but is not capable to explain completely
the aging of the viscoelastic properties of cement paste as it fails to account for
viscoelastic effects.
The dissolution–precipitation approach is unable to account for long-term creep or
aging that occurs in the absence of reaction The time shift approach also is not
able to fully account for the aging effect of cement pastes. [7] shows that The
combination of both solidification and time shift approach will give better
understanding of aging viscoelastic properties of cement paste. It means that the
ultimate characterization of viscoelastic aging behavior of cement paste is
accounted by combining hydration related effects and inherent aging of gel.[]
.more samples need to be tested to validate the combined time shift solidification
approach .

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References
[2]Microstructural Modeling of Early-Age Creep
in Hydrating Cement Paste
Quang Huy Do1; Shashank Bishnoi2; and Karen L. Scrivener3
[3]
MODELING OF THE AGING VISCOELASTIC PROPERTIES OF CEMENT PASTE USING
COMPUTATIONAL METHODS A Thesis by XIAODAN LI
[4] Mech Time-Depend Mater (2007) 11: 27–46
DOI 10.1007/s11043-007-9030-9
The viscoelastic response of cement paste to
three-dimensional loading
Zachary C. Grasley · David A. Lange
[5] The Effects of Early-Age Stress on the Elastic and Viscoelastic
Behavior of Cement Paste
Christopher L. Galitz
[6]Multiscale estimation of ageing viscoelastic properties of cementbased
materials: a combined analytical and numerical approach
to estimate the behaviour at early age
Tulio Honorio corresponding author, tulio.honorio-de-faria@enpc.fr , +33 01 64 15 37 50
CEA, DEN, DPC, SECR, Laboratoire d’Etude du Comportement des Bétons et des Argiles, F-
91191 Gif-sur-Yvette, France
LMT (ENS Cachan, CNRS, Université Paris Saclay) 94235 Cachan, France
Current adress : Ecole des Ponts Paristech, Laboratoire Navier, 6/8 Avenue Blaise
Pascal, 77420 Champs sur Marne, France
Benoit Bary
CEA, DEN, DPC, SECR, Laboratoire d’Etude du Comportement des Bétons et des Argiles, F-
91191 Gif-sur-Yvette, France
Farid Benboudjema

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