Understanding the origin of

rheology – Complex materials

P. V. Ponambala Moorthi
Why materials behave differently?
• Retention of the shape of a solid material on application of a force
characterizes a material
• This innate ability of the material to retain a shape can be described
by an appropriate variable
• Why does this appropriate variable that describes the behavior of a
material deviates?
• How this deviation can be related to its microstructure ?

02-Nov-16 2
 Why materials behave differently?
• Arrangement of this fundamental
elements in a material defines a
materials mechanical properties

• Behavior and classification of a material

as solid or liquid depends upon the
distribution of this elements

• The interaction of this system of

elements with its neighbors can be via
van der Waals forces, covalent forces or Fig: The dependence of attractive, repulsive
ionic forces and net forces on interatomic separation; The
Fig Ref: Callister, W.D. Jr (2007) Materials science and dependence of attractive, repulsive and net
engineering: An introduction, 7th edition, John Wiley & Sons. potential energies on interatomic separation
02-Nov-16 3
Tendency of material to deform
• As when a low stress is applied, each atom gets displaced from its
equilibrium position due to increase in potential energy
• Which causes relative displacement of atoms from its neighbor
• For sufficiently large stress some atoms in the material gets out of
their potential well causing
• Dislocation (plastic behavior)
• Breakage
• This explains how deformation from microscopic origin can be related
to macroscopic scale of observation

02-Nov-16 4
Rheology
• The science of the deformation and flow of matter
• Based on the mechanical characteristics exhibited by a material.
Materials can be classified broadly which exhibits solid behavior and
liquid behavior
• Deformation of a particular material such as soft solids depends upon
the concentration of a particular element
• Resistance offered by colloidal system and a solid against the same
deformation (order of power in energy required for separation differs
by more than 30)

02-Nov-16 5
Rheology of soft solids and Newtonian fluids
• In a system of soft solids (different types of
interactions will be there) due to wide
range of mesoscopic elements (eg:
concrete, muds, toothpastes etc.)

• In case of fluids behavior description can

be better comprehended by flow rate
rather than deformation
Fig: Principle of a simple shear: relative motion of material
• For a Newtonian materials, the applied planes
shear stress and shear rate can be related
by ̇ Δ
= ̇ ℎ , ̇= =
Δ
• Where, – shear stress; - material
viscosity; ̇ - shear rate
Fig Ref: Roussel, N (2012) Understanding the rheology of
02-Nov-16
concrete, Woodhead Publishing. 6
Rheology of suspensions
• Mesoscopic objects dispersed in a Newtonian liquid

• Because of their presence fluid layer follows more complex paths in a

simple shear experiment resulting in larger viscous dissipation

• The suspension remains Newtonian until the distribution of elements

remains isotropic and constant

• Increase in this mesoscopic elements increases the viscous dissipation due

to friction between suspended grains rather than hydrodynamic dissipation

02-Nov-16 7
Rheology of suspensions
• This increase was depicted with
change in suspension (non-
colloidal grains) volume fraction
as given by

= 1 + 2.5

• Where, – suspension volume

fraction; - relative viscosity
of a suspension for increase in
volume fraction; - viscosity of
Newtonian material without Fig: Variation in relative viscosity as a function of solid
suspension (valid for < 2%) fraction in Newtonian fluids
Fig Ref: Roussel, N (2012) Understanding the rheology of
concrete, Woodhead Publishing.
02-Nov-16 8
Rheology of non-Newtonian fluids
• In case of non-Newtonian materials its viscosity varies with respect to
applied shear rate and given by
=
̇
• Where, – shear stress; - apparent viscosity; ̇ - shear rate

• The origin of viscous dissipation is modified by the flow

• Example suspension of asymmetrical elements in fluids

02-Nov-16 9
Rheology of non-Newtonian fluids – shear
thinning
• This alignment of asymmetrical elements can be rapid with respect to
applied shear rate (i.e.) apparent viscosity decreases with shear rate

̇ <0
• If this alignment takes some time to develop ‘thixotropic’ effects will
be observed (i.e.) apparent viscosity for a given shear rate varies with
time

( ̇)
≠0

02-Nov-16 10
Rheology of non-Newtonian fluids – shear
thickening
• Shear thickening is considered as opposite of shear thinning (i.e.) apparent
viscosity increases with increase in shear rate

̇ >0

• In reality, the trend is quiet different. In general, apparent viscosity remains

constant until a critical shear rate value

• Further increase in shear rate increases the apparent viscosity dramatically

02-Nov-16 11
Rheology of yield stress fluids
• Materials which behave both as solid as well as liquid based on
applied stress

• Beyond certain critical stress solid materials tend to break apart and
then transforms into liquid material

• Example of such materials varies widely from creams, muds,

foodstuffs, food pastes, mineral waste suspension, fresh concrete etc.

02-Nov-16 12
Rheology of yield stress fluids
• The critical stress value at which this transition takes place for a material is
called as yield stress ( )

• This transition from one physical state to another physical state requires
transformation in basic physical properties such as apparent viscosity ( )
tends to infinity

• Since apparent viscosity is given by = ( / ̇ ) which tends to infinity if

shear rate ( ̇ ) tends to zero

• Which increases the yield stress value considerably for a solid during
transformation of liquid to solid regime

02-Nov-16 13
Rheology of yield stress fluids
• Description of above model was given by many researchers based on
their experimental works

• Bingham model as = + ̇
• Herschel-Bulkley model = + ̇
• Casson model = + ̇
Fig: Apparent flow curve obtained for yield stress fluids
• Where, – shear stress; - yield stress; – plastic viscosity; ̇ -
shear rate; and are material parameters
Fig Ref: Roussel, N (2012) Understanding the rheology of
concrete, Woodhead Publishing.
02-Nov-16 14
Rheology of thixotropic fluids
• Characterization of thixotropy in a solid regime can be given well by
calculating elastic modulus by applying a small deformation

• The trend that can be obtained to describe this evolution illustrates

the elastic modulus as a function of time

• This increase in elastic modulus is ascribed due to the formation of

interlinking between particles relatively leading to increased jamming
of the system

02-Nov-16 15
Rheology of thixotropic fluids
• In both liquid as well as solid regime, structural deformation and
reformation with respect to applied shear stress or shear rate

• Which play a vital role in the determination of rheological properties of

such fluids

• Structural evolution can be given as

= − ( , ̇)
• Where, – is development state parameter of the structure of the
material; ̇ - shear rate

02-Nov-16 16
 Rheological behavior of different materials

Fig Ref: http://www1.lsbu.ac.uk/water/rheology.html

02-Nov-16 17
Rheology of cement system
• Cement systems are considered as a yield stress fluid possesses both
solid as well as liquid characteristics

• Influenced by several factors affecting their microscopic bonding and

microscopic structural development during the progress of time

• During its hydration process products are formed, so their flow

behavior at this stage highly depends upon the structure and the rate
of formation of hydration products

02-Nov-16 18
Rheology of cement system
• On application and removal of stress if the hysteresis loop is formed in such
a way that the loop gets displaced towards lower stress then the behavior
of the material is thixotropic in nature.

• If the loop displaces away from then the material is said to be behave as
anti-thixotropic.

• In former case the cement system becomes more workable and more fluid.

• In later case the cement system becomes stiffens on continuous working.

02-Nov-16 19
Effect of chemical admixture on rheology of
cement system
• Now-a-days for most of the construction process chemical admixture
has become mandate

• Chemical admixtures primary action is through the adsorption gets

adsorbed on the surface of the cement system

• Which reduces the plastic viscosity and yield stress

• Development of plastic viscosity is attributed due to the growth of

irreversible crystalline network
02-Nov-16 20
Effect of chemical admixture on rheology of
cement system
• This rate of formation of crystalline network is controlled by the
availability of surface or site necessary for nucleation

• The availability of surface for the nucleation process can be controlled

by stability or dispersion effect of chemical admixtures used for a
particular purpose

• Chemical admixtures works in a fashion of reducing the inter-particle

attractive forces thereby reducing the yield stress

02-Nov-16 21
Effect of chemical admixture on rheology of
cement system
• The origin of attraction between inter-particles is mainly due to the
weakest and short range primary forces called electrostatic force and
van der Waals force an origin of secondary force

• Lignosulfonates were used as water reducers and set retarders.

Lignosulfonates are 1st generation water reducers which improves the
workability of concrete mixtures by improving the plasticizing effect

• Molecular weight of lignosulfonates determines its ability in

plasticizing effect

02-Nov-16 22
Effect of chemical admixture on rheology of
cement system
• The dispersion effect of polynaphthalene sulfonates (PNS) is cement
dependent

• In case of cement with higher alkali content PNS of higher molecular

weight is required for producing better fluidizing effect

• PNS has better dispersion effect increasing greatly the fresh concrete
fluidity, but immediate slump loss was attributed with specific cement
combination due to incompatibility

02-Nov-16 23
Effect of chemical admixture on rheology of
cement system
• Polycarboxylic ethers (PCE’s) were capable retaining good workability
and slump life

02-Nov-16 24
Concluding Remarks
• Rheology and microstructural origin
• Rheological behavior of different materials
• Rheology of cement system
• Influence of chemical admixtures on rheology of cement system

02-Nov-16 25
References
[1] P. Coussot, Introduction to the rheology of complex fluids, in: N. Roussel (Ed.), Underst. Rheol. Concr., 1st ed., Woodhead
Publishing, Philadelphia, USA, 2012: pp. 3–22.
[2] W.P. Limited, Understanding the rheology of concrete, 1st ed., Woodhead Publishing, Philadelphia, USA, 2012.
[3] F.M. Lea, Rheology of cement paste, in: Chem. Cem. Concr., 3rd ed., Edward Arnold Publishers, Glasgow, Great Britain, 1970: pp.
364–366.
[4] F.M. Lea, Theories relating to portland cement, in: Chem. Cem. Concr., 3rd ed., Edward Arnold Publishers, Glasgow, Great Britain,
1970: pp. 253–260.
[5] N. Spiratos, M. Pagé, N.P. Mailvaganam, V.M. Malhotra, C. Jolicoeur, Superplasticizers for concrete, in: Suppl. Cem. Mater. Sustain.
Dev. Inc., Ottawa, 2003.
[6] R.J. Flatt, P. Bowen, Electrostatic repulsion between particles in cement suspensions: domain of validity of linearized Poisson–
Boltzmann equation for nonideal electrolytes, Cem. Concr. Res. 33 (2003) 781–791.
[7] C. Plassard, E. Lesniewska, I. Pochard, A. Nonat, Nanoscale experimental investigation of particle interactions at the origin of the
cohesion of cement, Langmuir. 21 (2005) 7263–7270.
[8] R. Flatt, Superplasticizers and the rheology of concrete, in: N. Roussel (Ed.), Underst. Rheol. Concr., 1st ed., Woodhead Publishing,
Philadelphia, USA, 2012: pp. 144–201.
[9] W.M. Danzinger, K. Saitoh, P. Jost, U. Maeder, New generation of admixture polymers and its role in concrete technology, in: G.
Grieve, G. Owens (Eds.), Proc. 11th Int. Congr. Chem. Cem., Durban, 2003: pp. 2271–2275.

02-Nov-16 26