Rheology and structure of COMPLEX FLUIDS

Jan Vermant Department of Chemical Engineering K.U. Leuven

Lecturer : Jan Vermant The material in this lecture is covered by some textbooks, some of them however being too limited, other ones being probably too detailed. For those among you who want to know more about rheology we advice the following books: Introduction to Rheology (Rheology Series) by H.A. Barnes, J.F. Hutton, K. Walters, Elsevier Science Ltd (1999-2nd edition) Rheology : Principles, Measurements, and Applications (Advances in Interfacial Engineering) by Christopher W. Macosko, Wiley-VCH (1994) The Structure and Rheology of Complex Fluids (Topics in Chemical Engineering) by Ronald G. Larson , Oxford Univ Press (1999)

For those of you who want to see what is available on the WWW, good starting places are: The rheology index, a list of rheology related web sites http://www.rheology.org/sorindex/default.asp The European Society of Rheology : http://www.rheology-esr.org/

What is Rheology??
= flow Rheology = The Science of Deformation and Flow
1920 : Eugene Bingham (Lafayette College)

Why do we need it? - measure fluid properties - understand structure-property relations - model behaviour - to predict flow behaviour of complex liquids under processing conditions

Rheology is defined as the science of deformation and flow. In principle, this definition includes everything that deals with flow, such as fluid dynamics, hydraulics, aeronautics and even solid state mechanics. However, in rheology we tend to focus on materials that have a deformation behaviour in between that of liquids and solids, i.e. with a funny material behaviors. The science of rheology started in the 1920s when polymers started to be produced, leading to novel polymeric substances and new colloidal fluids (e.g. paints). Hence the Newtonian fluid and the Hookean elastic solids are outside the scope of rheology and material behaviour intermediate to these classical extremes will be studied here. The term viscoelastic is used to describe this behavior. Some fluids are however essentially inelastic, but have a viscosity which changes with the deformation state, they are called Non-Newtonian fluids. Rheology is an applied science, and its aim is twofold: Firstly, rheologists try to understand the relation between structure and flow properties.This important for the intelligent design and/or formulation of materials for certain applications. Secondly, by studying the material behavior using simple deformations, fundamental relations will be derived between deformation and force. Such equations are called constitutive equations. These equations can then be used to predict the material behavior in complex deformation histories as they take place in typical process operations: e.g. extrusion, polymer film blowing, spraying, pumping etc.

1. Viscoelasticity
I - Silly Putty G(t) t>

t<

Polydimethylsiloxane + Borax
Dr. James Wright, a GE engineer, came upon the material by mixing silicone oil with boric acid. Peter Hodgson borrowed $147, bought the production rights from GE, and began producing the goo. He renamed it Silly Putty, and packaged it in plastic eggs because Easter was on the way. Peter Hodgson's product left him an estate of $140 million at his death in 1976.

Probably the best-known example of a material with a funny material is the so-called Bouncing or silly putty. When this material is rolled into a small ball and dropped on a surface, it will bounce. When it left to sit on a flat surface it will flow or like any liquid will take on the shape of the container that holds it. Depending on the time scale on which the deformations take place, the material will behave like either a solid (short times) or a liquid (long times). But most of the the time the material will show an intermediate behavior, displaying characteristic of a solid and a liquid at the same time. We will see later that we can describe this by a time-dependent modulus G(t). We will also learn how we can quantify to which extent a material is fluid or solid-like, by means of linear viscoelastic measurements. Like the modulus, the viscosity is also not always a constant. Three examples are given above. Mayonnaise is an example of a shear-thinning fluid. When it sits on a knife the only forces exerted on it are gravitational (low stresses) and the viscosity is high. When the mayonnaise is applied to a sandwich, it is being sheared at high stresses and the viscosity is low. The viscosity will be dependent on the rate at which the material is being deformed, and decreasing as the shear rate is increased. This is a behavior also typically encountered in polymers. Ketchup is an example of a material which will not flow below a certain stress level, called a yield stress. It also has a viscosity which, in addition is strongly dependent on the deformation history and changes its value in time, this phenomenon is called thixotropy and is sometimes encountered in suspensions. Concentrated dispersions can exhibit even different features : a viscosity which increases with the deformation rate. This behaviour called shear-thickening.

2. Non-Newtonian behaviour
II - Mayonnaise - Ketchup - Starch - Liquid Body armor

"( ! , t )

http://www.ccm.udel.edu/STF/index.html

Probably the best-known example of a material with a funny material is the so-called Bouncing or silly putty. When this material is rolled into a small ball and dropped on a surface, it will bounce. When it left to sit on a flat surface it will flow or like any liquid will take on the shape of the container that holds it. Depending on the time scale on which the deformations take place, the material will behave like either a solid (short times) or a liquid (long times). But most of the the time the material will show an intermediate behavior, displaying characteristic of a solid and a liquid at the same time. We will see later that we can describe this by a time-dependent modulus G(t). We will also learn how we can quantify to which extent a material is fluid or solid-like, by means of linear viscoelastic measurements. Like the modulus, the viscosity is also not always a constant. Three examples are given above. Mayonnaise is an example of a shear-thinning fluid. When it sits on a knife the only forces exerted on it are gravitational (low stresses) and the viscosity is high. When the mayonnaise is applied to a sandwich, it is being sheared at high stresses and the viscosity is low. The viscosity will be dependent on the rate at which the material is being deformed, and decreasing as the shear rate is increased. This is a behavior also typically encountered in polymers. Ketchup is an example of a material which will not flow below a certain stress level, called a yield stress. It also has a viscosity which, in addition is strongly dependent on the deformation history and changes its value in time, this phenomenon is called thixotropy and is sometimes encountered in suspensions. Concentrated dispersions can exhibit even different features : a viscosity which increases with the deformation rate. This behaviour called shear-thickening.

III. Weissenberg effect

N1

A spectacular example of elasticity in an fluid is the so-called Weissenberg or rodclimbing effect. When a rod is set to rotate in a Newtonian fluid, the inertial forces push the material to the outside of the container. In a visco-elastic fluid that is subjected to deformation stresses will develop along the normal axes of the flow field. In the case of a rotating rod, the stream lines are circular. If the normal stress in the circular direction of the flow is greater in magnitude than the two mutually perpendicular components, a tension in the flow direction results. These circular normal stresses that arise will strangle the material around the rod, pushing it up. The above photograph was prepared by dissolving a high molecular weight Polyisobutene (Oppanol B200) in a low molecular weight sample of the same chemical composition (From Boger and Walters, Rheological Phenomena in focus,Elsevier ,1993). Die-swell of a fluid is another phenomenon which is typical for viscoelastic fluids. The above photos compare the behavior of a Newtonian material with a polymeric fluid exciting from a die. The ratio of the diameter of the jet to the capillary diameter is 113% for the Newtonian case (low Reynolds number) whereas it can be as high as a few 100% for the case of polymeric fluids. This is a very important phenomenon when extruding products. The die-swell will need to be accounted for (think about how you would make a square duct by extrusion). Again the die swell arises mainly because of differences in the normal stresses along and perpendicular to the stream lines in the tube. They relax as the fluid exists from the tube causing a contraction in the longitudinal direction. In the above pictures the Reynolds number is 0.001. The fluid on the top is a Newtonian oil, the second fluid is an elastic fluid prepared in the same manner as discussed previously (From Boger and Walters, Rheological Phenomena in focus (Elsevier 1993).

IV. Die Swell

Weissenberg effect

McKinley et al (MIT)

N1

A spectacular example of elasticity in an fluid is the so-called Weissenberg or rodclimbing effect. When a rod is set to rotate in a Newtonian fluid, the inertial forces push the material to the outside of the container. In a visco-elastic fluid that is subjected to deformation stresses will develop along the normal axes of the flow field. In the case of a rotating rod, the stream lines are circular. If the normal stress in the circular direction of the flow is greater in magnitude than the two mutually perpendicular components, a tension in the flow direction results. These circular normal stresses that arise will strangle the material around the rod, pushing it up. The above photograph was prepared by dissolving a high molecular weight Polyisobutene (Oppanol B200) in a low molecular weight sample of the same chemical composition (From Boger and Walters, Rheological Phenomena in focus,Elsevier ,1993). Die-swell of a fluid is another phenomenon which is typical for viscoelastic fluids. The above photos compare the behavior of a Newtonian material with a polymeric fluid exciting from a die. The ratio of the diameter of the jet to the capillary diameter is 113% for the Newtonian case (low Reynolds number) whereas it can be as high as a few 100% for the case of polymeric fluids. This is a very important phenomenon when extruding products. The die-swell will need to be accounted for (think about how you would make a square duct by extrusion). Again the die swell arises mainly because of differences in the normal stresses along and perpendicular to the stream lines in the tube. They relax as the fluid exists from the tube causing a contraction in the longitudinal direction. In the above pictures the Reynolds number is 0.001. The fluid on the top is a Newtonian oil, the second fluid is an elastic fluid prepared in the same manner as discussed previously (From Boger and Walters, Rheological Phenomena in focus (Elsevier 1993).

V. Entry flows : vortex enhancement

N1, e

In more complex flows, the material characteristics will strongly alter the flow fields. The above pictures are examples of flow-visualization of a contraction flow at different flow rates. As the flow rate is increased, the fluid behaves more and more as a elastic material. The Deborah number, which compares the characteristic time of the process to the characteristic relaxation time of the fluid, hence expresses how important elasticity will be. As the Deborah number is increased, Vortices are enhanced. These vortices can even become unstable and start to swirl in the die. Two often related aspects are important in entrance flow, the normal stresses and the elongational viscosity. The fluid used in the experiments was a solution of 0.04% High Mw polyacrylamide in a water/corn syrup mixture. This fluid is a so-called Boger Fluid, which has an essentially shear rate independent viscosity and a pronounced elasticity. The Reynolds number in the above experiments were small, ranging from 0.0005 to 0.02. The Deborah Number was 0.08 and increased to 0.2. If the flow rates are increased further, the vortices become unstable and dance in the barrel, causing unstable flow. This is not related to turbulence, but is an instability due to the elastic nature of the fluid.
The above pictures are from : D.V. Boger, D.U. Hur, R.J. Binnington, J. Non-Newt. Fluid Mechanics, 20, 31 (1986) .

VI : Ductless Syphon

Tubeless syphon

McKinley et al (MIT)

D. Joseph and coworkers (UMinn)

When a liquid containing large macromolecules or high aspect ratio particles is stretched the molecules and/or particles are aligned in the direction of stretching resulting in a substantial increase of the resistance to flow. The elongational viscosity can be many times higher as compared to the shear viscosity, especially at high deformation rates. The above pictures show the open or ductless-syphon effect. The slightest spilling will empty the beaker. When an initial thread of the material has been drawn over the side the beaker empties itself. The material in the above experiments is an aqueous solution f a water soluble polymer (polyox WSR301) in water. (From Boger and Walters, Rheological Phenomena in focus,Elsevier ,1993).

VI : Reduction of Misting

Elongational viscosity and elasticity of fluids can also be important in high Reynolds applications, for example the break-up of a jet from a nozzle. The picture on the left is for Water. The picture on the right is for a 200 ppm (!) solution of a high molecular weight solution of a high Mw polyethylene oxide. (from JW Hoyt and JJ Taylor, Phys. Fluis, 20 S253 (1977)). This is e.g. important in spraying or coating applications. Another example of the same effect relates to drag reduction in turbulent flow.

Aim of this lecture:

1. Qualitative insight of the behavior of non-Newtonian fluids. 2. Discuss measurement techniques for a given problem 3. Demonstrate link rheological properties // microstructure

10

Rheology

Finite Deformation Tensors

We now have a way to determine the state of stress in a material. Now we need a similar three-dimensional description of the state of deformation in a material. Relating stresses and deformations leads us to the constitutive equations that we are looking for. How do we proceed? Do we look to describe all the velocities in a fluid? This is of not much use (fortunately)- we need the relative deformations. At the end of this session we should have a description for: - deformations (relative) - deformation gradients Lets keep this in mind: If we write Hookes law in three dimensions, with the stress and strain being proportional, the deformations tensors should be such that rotations do not give rise to a stress. Likewise we will try to see if we can write Newtons law in three dimensions.

11

1. Deformation gradient tensor:

y

dx' x z dx

Uniaxial elongation dx = F.dx

Consider a cube of material as drawn above. Two points in that body are separated by a vector dx at time t . Now let the body be deformed to a new state, e.g. the deformation given above is a uniaxial elongation. The two points will move with the body and the displacement vector between them will be stretched and rotated as indicated by a new vector dx. Now we wish to relate dx (the present state) to dx (the rest or past state at t). This will be given by another linear transformation, called the deformation gradient tensor F. Just as the stress tensor describes the force acting on any plane, the deformation gradient tensor relates the state of deformation and rotation for any material point. For the example of uniaxial elongation stresses will develop along the normal axis of a piece of e.g. rubber. Keeping in mind Hookes law, we hence know what to expect for the deformation tensor (which components will be non-zero?).

12

Simple shear
S

! = s/h

Solid body rotation

"

Above are two other simple deformations which can be given to bodies. They are a bit more critical to check whether or not we have a good deformation measure: The simple shear deformation will lead to shear stresses, and again based on Hookes law (proportional) now know to expect shear components in the deformation measure. By the symmetric nature of the stress tensor, both the xy and yx components should also be present in a suitable deformation tensor. Likewise, a solid body rotation forms another critical test. Material elements are not stretched, only rotated and no stresses should develop. A suitable deformation measure should hence yield the identity tensor for this type of deformation Now is F a good measure for deformations?

13

! (x # (x' # (y F=# (x' # # (z " (x'

(x (y ' (y (y ' (z (y '

(x $ (z'& (y & (z'& (z & & (z'%

Deformation gradient tensor

uniaxial extension x = )x' y = ) '1/ 2 y' z = ) '1/ 2 z' 0 0 $ !) F = # 0 ) '1/ 2 0 & # '1/ 2 & 0 ) "0 %

Simple shear x = x'+ 'y' y = y' z = z' ' ! 1 ' 0$ F = # 0 1 0& # 0 0 1& " %

Solid body rotation x = x'! cos ) " y'! sin ) y = x'! sin ) + y'! cos ) z = z' ' # cos ) " sin ) 0& ( F=% % sin ) cos ) 0( 0 1' $ 0

If we look at what F evaluates to for a uniaxial elongation, we can be satisfied. When we look at either simple shear or a solid body rotation, however, we see that we are in trouble: F is not always symmetric! F is not zero for a solid body rotation! F is hence not a good deformation measure for our purpose. It describes both rotation as well as a shape change. Somehow we must eliminate this rotation. The material response is determined only by the amount of stretching, not by a solid body rotation.

14

2. The Finger tensor:

Remove the rotation: multiply F by its transpose

Simple shear

C-1 = F.FT

1 + ) 2 ) 0% " 1 ) 0% " 1 0 0% " $ ' C!1 = $ 0 1 0' ( $ ) 1 0' = $ ) 1 0' ' $ $ 0 0 1' $ # & # 0 0 1& # 0 0 1' & Uniaxial elongation
!1

" *2 0 0 % $ ' !1 =$ 0 * 0 ' $ 0 0 * !1' # &

We know from matrix algebra that multiplying a matrix by its transpose, yields a symmetric matrix. Can we, by doing this also remove the rotation and get a symmetric tensor? We can express the deformation gradient F as a product of both a stretch and a rotation. F= V.R. as a rotation followed by an inverse rotation gives I: F.FT = V.R.RT.VT = V.VT The dot product of F with its transpose is called the Finger Tensor, and it is a good deformation measure. Note that other deformations measures are possible e.g. FT.F. The physical meaning of the Finger tensor is that it relates the change in area within the sample.

The good news is now that we can write Hookes law in 3D! =GC-1

15

2. The Finger tensor:

Remove the rotation: multiply F by its transpose

Simple shear

C-1 = F.FT

1 + ) 2 ) 0% " 1 ) 0% " 1 0 0% " $ ' C!1 = $ 0 1 0' ( $ ) 1 0' = $ ) 1 0' ' $ $ 0 0 1' $ # & # 0 0 1& # 0 0 1' & Uniaxial elongation
!1

" *2 0 0 % $ ' !1 =$ 0 * 0 ' $ 0 0 * !1' # &

We know from matrix algebra that multiplying a matrix by its transpose, yields a symmetric matrix. Can we, by doing this also remove the rotation and get a symmetric tensor? We can express the deformation gradient F as a product of both a stretch and a rotation. F= V.R. as a rotation followed by an inverse rotation gives I: F.FT = V.R.RT.VT = V.VT The dot product of F with its transpose is called the Finger Tensor, and it is a good deformation measure. Note that other deformations measures are possible e.g. FT.F. The physical meaning of the Finger tensor is that it relates the change in area within the sample.

16

3. Neo-Hookean Solid:
Using the Finger tensor we can come up with a general form of Hookes law
Simple shear

= G . C-1

$1 + # 2 $ 1 # 0' $ 1 0 0' ! = G.C = & 0 1 0 ) * & # 1 0 ) = G.& # & & ) & ) & % 0 0 1( % 0 0 1( % 0
"1

# 0' 1 0) ) 0 1) (

! xy = G#
Uniaxial elongation $+ 2 0 0 ' ! = G.C = G.& 0 + "1 0 ) & ) & 0 + "1 ) % 0 (
"1

! xx = " p + G+ 2 =

G " G (1 + , )2 1+ , 3, + 3, 2 + , 3 =G - 3, G = E, 1+ ,

The good news is now that we can write Hookes law in 3D! =GC-1 Actually Hooke observed the proportionality between force and stress for a springy body as early as 1678 and it took almost 150 years to formulate this model in 3D. For an incompressible solid, the above calculation shows the link between the shear modulus G and Youngs modulus E. For compressible materials, a Poisson-coefficient needs to be used. For more details we refer to the textbook by Macosko or the course Sterkteleer.

17

4. Velocity Gradient:

" )v x )v x )v x % $ )x )y )z ' $ )v y )v y )v y ' !v = $ ' $ )x )y )z ' ) v ) v ) v z z' $ z # )x )y )z & uniaxial extension !x vx = * ! (* vy = y 2 ! (* vz = z 2 " $* ! $ !v = $ 0 $ $0 # 0 ! (* 2 0 % 0 ' ' 0 ' ' !' (* 2&

The velocity gradient tensor describes the steepness of the velocity variation as one moves from one point to the other. This tensor has again two directions associated with it : one of the velocity and one of the gradient. It operates on a local displacement vector to to generate the magnitude and direction of the changes in the velocity. For the case of uniaxial elongation, it seems to give a good deformation measure. But once again, solid body rotations and shear flows are more critical tests.

18

Simple shear !y vx = ( vy = 0 vz = 0 ! " " 0 ( 0% !v = $ 0 0 0 ' $ 0 0 0' # &

no slip

y U d

x U linear velocity field: u x = ---y d

stretching

rotation

Lets consider the case of steady state shear flow. Again, we want the deformation measure we use to yield a symmetric tensor in order to write our constitutive equations. The kinematics of simple shear flow can be obtained by taking the time derivatives of the displacement functions of simple shear we have used before. We see that the velocity gradient tensor is not symmetric! Like the deformation gradient F, the velocity gradient tensor contains both rotation as well as stretching. A steady state shear flow can be viewed as a combination rotation and stretching. We can remove the rotation from the velocity gradient by recalling that we could decompose F in terms of a stretch and rotation F= V.R if we differentiate this with respect to time:

! =V ! !R + V !R ! F lim V = lim R = I x'" x x'" x ! = #v = V ! +R ! lim F x'" x !T = V ! +R ! T lim F x'" x ! = 2D = (#v)T + #v V

19

5. Rate of Deformation Tensor

2D = (!v) + (!v)
T

uniaxial extension D= (" ! 0 0 1 *$ . ! /2 0 !. 0 2 *$ ! /2 0 !. )# 0 % ". ! ! 0 0 % + ". 0 0 % ' + $ 0 !. ' - = $ 0 !. ! ! / 2 0 / 2 0 ' $ ' $ ! / 2' ! / 2' 0 !. 0 !. &- #0 & & #0 ,

Simple shear 1 ! ! 0$ # 0 & 2 & ! 0 0 0$ * # 1 ! 0 0& , = # ! 0 0& + ## & #2 & " 0 0 0% , + # 0 0 0& # & " %

D=

! 0$ ' 0 1 )! # 0 0 0& 2 )# 0 0 0& % ("

Hence we obtained a new tensor 2D, which should be symmetric as is checked above for the two types of deformation : uni-axial extension and shear flow. As can be seen above, we again obtained a good measure to look at deformation rates - it is symmetric in shear flow and you can check for yourselves that it yields I for a solid body rotation.

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General Newtonian Constitutive Equation

In the Newtonian model, the stress is assumed to be proportional to the shear rate with viscosity being the proportionality constant. Since the stress tensor is symmetric, it should be related to the rate of strain, D, and not the velocity gradient tensor.
! = 2 (D 1 " ! 0% ) $ 0 ' 2 $1 ' ! 0 0' ! = 2($ ) $2 ' $ 0 0 0' $ ' # &
y U d

no slip

x U linear velocity field: u x = ---y d

We now have derived all the tools that we need to extend Newtons law in three dimensions. Note that the above equations relate the extra stress tensor and the rate of deformation tensor. When we write the equation in its components for simple shear flow, we find the definition that we know from e.g. transport phenomena or hydraulics. The Newtonian constitutive equation is the simplest equation there is for viscous liquids and forms the basis of fluid mechanics. When you are faced with a new problem, this model will be the best place to start. Fluids which obey Newtons law are e.g. low-molecular weight liquids, dispersions at small volume fractions of dispersed phase, but even high Mw polymers at low deformation rates

21

uniaxial extension ! 0 0 % "( ! /2 0 ' D=$ $ 0 !( ! / 2' # 0 0 !( & ! ! =( + ) = 2 *D ! )11 = !p + 2 *( ! ) 22 = ) 33 = !p - *( ) ! ) 22 *e = 11 ! ( *e = 3 *

TROUTON ratio

The above calculation shows the value of using the tensor form of Newtons law. The result that the extensional viscosity is three times the shear viscosity is also observed for polymer melts at low rates. It is actually often used to check the validity of results of elongational rheometry and we will probably come back to this.

22

Linear Viscoelasticity

In this chapter we will see one of the most important aspects of rheology: the description of linear viscoelasticity. Linear viscoelasticity is important for a number of reasons: It is an important goal of rheology that we are able to describe and characterize material behavior that is intermediate between solid and liquid behaviour. The linear regime is important because it is the building block for further work: how complicated the non-linear regime might be, we should always find the linear viscoelastic behavior as a limiting case. Last but not least linear viscoelasticity is of practical importance: For example for linear polymer chains, measurements characterizing the linear viscoelastic properties provide insight in to how the material will behave in some non-linear flows. At the end of this chapter you should be able to: define linear viscoelasticity. understand it from an energetical point of view. be able to describe linear viscoelasticity mathematically know which properties can be determined experimentally and how they are interrelated : relaxation modulus, compliance, storage and loss modulus and relaxation spectrum

23

What are viscoelastic fluids? = fluids with a finite memory !

Memory =

Real fluid/solid

Memory =

The memory point of view: Viscoelastic fluids are defined as fluids which have a finite memory. The two material classes we have worked with up to now; the perfect solid (Hookes law) and the perfect liquid (Newtons law) do not obey this definition. A perfect solid will remember the deformation indefinitely and return to its initial shape. A perfect liquid will stop deforming instantaneously when the stress is removed and never recover to its previous shape. All real fluids and solids show intermediate behavior. I cannot recuperate the energy that I put into a deformed solid. There will always be some internal dissipation of energy. For example car tyres heat up during driving, not soo much due to the friction, but due to the internal heat dissipation.

24

What are viscoelastic fluids? = fluids that store and dissipate energy !

Energy storage

Energy dissipation

Real fluid/solid

The energy point of view:

When we apply a stress and a body is deformed, this implies that workis being defined as force x deformation, is done. The perfect solid will store this energy. According to Hookes law, the potential energy "

! xy xy cannot be dissipated. If a perfect body would be deformed by a certain deformation g, and subsequently it 0 liquid on the other dissipates all the would be released, it would oscillate indefinitely (in vacum). A perfect energy , to keep the fluid going I need to put energy into the fluid.
All real fluids have a finite memory. Even water has a time constant of about 10-12 s. Deformed slower than that it will flow, deformed more rapidly it will behave as a solid. Some materials have time constants on the order of 1017s. Most polymeric liquids will have time scales which are on the order of 10-3 to a few seconds. In addition , they will often show a wide distribution of relaxation times. Whether or not you have to take viscoelasticity in to consideration when designing a process or product will depend on the time scales of the product and the process.

E = # d"

25

1. Viscoelastic phenomena : 1.a. CREEP

Compliance

J( t) =

! ( t) "0

The inverse of the creep experiment is an experiment were a strain is suddenly applied and the resulting stress is measured. Either the a constant strain rate can be applied or a a constant strain is suddenly applied. The stress in a viscous (Newtonian) liquid (VL) will drop to zero instantaneously. The elastic solid (ES) reacts to a constant strain by an instantaneous stress that remains constant in time. What happens with a VE fluid in a stress relaxation experiment? As the name of the experiment suggest, the stress gradually relaxes. We can convert this data into a RELAXATION modulus . Note that the above examples are for shear deformations but the concepts and models we discuss can be applied to other types of deformations. But because we are dealing with small strains, typically only shear deformations are of interest. Questions : Stress relaxation experiments are not always in the linear response regime. Think about what condition needs to be satisfied for a step strain experiment to be a linear measurement.

26

1.B. stress relaxation

fast

Apply strain

Relaxation modulus

G( t) =

!( t ) "

The inverse of the creep experiment is an experiment were a strain is suddenly applied and the resulting stress is measured. Either the a constant strain rate can be applied or a a constant strain is suddenly applied. The stress in a viscous (Newtonian) liquid (VL) will drop to zero instantaneously. The elastic solid (ES) reacts to a constant strain by an instantaneous stress that remains constant in time. What happens with a VE fluid in a stress relaxation experiment? As the name of the experiment suggest, the stress gradually relaxes. We can convert this data into a RELAXATION modulus . Note that the above examples are for shear deformations but the concepts and models we discuss can be applied to other types of deformations. But because we are dealing with small strains, typically only shear deformations are of interest. Questions : Stress relaxation experiments are not always in the linear response regime. Think about what condition needs to be satisfied for a step strain experiment to be a linear measurement.

27

LDPE

[Laun, Rheol. Acta, 17,1 (1978)]

The figure shown above contains the relaxation modulus for a low density polyethylene at 150C (data from H.M. Laun, BASF, Rheol. Acta 1978). Data at two different strains are shown. Note that the time scale over which the modulus decreases expands up to a few 100 s!!! So this material has considerable memory for the applied deformation. The data is represented on a log-log scale. The modulus decreases rapidly, but it is not a single exponential decrease. Remark: Come back to this figure at the end of this chapter: then you will understand that the line in the figures represents a fit to eight exponential relaxation times.

28

1.C. Sinusoidal oscillations

STRAIN: ! = ! 0 sin("t ) ! = ! 0 exp(i"t ) STRAIN RATE ! = ! 0 " cos("t ) = ! 0 sin("t + 90 ) ! = i "! 0 exp(i"t ) HOOKEAN SOLID # = G! = G! 0 sin("t ) # = G! 0 exp(i"t ) NEWTONIAN FLUID ! = $! 0 " sin("t + 90 ) # = $! # = $i! 0 " exp(i"t ) = $i!"

The creep experiments are especially suited for the long time scales. The stress relaxation experiments can access time scales between 0.1 (because of transducer resolutions) and a few 100 s. So we need other types of experiments in which the time scale can easily be varied. The small strain oscillatory measurements present us such a tool! The sample is deformed sinusoidal. After a few cycles of start-up, the stress will also oscillate sinusoidal. For a Viscous Liquid (VL) and an Elastic Solid (ES) the response can be easily calculated by invoking the appropriate constitutive equations. From the above equations it can be seen that the stress in an ES will oscillate IN PHASE with the applied deformation, whereas for a VL the stress will be DEPHASED by 90 with respect to the oscillatory deformation. Again, we found a way to compare a elastic solid and a viscous liquid. Note also that for the VL the stress amplitude will depend on frequency whereas for an ES it will not!

29

VISCOELASTIC MATERIAL ! = ! 0 sin("t + # ) ! = ! 0 exp(i"t + # ) complex mod ulus: ! = G &$ ! = G & $ 0 sin("t + # ) ! = G & $ 0 [sin("t ).cos(# ) + cos("t ).sin(# )] ! = G & cos(# ) % $ 0 sin("t ) + G & sin(# ) % $ 0 cos("t )

! = [G '% sin("t ) + G "% cos("t )]$ 0 ! = (G '+ iG " )$

Storage and Loss modulus

tan ! =

G' ' G'

Now what do we get for a VE liquid: The total stress can be viewed as the combination of in part a viscous and in part an elastic component, resulting in a complex modulus with a real elastic part, and an imaginary (viscous) part The stress response will be dephased by an angle . This angle will be a measure for how elastic or how viscous my fluid is. If the fluid is viscous the phase angle will tend to 90. When the fluid is dominantly elastic, the phase angle will tend to zero. The phase angle is hence a nice way to characterize the material on a viscoelasticity scale. It is convenient to analyze the stress wave into two waves, one in phase and the other one out of phase with the strain wave. This decomposition suggest the existence of two dynamic moduli: G the in-phase, elastic or storage modulus G the out-of-phase, viscous or loss modulus. Hence we see the definition of VE in terms of energetic behaviour reappearing from this experiment. The figure on the right shows oscillatory data on the same LDPE as shown before in a creep experiment. We will try later to calculate the creep from the dynamic moduli (a nice feature of linearity all Linear viscoelastic functions are interrelated)

30

Newtonian MATERIAL ! # = %" # = [G '! sin($t ) + G"! cos($t )]" 0 # = ( G" ) " G" = G = Loss modulus

tan ! = ? !=?

Elastic " (Hookean) MATERIAL $ = G# $ = [G '! sin(%t ) + G"! cos(%t )]# 0 $ = (G ' ) # G' =

tan ! = ? !=?

For a Newtonian liquid: G is known as the viscous loss modulus. It characterizes the viscous contribution to the stress response. What is the phase angle in this case? For an Elastic material : For Hookean solids, stress is proportional to strain and we find another limiting result G is thus known as the elastic storage modulus. It characterizes the elastic contribution to the stress response. Remind yourseld : what is the phase angle in this case?

31

VISCOELASTIC MATERIAL ! = ! 0 exp(i"t + # ) complex vis cos ity : ! ! = $3 % ! = ( $'+ i$" )i"% = ( $"& i$')"% $' = $" = G" " G' "
1/ 2

-' G '* 2 ' G "* 2 0 $3 = /) , + ) , 2 ( + ("+ 2 / . " 1

1 3 G "

Another way to view the experiments is in terms of of a sinusoidal strain rate. This leads to the definition of a dynamic viscosity. This is also a material function. We can now define a dynamic viscosity for the magnitude of the viscous stress to the strain rate and an elastic part of the dynamic viscosity . The typical low frequency behaviour for the materials function for polymer melts and solutions is sketched in the above graph (A). It shows a plateau modulus G0 and decreases with 2 for G and proportional to for G at low frequencies. This is an important feature to check when doing measurements. For rubbers (fig: B) on the contrary G is essentially constant over the entire frequency range.

32

Mirror relation

Terminal zone :

Time (s)

When the frequency range for a polymer melt is extended, we find again the behaviour that is known from the courses on polymer science. The different regions are indicated on the graph. The graphs on the right hand side also indicate the link between dynamic moduli and the relaxation modulus. In an oscillatory experiment, the sample is interogated at each frequency. The relaxation modulus corresponds to an integral over the spectrum of relaxation times : i.e. at short time all modes contribute to the stress, whereas some start to relax as time increases. For a VE liquid the limiting relations for the terminal zone, shown above should always be true when the material is tested in the linear viscoelastic regime. Hence such relations are extremely useful for testing the internal consitency of data. You can use the relations above to check whether data from different types of experiments agree and even if data from non-linear experiments gives in the limit for vanishing shear rates the VE result.

33

Effect molecular weight on the LV moduli of polymer melts

The above graphs show the dependence of the moduli on molecular weight for a set of monodisperse PS polymer melts. These results point us to an application of rheology as an analytical tool : LV measurements will give us detailed information about the distribution of molecular weigths. To do this well need to develop a theoretical description. Even than theres a catch : the calculation of the molecular weight distribution is an example of an inverse problem (and hence intrinsically and often numerically difficult).

34

Effect of volume fraction on the dynamic moduli of dispersions

104

! d 2* $ # 2& " dr % 5+ ! G ') 6, c $ F( r ) = = ( # & d c ' kT 0.639 N " kT +d 3 c%

"c 0.421 0.426 0.437 0.452 0.455 0.471 0.482 0.502 0.515 0.534

10

102

101

: pairwise interaction potential N : coordination number (7.5) G: high frequency modulus dc : particle core diameter c : core volume fraction
!(r)/kT !d/kT

100

The above graphs show the dependence of the storage modulus on frequency and volume fraction. Again an application of the linear viscoelastic measurements arises : we will be able to use rheological measuremenbts to characterize the interactions between particles. As we will see in the chapter on microrheology of dispersions, we will make use of rheology as a sensitive measurement technique to asses dispersion stability and predict the (non-linear) viscosity curves.

G' (Pa) G"(Pa)

10

-1

10-2 10-2

10-1

100

101

102

! (rad/s)

!(r)/kT r

35

2. Differential models : The Maxwell model

Phenomenological models Hookean Spring

! 1 = G" 1
Newtonian Dashpot

Maxwell

Kelvin-Voight

!2 !2 = " $ #

Lets now try to describe the dual nature of these fluids and solids by simple mathematical models. We can start from simple phenomenological tools. A Hookean spring will be our model for a perfect solid. A dashpot will be our conceptual model for a perfect fluid. We can now start combining these elements in parallel or in series and so on. We could as well draw an analogy on electrical elements, using resistors and capacitances. Maxwell (1867) first proposed the in series model for the viscosity of gases. Question : from the above cartoons, which one will be the best for describing a fluid? Which one will describe a solid?

36

Maxwell model = VE Fluid two elements in series

! = !1 + ! 2 " = "1 = " 2 ! = !1 + ! 2 != ! 1 "2 " + G0 #0

%# ( ! = #0 ! " + ' 0 *" & G0 ) ! = #0 ! " + $"

= relaxation time

Now lets assume we take the Maxwell model, using the elements in series. When we apply a deformation to this model the total deformation will be split by both elements. The stress in both elements is the same and equal to the total stress. Assuming a homgeneous deformation, the deformation rate can also be assumed to consist of a sum of the two individual motions. We can then rewrite the equations, leaving us with a differential equation. This differential equation is know as the MAXWELL model; In the next few pages we will try to see if this model can capture some of the observed phenomena of linear viscoelasticity.

37

Relaxation (Step strain) experiments for a Maxwell element

12 G0

! = !0 t $ 0 "+# d" =0 dt

10

8 " 6

G(t)
4

t = 0; " = G0 ! 0 "(t ) = G(t ) = G0 % exp( &t / #) !

0 0.01

0.1

10

! [rad/s] Time (s)

Fading memory

Lets first calculate the response of the Maxwell model to a step in strain. As boundary conditions we impose the strain of g0 at times > 0. We can easily calculate the stress at time zero (purely elastic response) and solving the differential equation gives use the time evolution of the stress and of the relaxation modulus. The full line on the curve gives the predictions of the above equations for a G0 of 10 Pa and a relaxation time of 1 s on a semi-logarithm plot. In reality, a single exponential is not always observed (remember the relaxation curve for the LDPE we showed previously). The dotted line shows a more gradual evolution of the relaxation modulus. We will see how we can modify the Maxwell model to take into account this behaviour.

38

Dynamic moduli

10

G0

G '(! ) = G "(! ) =

G0 ! 2 " 2 1+ ! " G0 !"

2 2
0.1

Moduli [Pa]

1 + ! 2"2

0.01 G' G" 0.001 0.01 0.1 1 10 100

w [rad/s]

Likewise you can calculate the response of a Maxwell model to an oscillatory strain. It is most easily done by using complex notation. What you can easily see from the evolution of the moduli is that for frequencies smaller than the inverse of the relaxation time, a dominantly viscous response is observed. This can be extended to all processes with slow motions indeed the dashpot or Newtonian behavior will dominate. At high frequencies the elastic behavior dominates. For rapidly changing stresses in general, the derivative term in the Maxwell model equation dominates and at short times this model then approaches elastic behavior.

39

Do Maxwell Fluids exist?

Water oil emulsion

Concentrated surfactant solution

Do Maxwell fluids exist? Well at least some fluids do behave according to the simple maxwell model, at least to a good approximation. These are fluids in which one very dominant relaxation mechanism exists. Two examples are given above: Emulsions : here the VE comes from the interface, the material now can store elastic energy as the droplets, which have an interfacial tension, can deform. The relaxation time of these fluids is determined by the medium viscosity, the droplet size and the value of the interfacial tension. When the droplets are fairly uniform in size, the system will respond with essentially one single relation time. The graph on the left compares two emulsions which were subjected to different mixing histories. Surfactants : A lot of shampoos come relatively close to being Maxwell fluids! Such surfactants can form - in a certain range of concentration - rodlike micellar objects. These objects are sometimes called Living Polymers as they resemble polymeric fluids but they can break and reform without too much effort. The characteristic time scale of these systems is the breaking or reconnection time.

40

Can we describe polymer melts?

As we already indicated a single exponential is not always observed. The relaxation curve for a PDMS sample is shown above and the LDPE was shown previously. We will see now we can modify the Maxwell model to take into account this behavior. Come back to this page and explain what the right hand side graph means.

41

Generalized Maxwell model

!TOT = % ! i
i

! i = #i $ ! !i + "i ! G(t ) = % G0 i exp( &t /" i )

i

Jeffreys model
! d$ ! = #% ! + "2 ( ! + "1! '$ * & dt )

An obvious way to generalize the Maxwell model is to allow for multiple relaxation times. This can be done by considering multiple dashpot-spring combinations in parallel. In this manner, several relaxation times are available to fit our experimental data. The relaxation data of the PDMS on the previous page could be described by selecting a set of relaxation times equidistantly spaced on a logarithmic axis and determining the Gks for the different modes by a linear regression analysis. (k = 0.01, 0.1, 1, 10, 100 s, Gk=2*105 , 105, 104,102,10) . Some molecular theories, like the Rouse theory for polymer dynamics (see later) suggest an infinite series of relaxation times where only two fit parameters remain.

Gk = G0 "k = "O k2

"k ! "k
k

42

3. General viscoelastic Integral model

&(t ) = $ G(t ! t ' )'%(t ' ) &(t ) = # G(t ! t ' )d%(t ' )
!" t t

&(t ) = # G(t ! t ' )

!"

d% dt ' dt '
fluid
t

&(t ) = G(0)%(t ) ! G(")%( !" ) !

Reference state @ t=0

!"

# %(t ' )dG(t ! t ' )

&(t ) = # M (s )%(s# )ds

0

! (t ) = $ M (s )" (s )ds

s = t ! t'

M (s ) = memory function =
M (s ) =

s =t !t'

dg(s ) is the memory function ds

dG(s ) ds

An arbitrary evolution of deformation in time can be approximated by a series of stepwise changes . If we assume that the stress a time t resulting from the given motion equals the sum of the partial stresses at time t from the individual strains at time (t) (this is what is called the linearity or Boltzman principle), the total stress can be calculated as indicated above. When the steps are taken to be infinitesimally small, the summation becomes an integration. Note that in rheology it is customary to use the configuration at time t as the reference. The equation can then be transformed by an integration by parts. Noting that G()=0 for fluids and is finite at time t = that (t)=0 is a reference for the deformation.

43

What is the relaxation function?

For a simple Maxwell model we used a single exponential

G(t ) = G0 exp( !t / +)
For a generalized Maxwell fluid this becomes

G(t ) = " Gi exp( !t / + i )

We can replace the discrete relaxation times by a continuous spectrum
* # !t & G(t ) = ) F ( +) exp% ( d+ $ +' 0

Often one use a logaritmic scale : the relaxation spectrum is defined as follows
* # !t & d+ G(t ) = ) H ( +) exp% ( $ +' + 0

Powerful way to characterize materials - albeit in the Linear region

The use of G(s) does not lead directly to a specific equation for the stress relaxation function. Specific expressions can be developed. By using a simplest expression is a single exponential decrease. In this manner we obtain the integral formulation of the Maxwell model. The integral form of the generalized Maxwell model can be easily obtained by using the relaxation spectrum as defined above. By using a relaxation spectrum, any arbitrary relaxation function can be fitted accurately in a unique manner. This provides a very powerful tool to characterize the rheological behavior of polymers. The relaxation spectrum allows one to obtain a dynamic fingerprint of the behavior of polymers. For linear polymers, the relaxation spectrum can be linked to the molecular weight and the molecular weight distribution.

44

Oscillatory flow

G and G from the general linear viscoelastic fluid:

! = ! 0 " cos("t ) # = ' G(t $ t ') % ! 0 " cos("t ')dt

$& t

= ! 0 " ' G(s ) % cos("t $ "s )ds

0

&

= ! 0 " ' G(s ) % cos("s )ds cos("t ) $ ! 0 " ' G(s ) % sin("s )ds sin("t )
0 0

&

&

G " = " ' G(s ) % cos("s )ds G ' = " ' G(s ) % sin("s )ds
0 0 &

&

For all linear viscoelastic materials, the shear stress is expected to be a sinusoidal function when a sinusoidal strain is applied. The above calculation demonstrated how the response for an arbitrary linear viscoelastic fluid can be calculated (continued on the next page). The only mathematical tool we use is that cos(a+b)=cos a.cos b + sin a . sin b

45

( ( N " % G " = , * G(s ) ! cos(,s )ds = , * $ + Gi e ) - i s ' ! cos(,s )ds & 0 0 # i =1

i =1

+ Gi
( 0

,- i 1 + (,- i ) 2

G ' = , * G(s ) ! sin(,s )ds =

i =1

+ Gi

(,- i ) 2 1 + (,- i ) 2

Weve assumed the relaxation spectrum to consist of a discrete spectrum of relaxation times. The equations that we have obtained were actually used to describe the moduli of the LDPE by Laun [Laun, Rheol. Acta, 17,1 (1978)]

46

Oscillatory flow

!'(" ) = ? !'(" ) = = G" "

Complex viscosity

1, . G(s ) $ " $ cos("s )ds "0

s 1 , %, H ( # ) - # ( $ e d# * $ " $ cos("s )ds '. . " 0 '0 # * & ) ,

' . $e . 0 # ' &0

H ( # ) %,

s #

( cos("s )ds * $ d# * )

%, ( b + ' . $e - bt cos(at )dt * = 2 for b > 0 2 &0 ) a +b

!'(" ) =

H ( #) d# 1 + ("#) 2 0

Here we give another example how a VE function, in this case the complex viscosity can be calculated. This time we have used a spectrum rather than a discrete set. You can try to show the what the equation becomes for ()

47

Some relations between viscoelastic functions

G( t) = 2 # G' % ' ! sin('t)d' &0'

( = % H( )))d ln )
$#

(=

2 # G'(' ) d ln ' % & $# '

H( )) "

dG' 1 d2 G' + d ln(' ) 2 d(ln ' )2 1/ ' = ) /

The relaxation spectrum also gives us a tool to interrelate the different viscoelastic response functions. The different response functions can hence be calculated from each other. This can be either time saving or can be used to verify the internal consistency of experimental data. Combining data from different types of experiments can also be used to calculate the relaxation spectrum (it is an ill-defined mathematical problem).

48

Conclusions Defined and described linear viscoelasticity. Using rheology as a spectroscopic technique!
MATERIAL FUNCTIONS : Our goal is to obtain constitutive relations for our fluids as this is too difficult for a complex flow - we try to find a number of functions in standard flows - the material functions relating to linear viscoelasticity are relaxation modulus G(t) Compliance J(t) storage and loss modulus [G() and G()] For the case of linear VE they are interrelated by the relaxation spectrum H()

This chapter we have taken a big step in describing rheological phenomena. Linear viscoelasticity is important in practical applications. Some real life deformations will be in the linear regime (especially for solid state rheology). Secondly, understanding and describing the fading memory effect is an important aspect of rheology. We have also provided a number of material functions that can be used to calculate relaxation spectrum and that are interrelated. In the next chapter we will now see how these material functions can be made non-linear. Then we will learn how all these properties can be measured.

49

Applied Rheology

Generalized Newtonian Fluids

Although Newtons law is of much practical use, at the beginning of this century researchers started to realize that not all fluids obey this simple linear relation. Many colloidal suspensions and polymer solutions show a decrease of the viscosity as the shear rate is increased. In the following, we will try to extend Newtons law in the most simple fashion, by making the stress depend on the rate of deformation (or better : on an invariant of the rate of deformation tensor). But as we are talking about viscosities and rate of deformations, maybe it is useful to start of with indicating a few orders of magnitudes which are likely to be encountered

50

Liquid Molten glass Asphalt Molten Polymers Syrup Paints Glycerin Light Oil Water Air

[Pa.s] 1012 108 103-105 101 100-101 100 10-1 10-3 10-5

The SI unit of viscosity is Pa.s (Pascal.second). The cgs unit of Poise (P) is also often used. 1 poise = 0.1 Pa.s. Centipoises are also often encountered, as 1 cP is the viscosity of water.

51

Process Sedimentation Leveling Draining under gravity Extrusion Chewing, Swallowing Dip Coating Mixing and stirring Pipe flow Spraying, brushing Rubbing Injection molding MILLING coating flows Lubrication

shear rate [s-1] 10-6 -104 10-3-10-1 10-1 100-102 101 -102 101 -102 101-103 100-103 103 -104 104 -105 102 -105 103-105 105 -106 103-107

Applications Medicines, Paints,... Paints, inks Emptying tanks Polymer melts, Dough Food Paints, confectionery Manufacturing liquids Pumping, blood flow atomization, painting, spray drying Skin cream and Lotion Polymer melts Paints, inks, coatings paper Engines

The range of shear rates encountered during various processes spans many decades. Rheological properties are important in slow processes such as sedimentation; some products will be tailored too have a very high viscosity at low shear rates for a good shelf-life. Some processes such as rubbing or chewing might seem odd to you, but the rheological properties determine to a large extent the waqy these products feel . Coating flows and printing operate at high rates. The flows, however, are still laminar. It will be quite a challenge to develop measurement techniques that can embrace this entire shear rate range!

52

Do real fluids behave according to Newtons law?

From Barnes (1989)

Just some examples of Non-Newtonian fluids are given above. Human blood (a) is a complex fluid with a very variable rheological behaviour. The most important consituents (rheologically speaking) are the red blood cells, which implies that it can be viewed as a dispersion of deformable particles. Another complex dispersion is yogurt (rheology can be used here as a tool to detect fermentation). Another natural material with a pronounced shear-thinning behaviour is Xanthan gum (b) . Here the structural units are macromolecules which interconnect to form a network that is constructively broken down by the shear flow. But increasing the shear rate does not always result in a decrease of the viscosity. In some cases a shear-thickening behaviour is observed, e.g. for concentrated dispersions containing large particles or associating polymers. As an examoke data for latex spheres in diethyleneglycol is given in fig (d). Note that a nonlinear behaviour of the viscosity not necessarilly implies visco elastic behaviour.

53

1. General viscous fluid

! = f(2D) ! = " pI + a1 # D + a2 # D2 + a3 # D3 +...

A. Cayley Hamilton theorem

! = " pI + f1 # 2D + f2 # (2D)2 f1(I2D , II2D , III2D ) f2 (I2D , II2D , III2D )

Reiner-Rivlin CE

Scalar functions of the Invariants of 2D

To describe non-linear properties the governing equations have to made non-linear. Newtons law stated a proporionality between stress and rate of deformation (y= A1+A2.x ). To make this equation nonlinear we can add higher order terms in a power series (y= A1+A2.x +A3.x2 +) The simplest manner to extend Newtons equation is to have a stress tensor that only depends on the rate of deformation tensor. The general expression can be expanded in a power series. The isotropic term is of course the pressure term. The Cayley-Hamilton theorem helps us in reducing the number of terms. As we are working in a two dimensional space, all terms of higher order then 2 will be zero. The functions f1 and f2 are scalar functions of the invariants. This equation is known as the REINER-RIVLIN constitutive equation. All that remains to be done is to determine f1 and f2

54

1. General viscous fluid

B. Do we need all invariants of D? e.g. et us consider shear flow
!0 ! 2D = # ' # "0 ! 0$ ' 0 0& & 0 0% !' ! 2 0 0$ # & ! 2 0& (2D) = # 0 ' # # 0 0 0& & " %
2

I2D = tr 2D = 0 1 II2D = I2D ! tr (2D2 ) 2 IIID = det(2D) = 0

C. Do we need the second order term in 2D?

$" ! 2 0 0' ! 0' $0 " & ) ! 0 0) + f2 & 0 " ! 2 0) ! = # pI + f1& " & ) & % 0 0 0( & 0 0 0) ) % ( ! xx # ! yy = 0 !2 ! yy # ! zz = f2 "

Firstly : The invariants of 2D can be easily computed. As it turns out, we do not need all invariants, in simple shear flow two of the three will be zero. Secondly: we can reduce the equations even more: the second order term gives rise to normal stresses that are however not physically observed. No N1 and a positive N2 think about the rod climbing experiment this is not what we observed. Typically N1 = xx-yy will be positive and N2 = -0.1 N1 We end up with a general equation for the GENERAL VISCOUS FLUID:

# = "pI + !(II2 D )2D

55

1. General viscous fluid

! = " pI + f1(II2D ) # 2D

The viscosity is now replaced by a function of the second invariant of 2D for a shear flow this becomes:
!2 $# ! ! xy = "1 #

()

and different forms for this function have been proposed

So we have gone through a lot of trouble to prove that the most sensible and mathematically and physically correct thing to do is to replace the viscosity by a scalar function that depends on the invariant of the rate of deformation tensor. For a simple shear flow, the viscosity will depend on the magnitude of the shear rate. Several forms have been proposed for this function. We will go through the different models, distinguishing them by the number of parameters that are used.

56

Viscosity curves :
102 101 100
0.43 # = 0.50 0.47

Styrene-ethylacrylate in H2O
2a = 250 nm

Data from Laun (1984)

The graph above shows the viscosity versus shear stress for aqueous suspensions of charged polystyrene-ethylacrylate spheres with a particle radius of 125nm. The volume fraction was varied from 0 to 0.50, temperature was kept constant at 25C. This graph reveals the typical fetaures that suspensions can display : At low volume fractions the viscosity of the suspensions remains essentially Newtonian and is only slightly greater than that of the dispersion medium. At higher volume fractions, the occurrence of shear-thinning and shear-thickening is very obvious in this figure. At very high volume fractions and low shear stresses, the Newtonian plateau tends to disappear, and a yield stress starts to develop. Not visible in the figure are eventual time effects. Especially for aggregated systems, gradual time-dependent changes in the viscosity can be observed, i;e. thixotropy is a typical property of such systems. The visco-elastic nature of suspensions will also be addressed in this chapter. Interaction forces between colloidal particles are potential forces and are elastic in nature. They will, for example, show up in the oscillatory testing of dispersions. Normal force differences are not very important.

(Pas) "

10-1 10-2 10-3 10-3 10-2 10-1 100 101 102

0.34 0.28 0.18

H2O

103

104

105

! (Pa)

57

Spherical particles : Zero shear viscosity

Dilute case (<0.05)
(Einstein, 1906,1911)

" = "m [ 1 + 2.5!]

Semi-Dilute case (<0.10)
(Batchelor, 1977)

" = "m 1 + 2.5! + 6.2!2

Up to maximum packing

(Krieger-Dougerthy,1959)

0 ' + ( = (m .1 ) . 'max + / ,

)[ ( ]' max

& ( ) (m # ! [(] = lim $ ! '*0$ % '(m "

Einstein calculated the viscosity dissipation produced by the flow around a single sphere. The result is given above. It is only valid for low concentrations, when the suspensions is dilute enough that the flow field around one particle is not appreciably influenced by the presence of neighbouring spheres. The equation states that the size does not affect the viscosity. This is true as long as the matrix cn be treated as a continuum When two spheres are close enough so that the drag on one particle is affected by the drag on a second one, the spheres are said to interact hydrodynamically. The velocity field around one sphere is felt by the another one. Such interactions which are far more complicated to calculate. Interactions between two spheres lead to a term that is proportional in 2, three body interactions lead to a term proportional to 3 and so on. Following an idea by Arrhenius, we can treat the suspension as an effective medium. The addition of a particle leads to an incremental increase of the viscosity. Ball and Richmond (1980) suggested that this viscosity increments is proportional to :

Where [] is the intrinsic viscosity, which is the dilute limit of the viscosity increment per unit volume fraction, divided by the particle volume fraction.

Intergration of this equation leads to the Krieger Dougherty equation (1959), which is an emperical equation for suspensions of spherical and non-spherical shape. Often the product of []max is constant and approximately equal to 2.

d) =

[)])md( &1 ' ( # $ (m ! % "

["] = lim
!$0

" # "m !"m

58

Spherical particles : Zero shear viscosity

1000

max
Einstein Batchelor Krieger-Dougherty

100

This figure compares the predictions for the Einstein, Batchelor and KriegerDougherty equation. For the KD equation, the divergence of the viscosity as the volume fraction approaches maximum packing is observed. For hard spheres, randomly packed, m ~0.63-0.64 (which will be relevant for the low shear viscosity).

"/"
10 1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

59

Spherical particles : Zero shear viscosity

Volume fraction dependences of latices

Particle size distribution effects

This figure shows some data on latices : Data on PS spheres x 5 mm (Manley and Mason, 1954) PS .42, 0.87 mm (Saunders, 1961) low shear viscosity, High shear viscosity (Krieger 1972) These equations only pertain to suspensions of monodispersed particles. For high volume fractions, effects of particle size distribution, and particle roughness are observed. The figure on the right shows the evolution of the relative viscosity against the fraction of large particles for a bimodal dispersion with 5:1 particle sizes, at various total volume percentages. The arrow P-Q shows the reduction of the viscosity by a factor of 50 when the volume fraction is kept constant, but the suspensions are replaced by a 50-50% mixture of large and small spheres. The arrow P-S shows that the volume fraction can be increased from 60 to 75 without increasing the viscosity (figure From Barnes et al, 1989). These issues are of extreme importance for slurry transport ot the design of products.

60

Viscosity curves :
102 101 100
0.43 # = 0.50 0.47

Styrene-ethylacrylate in H2O
2a = 250 nm

Data from Laun (1984)

The graph above shows the viscosity versus shear stress for aqueous suspensions of charged polystyrene-ethylacrylate spheres with a particle radius of 125nm. The volume fraction was varied from 0 to 0.50, temperature was kept constant at 25C. This graph reveals the typical fetaures that suspensions can display : At low volume fractions the viscosity of the suspensions remains essentially Newtonian and is only slightly greater than that of the dispersion medium. At higher volume fractions, the occurrence of shear-thinning and shear-thickening is very obvious in this figure. At very high volume fractions and low shear stresses, the Newtonian plateau tends to disappear, and a yield stress starts to develop. Not visible in the figure are eventual time effects. Especially for aggregated systems, gradual time-dependent changes in the viscosity can be observed, i;e. thixotropy is a typical property of such systems. The visco-elastic nature of suspensions will also be addressed in this chapter. Interaction forces between colloidal particles are potential forces and are elastic in nature. They will, for example, show up in the oscillatory testing of dispersions. Normal force differences are not very important.

(Pas) "

10-1 10-2 10-3 10-3 10-2 10-1 100 101 102

0.34 0.28 0.18

H2O

103

104

105

! (Pa)

61

1. Large particles: Hydrodynamic Forces

Stokesian dynamics simulations (J. Brady and coworkers)

So far, we have only discussed the effects of particle volume fraction on the increase of the low shear viscosity. The viscosity of suspensions is, however, strongly dependent on shear rate. The shear rate dependence of the viscosity occurs because shear flow will be able to distort the equilibrium microstructure. The interparticle spacings will be altered, changing the magnitudes of both the hydrodynamic and the interparticle forces. This will lead to shear thinning and shear thickening. The microstructural changes in flowing dispersion can be complex in nature. The mechanism of shear-thinning in hard sphere suspensions has been elucidated by computer simulations. J. Brady and coworkers introduced a technique called Stokesian Dynamics (see e.g. Brady and Bossis, Annual Review of Fluid Mechanics Vol. 20: 111-157 (1988)), where the Stokes equations are solved for all particles. The distortion of the equilibrium structure changes the interparticle spacing, and the Brownian contribution to the viscosity changes. Particles can be even observed to line-up into strings parallel to the flow direction. When the shear rate is increased, particles can, however, be brought into close proximity by the flow leading to the formation of so-called hydroclusters. The deformation of such clusters is difficult as the small separation in between the particles lead to large lubrication stresses in the gap. For hard sphere systems, we will see that this leads to shear-thickening. When colloidal forces are important, the microstructural reorganizations can have an even more complex dependence on the flow rate. We will now first address the question if we can predict the transition to shear thinning.

62

Scaling for Brownian hard spheres

> 0.3 - shear rate dependence of the viscosity
Brownian motion is suppressed if

! $1 < t d a2 k T td = = a 2/ B D0 6#"m a " a ?! Pe = m k BT

As increases: replace medium by an effective viscosity

Dimensionless shear stress

!r =

! $ a3 !) $ # "susp ( # kT

Distortion of the particulate microstructure will only occur when the rate at which the particle equilibrium is recaptured is smaller than the rate at which it is being deformed. The rate at which the structure regains its configuration is controlled by the particle diffusivity, D0. For spherical particles the diffusivity is given by the Stokes-Einstein relation: kBT

D0 =

6!"ma

Where kB is Boltzmanns constant, T is the temperature, m is the medium viscosity and a is the particle radius. The time tD for a particle to diffuse a distance equal to its radius is given by a2 / D0. The Pclet number is a dimensionless group which will compare the time scales for diffusion and convection, or weigh the hydrodyanmic forces with respect to the Brownian forces. When is the Pclet number small? The definition of the Pclet number implies that the particles are seeing the viscosity of the medium. Especially at higher volume fractions, it is better to use the effective, suspension viscosity as the medium viscosity that a particle feels. Hence a dimensionless shear stress is more appropriate.

63

( $ ', ) , t ,Pe,Re # ! (r = (susp = f& r % " med

$ ',Pe # ! (r = f & % "

10000

, 1, / + ) 0r = f . *

"r0
1000

"r #

max!

& 1 # 0r = $1 ' ! % 1max " 0r = 0r (

'[0]1max
100
r

"
10

& 0 ' 0r ( # + $ r0 ! % 1 + b/r "

1 0.0

0.2

0.4

0.6

0.8

1.0

& 0 ' 0r ( # 0r = 0r ( + $ r 0 m! % 1 + (b/r ) "

64

Shear thickening
16 14 12 10 8
r

Stokesian dynamics simulations (J. Brady and coworkers)

So far, we have only discussed the effects of particle volume fraction on the increase of the low shear viscosity. The viscosity of suspensions is, however, strongly dependent on shear rate. The shear rate dependence of the viscosity occurs because shear flow will be able to distort the equilibrium microstructure. The interparticle spacings will be altered, changing the magnitudes of both the hydrodynamic and the interparticle forces. This will lead to shear thinning and shear thickening. The microstructural changes in flowing dispersion can be complex in nature. The mechanism of shear-thinning in hard sphere suspensions has been elucidated by computer simulations. J. Brady and coworkers introduced a technique called Stokesian Dynamics (see e.g. Brady and Bossis, Annual Review of Fluid Mechanics Vol. 20: 111-157 (1988)), where the Stokes equations are solved for all particles. The distortion of the equilibrium structure changes the interparticle spacing, and the Brownian contribution to the viscosity changes. Particles can be even observed to line-up into strings parallel to the flow direction. When the shear rate is increased, particles can, however, be brought into close proximity by the flow leading to the formation of so-called hydroclusters. The deformation of such clusters is difficult as the small separation in between the particles lead to large lubrication stresses in the gap. For hard sphere systems, we will see that this leads to shear-thickening. When colloidal forces are important, the microstructural reorganizations can have an even more complex dependence on the flow rate. We will now first address the question if we can predict the transition to shear thinning.

6 4 2 0 Hydrodynamic viscosity Brownian viscosity Total viscosity

1e-2

1e-1

1e+0

1e+1

1e+2

1e+3

1e+4

1e+5

Pe

65

Non-Linear Viscoelasticity
Phenomena and modeling

In the previous two chapter we have gradually added complexity to the description of material behaviour. Still the cases presented before are only limiting cases of material behaviour. The generalized Newtonian fluid describes non-linear but inelastic materials at large deformations. The Linear Viscoelastic fluid presents a viscoelastic material but it will only be valid for small deformations. Hence two parameters are important, one being the magnitude of the deformation e.g. strain amplitude, the other being the Deborah number which is defined as the characteristic relaxation time divided by the characteristic time of the process.

De =

# ! !1 "

???

We now have to start describing a very wide range of nonlinear phenomena. Let us first try to make a round up of the phenomena we at least want to describe

LVE

De

66

1. Non-linear VE phenomena 2. Additional mathematical tools 3. The second-order fluid 4. Quasi-linear models 5. Non-linear models

67

1. Nonlinear Phenomena
A. Normal stress differences in shear flow
Stresses Material functions

vx

! xy N1 = ! xx " ! yy N 2 = ! yy " ! zz

%=

" xy ! " xx # " yy !2 " yy # " zz !2

$1 = $2 =

When a viscoelastic material is subjected to a shear flow, in addition to the viscous shear stress (xy), there are normal stress differences that occur. The difference between the xx and the yy component is called the first normal stress difference and the the difference between the normal stress component on the x-plane and the normal stress component on the y-plane. The second normal stress difference is defined in a similar fashion for the normal stress components on the y-plane and zplane. Normal stress differences will be one of the first aspect we want to describe. N1 is typically positive (an exception are liquid crystalline polymers at intermediate to high shear rates). N2 is of the opposite sign and the ratio -N2/N1 lies in the range 0.010.3. At sufficiently low shear rates, the shear stress will always become proportional to the shear rate. Similarly the normal stress differences (which are even functions) will become proportional to the (shear rate)2. The material functions that hence can be defined are called the primary and secondary normal stress coefficient.

68

A. Normal stress differences in shear flow

The above figure presents the shear and normal stress differences for a solution of 1.2% polyisobutene in decalin (data from Keentok, et al, JNNFM, 1980). N1 is positive and is the property responsible for rod-climbing. N2 is typically a factor of ten smaller and has the opposite sign of N1 . The ratio between N1 and N2 is an important check for the validity of models as it depends very strongly on how nonlinearity is being described (biaxiality?). Think about this : why are these non-linear properties? N1 can be easily measured in rotational devices, e.g. in a cone and plate rheometers it can be derived from the total axial trust on the cone (see next chapter on rheometry). The measurement of N2 is much more difficult. It requires measurements of the pressure gradients along a cone or can be measured using rheo-optical methods. It is rarely being measured in the industrial laboratories.

69

B. Shear thinning of and 1

The above figure (from Laun, Rheol. Acta, 1978 ) shows the steady state viscosity and the primary normal stress coefficient for our favorite LDPE melt which weve already encountered previously. This figure shows that the shear thinning in the viscosity is typically accompanied by a decrease of the primary and secondary normal stress coefficients for polymer melts and concentrated polymer solutions. We will provide a physical explanation for this in the chapter on rheology of polymeric liquids based on the concept of entanglements. The data in the above figure were obtained by shifting data to a master curve by using a shift factor. We will come back to the time-temperature superposition principle later on.

70

B. Shear thinning shows up in time-dependence

Shear thinning also shows up in time dependent viscosity after starting up the flow at a constant shear rate. The above figure shows data from Menezes and Greassley (1980) on a polybutadiene in an organic oil. The lowest shear rate gives us the behavior that we already can describe in the framework of linear viscoelasticity. As the shear rate increases, an overshoot appears, at least for deformations that are sufficiently large and shear rates rates that are sufficiently high. The presence of an overshoot will be typical for measurements in the shear-thinning regime.

71

C. Relaxation modulus at large strains

Let us see what happens with another LV property, the relaxation modulus, when we increase the strain amplitude. The above figure gives us the response for the IUPAC LDPE (data from Laun). At small strains, we find the LVE response which weve described previously. As the strain is increased, we find a systematic decrease of the relaxation modulus both the modulus of the shear and the first normal stress difference. If you think about this figure it already indicates to us a route to describe non-linear viscoelastic behavior. The intrinsic shape of the modulus/time curve remains the same, it is only shifted to smaller values on the vertical axis. Hence a description of the time effects (the memory function) and the strain effects (a damping function), would seem to be an attractive route to model NLVE behavior. A (mathematical) separation of these effects might lead to tractable equations.

72

D. Extensional Thickening in uni-axial flow

1e+7

1e+6 0.5 s 1e+5 1s

-1 -1

0.1 s

-1

Up to now only nonlinear phenomena in shear flow have been discussed. One of the annoying things about non-linear behavior is that we cannot necessarily extrapolate the behavior in shear flow to any other type of deformation. A number of polymeric fluids exhibits strain hardening in elongational flow. The above example is for a LDPE (related to the samples studied by Laun in the 70s). At large deformations, the viscosity deviates from what would be expected on the basis of linear viscoelasticity. The elongational viscosity drastically increases. This is an important aspect for processes such as fiber spinning and film blowing. In the chapter on rheology of polymeric fluids, we will discuss the physical origin of this strain hardening.

(Pa.s) !

1e+4

fiber windup
1e+3 RME 3*!LV

1e+2 0.01

0.1

1 t (s)

10

100

73

E. Phenomena in complex flows

- Contraction Flows : mixed shear / elongational flow

extension

shear
- Hyperbolic flow fields

stagnation point

Up to now only nonlinear phenomena in simple shear or uni-axial elongational flows have been discussed, but in the introductory lecture we already encountered a wide variety of phenomena related to non-linear material behavior. The reliability of a constitutive equation needs to be verified for such complex flows, as a successful prediction of properties in shear and uni-axial elongation do not imply that the constitutive model works good. Hence a comparison of model predictions and stress measurements (by optical techniques) is crucial for the evaluation of models. Such experiments and calculations are available in the literature for a number of constitutive equations.

74

2.Tools for Non-Linear Models

Need additional mathematical tools:
A. Deformation measures:

C = FT ! F C "1 = B = F ! F T
B.Time derivative : Upper convected
!

Cauchy-Green Finger tensor

!T ! " $ (!v ) " A $ A " !v A=A ! " = # A+v A " !A #t

UC Material time der.

We already introduced the Finger tensor in the chapter on finite deformation tensors. Physically, the Finger tensor gives us the relative local change in area within the sample.
1 C! = ij

Another tensor which describes relative deformations is the Cauchy Green tensor. It relates the local extension ratios with each other.

#xi #x j " #x'k #x'k

"x deformations "x Both C and C-1 are adequate measure of relative and are useful to build constitutive Cij = k ! k equations. "x' "x'
i j

Now we have one more step to take: are the derivatives we know sufficent? Consider the following example of an expanding duct:

for an external observer the fluid motion is stationary, but for e.g. a polymer molecule in this flow field (an observer travelling with the stream), it observes a deceleration and hence the time derivative is not zero.

75

2.Tools for Non-Linear Models

B.Time derivative : Upper convected
! !T ! " $ (!v ) " A $ A " !v A=A ! " = # A+v A " !A #t

UC Material time der.

We know from our courses on Transport Phenomena how to solve this: we use the Material Time Derivative. This improves the description of what the molecule sees. It is, however, not sufficient. Remember that solid body rotations should not result in stresses, neither should the derivatives - neglecting inertia effects (which we can do), it shouldnt matter how fast a molecule is being rotated. The upper convected derivative is the derivative in a coordinate system embedded in the fluid. The coordinate axes are defined such that they deform with material lines ( We can also choose a coordinate axes defined by the material planes of an element - this would lead to the lower convected derivative). When we use the upper convective derivative we obtain a description that gives only stresses when a material element is being deformed. Note that the convective term introduces nonlinear terms! It is also instructive to note that the UC derivative of the Finger tensor (which describes relative deformations!) is zero, because of the way that they are both defined. So we will need UC derivatives of D or to introduce nonlinearity.

76

3. The Second-Order Fluid

& = #pI + 2%O D # "1, 0 D+ 4"2, 0 D ! D
$

Simplest

CE capable of predicting a first normal stress difference

Three coefficients needed to characterize material behavior Only applicable for slow flows

the second order fluid is a logical extenion of the Newtonian CE. We already know that the term in D.D is only capable of predicting a second normal stress difference. Hence we need a term giving us a first normal stress difference. We will assume a small perturbation of the behavior at rest. There is a class of constitutive equations that we can form in this manner : they are called the retarded motion expansion . The above equation belongs to this class and is called the second-order fluid. It uses an additional term containing the upper convective derivative of the rate of deformation. This term introduces a weak-elastic memory into the equation. It can be shown that under quite general conditions, that a VE fluid will obey the 2nd order fluid, provided the flow is sufficiently slow and slowly varying, to ensure that the deviations from Newtonian behaviour. Lets first see what this equation predicts in shear flow.

77

2nd order fluid in steady state shear flow

)0 0 0& )0 $ ' 1' " " 0 0$ "' + " D = D* '+ 2' $ ' (0 0 0% (0 ! " = # D+ v D " !D = 0 #t
!

" 0& + )0 $ 1' " 0 0$ * ' + 2' $ 0 0% (0

" 0& )0 0 0& "2 )+ + ' $ ' $ " 0 0 $ = *' 0 0 0$ "' + '0 ' $ 0 0$ % (0 0 0% (

0 0& $ 0 0$ 0 0$ %

Steady state flow

Homogeneous

& + xx $ $ + yx $ 0 %

+ xy + yy 0

0 # &0 ! 1$ ! 0 ! = ( pI + 2*0 $ ) 2$ ! + zz " %0

! ) 0 0

!2 &) 0# $ ! 0 ! + '1, 0 $ 0 $0 0! " %

0 0 0

!2 &) 0# ! 1$ 0 ! + 4'2, 0 $ 0 4$ 0! " %0

0 !2 ) 0

0# ! 0! 0! "

%0 =

$ xy ! #

!1 =

$ xx " $ yy = !1, 0 !2 #

!2 =

$ yy " $ zz = !2, 0 !2 #

We assume a steady state flow the time derivatives are zero. When we are considering a homogeneous shear flow, the divergence of the stress tensor will be zero as well (there will be no gradients in the stress this is the definition of a homogeneous flow). As you can see, the resulting equation is not all that hard to solve. You can also see how the upper convected derivative works : when material elements are deformed, a stress is produced. And it produces a term that gives rise to a first normal stress difference. Note that we defined the coefficients of the second-order fluid also in a correct manner. In shear flow, the viscosity is predicted to be constant, and a first and second normal stress difference are predicted, with constant normal stress coefficients. Hence the model cannot deal with shear-thinning, but predicts normal stresses. Let us consider the behaviour in extensional flow.

78

2nd order fluid in steady state uniaxial elongational flow

& + xx $ $ 0 $ 0 % 0 + yy 0 ! 0 # & 2) ! $ 0 ! = ( pI + *0 $ 0 $0 + zz ! " % 0 ! () 0 !2 & 4) 0 # $ ! 1 0 ! + '1, 0 $ 0 2 $ 0 !! () " % 0 !2 ) 0 !2 & 4) 0# ! $ 0 ! + '2, 0 $ 0 $ 0 !2 ! ) " % 0 !2 ) 0 0# ! 0! !2 ! ) "

" E = 3"0 +

3 #1 + 2#2 , 0 ! 2 ,0

2nd order fluid in transient flow?

xy

! !0 "

!+ 3!0"
E

3 !2 (#1,0 + 2#2,0 )" 2

As a first example, solve for a steady state, homogeneous, uniaxial elongational flow. The elongational viscosity at zero stretching rate equals the Newtonian one, but an extensional hardening is predicted when -2,0 / 1,0 < 0.5 , where E increases linearly with increasing stretch rate. Note that here we see the power of the CE, once the three coefficients are known from the behaviour in shear flow we can predict the behaviour in extensional flow. As the second-order fluid contains only terms in D and its higher order terms and a UC derivative, it will not be able to do a good job for predicting time dependent phenomena. For example, for a stress relaxation experiment the stress will vanish as soon as the flow is stopped. This will be a general result for ANY retarded motion equation. Above are the predicitions for start-up of shear and elongational flow. This is what we mean by saying that the second order fluid predicts only weak elastic effcts, some nonlinear effects are predicted, but time-dependent characteristics, even in the LV regime are not described. Most flow of polymeric liquids will not be slow enough for the 2nd order fluid or any of its colleagues to be valid. So well have to abandon this route for writing good CEs. Our efforts have, however, not been in vain. Any model that describes a smooth evolution of stress and structure, should, in the limit of slow flows, yield the second order fluid as a limiting case. So apart from LV behaviour, we have slow flow behaviour as a good test for any non-linear models.

79

4. Quasi-linear Models
A. Differential form: Upper convected Maxwell model

! + # ! = 2 $0D
Simplest way to combine time-dependence and elasticity Non linear because of the UC derivative but linear in the convected reference frame

"

Extending the linear viscoelastic Maxwell model into the nonlinear regime can be done by replacing the material derivative in the Maxwell equation with an upper convective derivative of the stress. This equation is called the Upper convected maxwell model. The equation is nonlinear as the UC derivative contains the product of the velocityb gradient and the stress tensor. For dmall strain amplitudes, the nonlinear terms vanish and a material derivative is all that remains- hence the limit of linear VE is recovered. Likewise, for very slow flows, the rate is small and Newtonian behaviour is recovered. Analyzing what will be the first perutbation as thedeformation rates is increased we have to evaluate the upper convected derivative of the Newtonian equation and :

& $ 2"0 D + second order terms

Hence, for slow flows, the Maxwell model reduces to a second order fluid with 1,0 = 20 and 2,0=0.

& $ 2"0 D+ third order terms & $ 2"0 D # 2"0 ! D+ ...

%

80

UCM in transient and steady state shear flow

!+%

& ! + %v # $! " % $v &t

( ) # ! " %! # ($v)= 2' D

T 0

! xy $! ! yy 0) 0 ) & 2 $! ! 0) & ! xx ! xy 0 ) &! ! &0 $ # ( xx xy (! ! + + ( + = % ($ ! ! 0 + " ! ! 0 , " $! 0 0 0 0+ xy yy yy 0 ( xy yy + ( + ( + ( + #t 0 0 ! ' 0 0 0* 0 0* ' 0 0 ! zz * ' ' 0 zz *
Steady state

! ! xy = "0 #

!2 ! xx = 2 "0 $#

! yy = ! zz = 0

Again, start from the steady state, homogeneous shear flow. The horrible looking equation is easily solved. We find a prediction for a constant viscosity, a first normal stress difference with a constant first normal stress coefficient and a zero second normal stress difference. This CE is not yet describing all the phenomena we want, but at least it looks promising, as we are finding the right limits for VE and slow flows.

81

UCM in transient and steady state shear flow

! xx + " ! xy + " #! xx #t #! xy #t . 2 "! xy $

. = %0 $

t=0, no stresses

transient flow, predictions of an UCM model !0=10, " = 1s

25

!( t) = !0 1 # e # t / "

t * # $ t '01 ( t) = 2 !0 " ,1 # e " & 1 + ) / % "( / , + .

20

15
1

We are more interested in the transient flows, again writing down the equations in component form, for a homogeneous flow, you find that the only terms of the stress tensor differing from zero are given above, and this can be easily solved. We see that for the shear stress we get the same result as the linear Maxwell model, BUT! we also predict an evolution of normal stresses in shear flow. The UCM nicely predicts a gradual increase of the stresses afte inception of flow.

, # !

10

! #1
0 2 4 6 8 10 12 14

t [s]

82

UCM in transient elongational flow

!E
10000

!0 . + . 1$ 2 " # 1$ " #

2 !0

1000

Using the same parameters as on the previous page, and using the velocity gradient for uniaxial elongation, the prediction of the elongational viscosity is obtained under steady state conditions as given above. Note that this is a quite dramatic non-linear behaviour. The viscosity is predicted to be extremely extensional thickening, and it rises to infinity when the strech rate approaches 1/2. In the limit of zero shear rate, the Trouton ratio of three is obtained, followed at slow rates by an evolution that can be aproximated by a linear dependency on the extensional viscosity on stretch rate, as for the second-order fluid. Typically, constitutive equations will differ more amongst themeselves in elongational flow predictions (this is a strong flow). Although the UCM model has some of the qualitative features of the rheology of polymeric fluids, it still fails to describe some essential aspects, such as shear-thiining, N2 and a limited rise of E. The UCM model or related CEs will do a good job for polymer solutions which are very dilute, such that the polymer molecules do not overlap. The viscoelastic properties of the solution will be fairly simple and determined by the properties of the individual molecules. A molecular theory can be constructed that boils down to the UCM (see part 3).

!
100 10 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

rate (s-1)

83

4. Quasi-linear Models
B. Integral form: Lodge model

!=

"#

m( t " t' ) C"1 " I dt'

# t# t$

!= &

'0 (
2

#%

"e

C (

#1

# I dt $

Simplest generalization of the LV integral model the UCM model can be derived from the Lodge model Results : identical to UCM

The linear Maxwell equation could be written in integral form. The non-linear upperconvected Maxwell model can also be written in integral form, provided the proper deformation measure, i.e. the Finger Tensor, is used. By using the fact that the upper convective derivative of the Finger tensor is zero (the upper convective derivative is a time derivative in a special coordinate frame whose base coordinate vectors are stretching and rotating with material lines), the UCM model can be derived from the Lodge model. Although equivalent to the differential UCM equation, some problems will be easier to understand or deal with with integral CE. The fact that real polymeric fluids posses a distribution of relaxation times is one of them. The Lodge model, like the UCM, is inadequate in describing most materials because its elasticity is that of a simple Hookean solid. We will see how we can get a more general CE.

84

5. Non-linear Models
A. Differential form: of the Maxwell type
# 1 " + " + fC ( " , D) + fD ( " ) = 2G0 D !

fC ( ! , D) fD ( ! )

Stress buildup Stress decay

Starting from the UCM, we can try to obtain an equation that modifies the rate at which the stress tends to build-up and decay. Two functionals will be introduced, one depending on the stress and rate of deformation tensor - describing the rate at which stress builds-up and a second one depedning only on the stress tensor that can accelerate the rate at which stress decays. Shear-thinning and strain softening can hence be introduced through fc and fd. In principle, they have a different effect on how non-linearities are introduced, but when sufficient relaxation times are present similar non-linear effects can be introduced through either fc or fd.

85

A.1. Differential form: Phan Thien Tanner (PTT)

fC ((, D) = +(D ' ( + ( ' D ) fD (() = 1 &) # exp$ tr ( ! I * %G "

Linear parameters , G0 Nonlinear parameters , Describes : shear thinning

variable N1 Nonlinear time effects extensional thickening unrealistic oscillations in shear flow no good description of linear limit

but :

Several forms have been proposed for fd and fc. Each of the equations has weaknesses and strengths. One example is the PTT model. The 1 parameter model describes shear thinning, Non-linear time effects and extensional thickening, without divergence. But some weird oscillations are obtained during start-up of flow. The multimode model works much better and can be used to describe a fairly wide range of polymer melts.

86

A. 2. Giesekus model

fC ( ! , D) = 0 # fD ( ! ) = ! "! G0
Linear parameters , G0 Nonlinear parameter Describes : shear thinning
variable N1, no N2 Nonlinear time effects extensional not soo good anisotropic drag!

The Giesekus model is attractive as it contains only one parameter, and still does a fairly good job. Note that the linear parameters can be obtained from Linear viscoelastic measurements, the non-linear parameter must be obtained from a nonlinear experiment.

87

B. Really nonlinear integral models

!=

m ( t " t' , I $ [
t "# 1

C "1

, IIC"1 ) C"1 + m2 ( t " t' , IC"1 , IIC"1 ) C dt'

one can assume m2=0 : problems N2 = 0, thermodynamics or assume m2 = m1. often one can assume factorable mi Kaye Bernstein-Kearsley-Zappas (KBKZ)

m1 = 2

"U "U , m2 = 2 "IC!1 "IIC!1

A very general CE for non-linear VE materials which is an extension of the Lodge model is presented above. Both the Cauchy and Finger tensor are used, this is to introduce both a first and a second normal stress difference. The simplemodels assume m2 =0 , there are some fundamental problems. The experimental data of the stress relaxation data and G(t) in the non-linear regime show that hey are nearly parallel on a log-log plot, meaning that the effects of strain and time are factorable. An expression for the functions m1 and m2 was proposed independently by Kaye and Bernstein, Kearsly and Zappas in 1962. The functions U are time dependent elastic kernel functions. Because these functions depend on strain invariants as well as time, often a lot of experimental data is needed to evaluate these functions, or some guidance of molecular theories is needed. Time-Strain separability (factorable mi), simplifies this equation considerably.

88

The above data refers to the LDPE by Laun. The damping function is obtained experimentally, the approximation with one (dashed line) and two exponentials (sum, line) is shown. For the single exponential version, only the exponent needs n to be determined as non-linear parameter. The Wagner model then can be used to predict the non-linear behaviour, and does a good job for example during start-up of a shear flow, for both shear and normal stresses. Calculating this evolution requires solution of an integral equation.

89

B. Really nonlinear integral models

m1 t ! t' , IC!1 , IIC!1 = m( t ! t' )h IC!1 , IIC!1

h is called the damping function Wagner model

h = f1 exp !n1 Ic !1 ! 3 ! f2 exp !n2 Ic !1 ! 3 h( " ) = exp( !n" )

When the strain-time separability can be applied, the only nonlinear material function needed to predict the behaviour is the damping function. It will, in general depend on the invariants of the Finger tensor. In some case, a simple exponential or for higher strains a sum of two exponentials is sufficient. This model was derived by Manfred Wagner (1976).

90

Conclusions
yield

Gen. Newt 0 N
2nd OF

NLVE Integral Differential .. LVE De

De =

# ! !1 "

91

Conclusions of part 1:
Material functions that we can use to describe viscoelastic behavior and NonNewtonian behavior have been rigorously introduced.

Bovenstaande grafiek - uit het boek van Morrison -

92

Outline
1. Introduction 2. Shear rheometry : drag flows 3. Rotational rheometers : practical design 4. Shear rheometry : pressure driven flows 5. Capillary rheometers : practical design 6. Extensional rheometry (7. On-line rheometry)

93

Introduction Why ?
1. Input for CE : material functions 2. Quality control 3. Simulate industrial flows

A rheometer is an instrument that measures both stress and deformation. indexer viscometer

What do we want to measure?

- small strain (LVE) functions - large strain deformations - steady state data

what are the difficulties?

Many!

94

Introduction: classification
Kinematics : shear vs elongation homogeneous vs non-homogeneous vs complex flow fields

type of straining: - small : G(), G( ), +(t), -(t), G(t), y - large : G(,), G(,), +(t,), -(t ,), G(t ,), (t,) - steady : ( !), 1( ! ) shear rheometry : Drag or pressure driven flows.

95

Shear flow geometries

Drag flows

Pressure driven flows

Sliding plates Capillary Couette Slit

Cone and Plate

Annulus Parallel plates

96

Requirements for shear rheometers:

1. Flow can be analyzed 2. Laminar flow 3. No secondary flow 4. Possibility to vary and shear rate 5. Boundary effects : negligible or correctable 6. Temperature homogeneity and control 7. Large strain expts: - homogenous - no inertia - fast response

97

1. Drag flows : Sliding plate rheometer

Fy

!=
Fx

v0 h
= Fx LW

" 12 " 22

=?

- difficult to keep plates parallel - difficult to achieve steady shear - edge effects very important, local measurements not easy - sample must be viscous or flows out - buckling occurs when sample too viscous - not very practical

98

Drag flows : Couette geometry

M. Couette (1890)

99

Drag flows : Couette geometry

2R0 2Ri

Concentric cylinders, inner one rotating : 1. Steady, laminar, isothermal flow 2. Negligible gravity and end effects 3. Symmetric in 4. vr=vz=0 and v=r
L

Equations of motion:
r: v2 1 !(r" rr ) " $$ % = %# $ r !r r r ! r 2 " r$ !r

$: z:

)= 0

% !p + #g = 0 !z

100

Drag flows : Couette geometry

Boundary conditions 1. v=Ri at Ri 2. v=0 at Ro
2R0 2Ri

Shear stress
" r # r! "r

!:

)= 0

# r! M Ro

# r! (Ro) & (2$ & Ro & L) =

' C = 2) r ) ) ( ) ) ) *

# r! =

M 2$ & L & r 2

Normal stress :
- causes rod-climbing - stress difference @ Ri and Ro : hard to measure

101

Drag flows : Couette geometry

-verry narrow gaps: shear stress is approximately constant. shear rate is approximately constant
!= R = " #R Ro $ Ri Ro + Ri 2 if Ri > 0.99 Ro

-if Ri/Ro <1:

shear stress is not constant over the gap. shear rate distribution
!= r "# "r d# d$
# (Ri ) 0

! = 2$

#(Ri ) = 2$(Ri )

% d# =

$(Ri )

$(Ro ) 2$

d$

d# = ! ($(Ri )) & ! ($(Ro)) d$(Ri )

102

Drag flows : Couette geometry

- if Ri~Ro constant shear rate - large measurement surface, good accuracy - quite good for settling materials - difficult to fill for high viscosity materials (bubbles) - secondary flow at high - limits max. shear rate - heavy geometry : inertia! - no good normal stress measurement possible - thermal control / viscous heating - solvent evaporation - end effects need to be reduced or corrected for:

conicylinder, recessed bottom or Double Couette

103

Drag flows : Cone and plate

Probably most popular geometry Mooney (1934) 1. Steady, laminar, isothermal flow 2. Negligible gravity and end effects 3. Spherical boundary liquid 4. vr=vz=0 and v(r,)

5. Angle < 0.1 radians Equations of motion:

r: $: %:

2 2 " $$ + " %% v$ 1 ! r " rr & = & # !r r r r2

1 !(" r$ sin $) cot $ & ' " $$ = 0 r sin $ !r r 1 !" $% 2 + cot $ ' " $% = 0 r !$ r

104

Drag flows : Cone and plate geometry

Boundary conditions 1. v(/2) = 0 2. v(/2-)=rsin(/2-)r

Shear stress
!: 1 d " #! 2 + cot ! & " #! = 0 r d# r
2$ R 0 0

( )

'

" #! =

M = ) ) r 2 " #! drd!

* ( Cte , , sin # , + , , , C
2

" #% =

3M 2$ & r 3

Independent of fluid characteristics because of small angle!

105

Drag flows : Cone and plate geometry

Shear rate: is also constant throughout the sample: homogeneous!
!= vr " $r " " = = % h(r ) r $ tg (# ) tg (# ) #

Normal stress differences: total trust on the plate is measured Fz

Fz =

"R 2 # $$ ! # %% 2

N1 =

2Fz "R 2

106

Drag flows : Cone and plate geometry

- constant shear rate, constant shear stress -homogeneous! - most useful properties can be measured - both for high and low viscosity fluids - small sample - easy to fill and clean - High visc: shear fracture - limits max. shear rate - low visc : centrifugal effects/inertia - limits max. shear rate - settling can be a problem - solvent evaporation - stiff transducer for normal stress measurements - shear and viscous heating

107

Drag flows : Parallel plates

Again proposed by Mooney (1934) 1. Steady, laminar, isothermal flow 2. Negligible gravity and end effects 3. cylindrical edge 4. vr=vz=0 and v(r,z)

Equations of motion:
r: $: z: v2 1 !(r" rr ) " $$ % = %# $ r !r r r !(" $z ) !z !(" zz ) !z =0 =0

108

Drag flows : Parallel plates

Shear rate: is not constant throughout the sample
!= vr " #r = h h

Shear stress

!=

$ d ln M ' 1 + & !R ) 2"R 3 % d ln # ( M

Normal stresses

N1 ! N2 =

Fz " d ln Fz % 2+ 2 $ !R ' d ln ) (R # &

109

Drag flows : Parallel plate geometry

- preferred geometry for viscous melts - small strain functions - sample preparation is much simpler - Shear rate and strain can be changed also by chaging h - determination of wall slip easy - N2 when N1 is known - edge fracture can be delayed - non-homogeneous flow field (correctable) - inertia/secondary flow - limits max. shear rate - edge fracture still limits use - settling can be a problem - solvent evaporation - shear and viscous heating

110

Rotational rheometers : practical designs

Stress controlled

strain controlled
Transducer

Drag cup motor

Normal force control

Torque control

Position sensor(s) optical

Air bearing

Platform

Geometries environments

Servo Controlled Motor

111

Pressure driven flows : capillary rheometry

Hagen (1839) Poisseuille (1840)

Non-homogeneous flow typically for high shear rates simpler to operate yet yield precise data!

112

Pressure driven flows : capillary rheometry

Q R

1. Steady, laminar, isothermal flow 2. No slip at the wall, vx =0 at R=0 3. vr=v=0 4. Fluid is incompressible, f(p)

!
Z

Equation of motion:
z: 1 !(r" rz ) !p # =0 r !r !z

Only a function of r

Only a function of z

1 d (r! rz ) dp = r dr dz

113

1 d (r! rz ) Po " PL = r dr L ! rz = Po " PL r C2 # + L 2 r because ! rz $ % @ r =0

C2 = 0

! rz (R ) = ! w = r R

Po " PL R # L 2

! rz (r ) = ! w

Note : independent of fluid properties

114

Q = 2) ! v z (r )rdr
0

Shear rate calculation from Q

R 0 dv z dr dr

Q = 2 )v z r r=

R 0

" 2) ! r 2 dr =

Integration by parts + assume :no slip

R * and *w
R 0

R d* *w
2

substitute r and dr

Q = "2 ) ! r 2

dv z dr dr

*w # R & = "2 ) ! % *( * $ 0 w '

dv z dr

R d* *w

Typical trick to deal with inhomogeneous flows: changing of variables

Q* w 3 )R
3

= " ! (* )
0

*w

2 dv z dr

d*

3Q! w 2 "R
3

dQ $ = % ! w 2 dv z dr "R 3 d! w
=

!w 3

!w

Differentiate with respect to w using Leibnitzs rule

! w = % dv z #
dr

3Q 4 "R
3

!w

3Q 4 "R
3

d ln Q d ln ! w

!w = #

!a & # d ln Q ) (3 + + 4 ' d ln ! w *

115

Weissenberg-Rabinowitsch Correction

!w =

!a # d ln Q & %3 + ( 4 $ d ln " w '

Correction factor accounts for material behaviour

Physical meaning:
e.g. power law fluid
>

2 n=1 n=0.7 n=0.3 n=0.01

!w =

!a " 1% $3 + ' 4 # n&

/v <v

Steepness of the velocity profile changes Shear rate is increased with respect to the Newtonian case:

0 0 1

r/R

!a =

4Q "R 3

116

Rabinowitsch Weissenberg correction : be careful - requires numerical differentiation

1000 Raw data "corrected data"

100

Schmmers method :

[Pa.s] !, !

10

typical data of a PP sample @ 230C

10 100 1000 10000

shear rate [s-1]

! ) = !a ( " !a) ! !( " ! " = 0.83 "

117

Are these conditions met ?

Problem 1: Melt distortion

1. Steady, laminar, isothermal flow 2. No slip at the wall, vx =0 at R=0 3. vr=v=0 4. Fluid is incompressible, f(p)

Melt fracture typically occurs at w 105 Pa

118

Are these conditions met ?

Problem 2: Viscous heating

.

1. Steady, laminar, isothermal flow 2. No slip at the wall, vx =0 at R=0 3. vr=v=0 4. Fluid is incompressible, f(p)

Na =

!"R2 # 4k

119

Are these conditions met ?

Problem 3: Wall slip

1. Steady, laminar, isothermal flow 2. No slip at the wall, vx =0 at R=0 3. vr=v=0 4. Fluid is incompressible, f(p)

" !a = " !+

4vs R

@ ! = cst

120

Extensional Rheometry
Extensional viscosities can provide an indication of chain structure.

thickening: flexible, dilute chains

3 thinning: rigid systems

thickening: branched melts

3 thinning: linear melts

Why is extensional rheometry important?

Most processing flows are complex superpositions of flow types and many contain substantial amounts of extensional character. The extensional viscosity is qualitatively different than the shear viscosity and complete characterization should include its measurement. Extensional flows are extremely difficult to realize in the laboratory. The available techniques can be divided into methods for melts and methods for solutions.

121

Extensional Viscosity of Melts

Extensional flows for melts can be generated more easily than solutions because these systems are sufficiently viscous to allow them to be mechanically stretched. Below is the Meisnner
device (Rheol. Acta 33, 1-21, 1994), other examples include the Mundstedt device.

sample F

frit air support

The major advantadges of the Meissner device are that effects of gravitation are nicely balanced by the air flow and that the deformation field is homogeneous. Nevertheless, sample preparation is not at all easy, slippage at the belts can occur and the range of deformation rates and forces is typically limited.

122

Macoskos Wind-up Technique

J. Rheol. 40, 473481 (1996)

!= "

!R D ,R D windup drum radius, L0

L 0 distance between clamp and drum

#11 $ # 22 =

!t ) M exp(" ,M torque, 2 !R D R 0

R 0 initial radius of the sample

This technique goes back to the 60s but was reintroduced and improved by Macosko. The advantages of the technique are that it can be mounted on a rotational rheometer, high extension rates can be achieved and the sample preparation is easy. The deformation field is however not perfectly homogenous (one end is clamped in think about this) and sagging under the effect of gravitation cannot be avoided.

123

LDPE (ATOFINA) @ 190C

1e+7

0.1 s-1 0.5 s-1 1 s-1

1e+6

3*!

These are typical data taken on a commercial LDPE sample in our lab using the FWU technique. The pronounced strain hardening that can be observed makes this a suitable material for e.g. film blowing.

[Pa.s]

1e+5

3*!afschuiving

1e+4 0.1

10

100

t [s]

124

Capillary Breakup methods

125

Current Research Topics - Linking rheology and structure: Rheo-optics, Rheo-scattering,... - Rheology of complex fluid interfaces - Microrheological methods - Rheology of soft matter composites - Role of rheology in biological systems

126

Current Research Topics - Rheology of soft matter composites

127

- Linking rheology and structure: Rheo-optics, Rheo-scattering,...

128

- Rheology of complex fluid interfaces

129

Aim of this lecture:

1. Qualitative insight of the behavior of non-Newtonian fluids. 2. Discuss measurement techniques for a given problem 3. Demonstrate link rheological properties // microstructure

130