38
Generalized LVE CM4650 3/4/2020 1 © Faith A. Morrison, Michigan Tech U. 1 Summary: Generalized Newtonian Fluid Constitutive Equations •A first constitutive equation •Can match steady shearing data very well •Simple to calculate with •Found to predict pressure-drop/flow rate relationships well •Fails to predict shear normal stresses •Fails to predict start-up or cessation effects (time-dependence, memory) – only a function of instantaneous velocity gradient •Derived ad hoc from shear observations; unclear of validity in non-shear flows PRO: CON: Done with Inelastic models (GNF). Let’s move on to Linear Elastic models Summary: Rules for Constitutive Equations Must be of tensor order Must be a tensor (independent of coordinate system) Must be a symmetric tensor Must make predictions that are independent of the observer Should correctly predict observed flow/deformation behavior The stress expression: Innovate and improve constitutive equations What we know so far… Chapter 8: Memory Effects: GLVE © Faith A. Morrison, Michigan Tech U. 2 f D total initial state no force final state force, f, resists displacement Maxwell’s model combines viscous and elastic responses in series dashpot spring total D D D Displacements are additive: Spring (elastic) and dashpot (viscous) in series: Professor Faith A. Morrison Department of Chemical Engineering Michigan Technological University CM4650 Polymer Rheology

Done with Inelastic models (GNF). · 2020. 3. 4. · Newtonian contribution contribution from t0 seconds ago contribution from 2t0 seconds ago ~ 1.8 ~ (t) t0 2t0 t 2.4 ~ The memory

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  • Generalized LVE CM4650 3/4/2020

    1

    © Faith A. Morrison, Michigan Tech U.1

    Summary: Generalized Newtonian Fluid Constitutive Equations

    •A first constitutive equation

    •Can match steady shearing data very well

    •Simple to calculate with

    •Found to predict pressure-drop/flow rate relationships well

    •Fails to predict shear normal stresses

    •Fails to predict start-up or cessation effects (time-dependence, memory) – only a function of instantaneous velocity gradient

    •Derived ad hoc from shear observations; unclear of validity in non-shear flows

    PRO:

    CON:

    Done with Inelastic models (GNF).

    Let’s move on to Linear Elastic models

    Summary:

    Rules for Constitutive Equations

    •Must be of tensor order

    •Must be a tensor (independent of coordinate system)

    •Must be a symmetric tensor

    •Must make predictions that are independent of the observer

    •Should correctly predict observed flow/deformation behavior

    The stress expression:

    Innovate and improve constitutive equations

    What we know so far…

    Chapter 8: Memory Effects: GLVE

    © Faith A. Morrison, Michigan Tech U.2

    f

    Dtotal

    initial stateno force

    final stateforce, f, resists

    displacement

    Maxwell’s model combines viscous and elastic responses in series

    dashpotspringtotal DDD

    Displacements are additive:

    Spring (elastic) and dashpot (viscous) in series:

    Professor Faith A. Morrison

    Department of Chemical EngineeringMichigan Technological University

    CM4650 Polymer Rheology

  • Generalized LVE CM4650 3/4/2020

    2

    Fluids with Memory - Chapter 8

    © Faith A. Morrison, Michigan Tech U.

    We seek a constitutive equation that includes memory effects.

    calculates the stress at a particular time, 𝑡

    2 Constitutive Equations so far:

    So far, stress at 𝑡 depends on rate-of-deformation at 𝒕 only

    3

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝑓 𝛾, 𝐼 , 𝐼𝐼 , 𝐼𝐼𝐼 , material info

    𝜏 𝜇𝛾 𝑡𝜏 𝜂 𝛾 𝛾 𝑡 𝛾 𝛾

    © Faith A. Morrison, Michigan Tech U.

    Newtonian

    Generalized Newtonian

    Neither can predict:

    •Shear normal stresses - this will be wrong so long as we use constitutive equations proportional to 𝛾

    •stress transients in shear (startup, cessation) - this flaw seems to be related to omitting fluid memory

    Current Constitutive Equations

    We will try to fix this now; we will address the first point when we discuss advanced constitutive equations

    4

    Fluids with Memory – Chapter 8

    𝜏 𝜇𝛾 𝑡𝜏 𝜂 𝛾 𝛾 𝑡 𝛾 𝛾

  • Generalized LVE CM4650 3/4/2020

    3

    Startup of Steady Shearing

    © Faith A. Morrison, Michigan Tech U.

    Figures 6.49, 6.50, p. 208 Menezes and Graessley, PB soln 5

    Fluids with Memory – Chapter 8

    𝑣 ≡𝜍 𝑡 𝑥

    00

    𝜍 𝑡 0 𝑡 0𝛾 𝑡 0

    𝜂 ≡ 𝜏 𝑡𝛾

    Ψ ≡ 𝜏 𝜏𝛾

    Cessation of Steady Shearing

    © Faith A. Morrison, Michigan Tech U.

    Figures 6.51, 6.52, p. 209 Menezes and Graessley, PB soln

    6

    Fluids with Memory – Chapter 8

    𝑣 ≡𝜍 𝑡 𝑥

    00

    𝜍 𝑡 𝛾 𝑡 00 𝑡 0

    𝜂 ≡ 𝜏 𝑡𝛾

    Ψ ≡ 𝜏 𝜏𝛾

  • Generalized LVE CM4650 3/4/2020

    4

    How can we incorporate time-dependent effects?

    First, we explore a simple memory fluid.

    © Faith A. Morrison, Michigan Tech U.

    Let’s construct a new constitutive equation that remembers the stress at a time t0 seconds ago

    “Newtonian” contribution

    contribution from fluid memory

    𝜼 is a parameter of the model (it is constant)

    This is the rate-of-deformation tensor 𝑡0seconds beforetime 𝑡

    7

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝜂𝛾 𝑡 0.8𝜂 𝛾 𝑡 𝑡

    © Faith A. Morrison, Michigan Tech U.

    What does this model predict?

    Steady shear

    ??

    ?

    2

    1

    Shear start-up

    ?)(?)(?)(

    2

    1

    ttt

    8

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝜂𝛾 𝑡 0.8𝜂 𝛾 𝑡 𝑡Simple memory fluid

  • Generalized LVE CM4650 3/4/2020

    5

    © Faith A. Morrison, Michigan Tech U.

    What does this model predict?

    Steady shear

    ??

    ?

    2

    1

    Shear start-up

    ?)(?)(?)(

    2

    1

    ttt

    9

    Fluids with Memory – Chapter 8

    Let’s try.

    𝜏 𝑡 𝜂𝛾 𝑡 0.8𝜂 𝛾 𝑡 𝑡Simple memory fluid

    Imposed Kinematics:

    𝑣 ≡𝜍 𝑡 𝑥

    00

    Steady Shear Flow Material Functions

    Material Functions:

    Viscosity

    © Faith A. Morrison, Michigan Tech U.10

    𝜍 𝑡 𝛾 constant

    𝜂 𝛾 ≡ �̃�𝛾𝜏𝛾

    Ψ 𝛾 ≡

    Ψ 𝛾 ≡

    Material Stress Response: 𝜏 𝑡

    𝜏𝑡0

    𝑡0

    𝛾

    𝜍 𝑡

    𝑡0

    𝛾

    𝛾 0, 𝑡

    𝑁 𝑡

    𝑁 ,𝑡0

    First normal-stress coefficient

    Second normal-stress coefficient

  • Generalized LVE CM4650 3/4/2020

    6

    𝑣 ≡𝜍 𝑡 𝑥

    00

    Start-up of Steady Shear Flow Material Functions

    Shear stress growth

    function

    © Faith A. Morrison, Michigan Tech U.11

    𝜍 𝑡 0 𝑡 0𝛾 𝑡 0

    Ψ 𝑡, 𝛾 ≡

    Ψ 𝑡, 𝛾 ≡

    𝑡0

    𝛾

    𝜍 𝑡

    𝑡0

    𝛾

    𝛾 0, 𝑡

    𝜏 𝑡

    𝑡0

    𝑁 𝑡

    𝑡0

    First normal-stress growth coefficient

    Second normal-stress growth coefficient

    𝛾 ,𝛾 ,𝛾 ,

    𝛾 ,𝛾 ,𝛾 ,

    Imposed Kinematics:

    Material Functions:

    Material Stress Response:

    𝜂 𝑡, 𝛾 ≡ �̃� 𝑡𝛾𝜏 𝑡𝛾

    Predictions of the simple memory fluid

    © Faith A. Morrison, Michigan Tech U.

    Steady shear

    0

    ~8.1

    21 The steady viscosity reflects

    contributions from what is currently happening and contributions from what happened t0 seconds ago.

    Shear start-up

    0)()(

    00

    ~8.1

    ~0

    )(

    21

    0

    0

    tt

    tttt

    tt

    12

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝜂𝛾 𝑡 0.8𝜂 𝛾 𝑡 𝑡

  • Generalized LVE CM4650 3/4/2020

    7

    © Faith A. Morrison, Michigan Tech U.

    Shear start-up

    0)()(

    00

    ~8.1

    ~0

    )(

    21

    0

    0

    tt

    tttt

    tt

    ~ ~8.1

    )(t

    t

    Figures 6.49, 6.50, p. 208 Menezes and Graessley, PB soln

    13

    Fluids with Memory – Chapter 8

    Predictions of the simple memory fluid

    𝜏 𝑡 𝜂𝛾 𝑡 0.8𝜂 𝛾 𝑡 𝑡

    © Faith A. Morrison, Michigan Tech U.

    Shear start-up

    ~ ~8.1

    )(t

    t

    0 t

    )(21 t

    What the data show:

    What the GNF models predict:

    0 t

    )(21 t

    Increasing 𝛾

    Increasing 𝛾

    What the simple memory fluid model predict:

    t0

    14

    Fluids with Memory – Chapter 8

    Predictions of the simple memory fluid

    For all rates, 𝛾

    𝜏 𝑡 𝜂𝛾 𝑡 0.8𝜂 𝛾 𝑡 𝑡

  • Generalized LVE CM4650 3/4/2020

    8

    Increasing 𝛾

    Increasing 𝛾

    © Faith A. Morrison, Michigan Tech U.

    ~ ~8.1

    )(t

    t

    0 t

    )(21 t

    What the data show:

    What the GNF models predict:

    0 t

    )(21 t

    What the simple memory fluid model predict:

    t0

    Adding that contribution from the past introduces the observed “build-up” effect to the predicted

    start-up material functions.

    15

    Fluids with Memory – Chapter 8

    Predictions of the simple memory fluid

    For all rates, 𝛾

    Shear start-up

    𝜏 𝑡 𝜂𝛾 𝑡 0.8𝜂 𝛾 𝑡 𝑡

    We can make the stress rise smoother by adding more fading memory terms.

    © Faith A. Morrison, Michigan Tech U.

    Newtonian contribution

    contribution from t0

    seconds ago

    contribution from 2t0

    seconds ago

    ~ ~8.1

    )(t

    tt0 2t0

    ~4.2

    The memory is fading

    16

    Fluids with Memory – Chapter 8

    For all rates, 𝛾

    𝜏 𝑡 𝜂𝛾 𝑡 0.8𝜂 𝛾 𝑡 𝑡 0.6𝜂 𝛾 𝑡 2𝑡

  • Generalized LVE CM4650 3/4/2020

    9

    © Faith A. Morrison, Michigan Tech U.

    )(t

    t

    The fit can be made to be perfectly smooth by using a sum of exponentially decaying terms as the weighting functions.

    0 1.001 0.372 0.143 0.054 0.02

    /0pte0pt

    (𝑡 /𝜆 scales the decay)17

    Fluids with Memory – Chapter 8

    start-up prediction:

    For all rates, 𝛾

    𝜏 𝑡 𝜂 𝛾 𝑡 0.37 𝛾 𝑡 𝑡0.14 𝛾 𝑡 2𝑡 0.05 𝛾 𝑡 3𝑡 ⋯

    𝜂 ∑ 𝑒 / 𝛾 𝑡 𝑝𝑡

    © Faith A. Morrison, Michigan Tech U.

    This sum can be rewritten as an integral.

    )'()('

    '

    0

    tptexiaftpptxi

    txtx

    ta

    tp

    NabxxxiafdxxfI

    N

    i

    b

    aN

    ,)(lim)(1

    18

    New model:

    ~ ~8.1

    )(t

    tt0 2t0

    ~4.2

    (Actually, it takes a bit of renormalizing to make this transformation actually work.)

    In the current formulation, 𝜂 𝑡 grows as N goes to infinity.

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝜂 ∑ 𝑒 𝛾 𝑡 𝑝𝑡

    → 𝑒 𝛾 𝑡 𝑝Δ𝑡′

  • Generalized LVE CM4650 3/4/2020

    10

    © Faith A. Morrison, Michigan Tech U.

    Maxwell Model (integral version)

    Relaxation time 𝜆 - quantifies how fast memory fades

    Zero-shear viscosity 𝜂 – gives the value of the steady shear viscosity

    Two parameters:

    19

    With proper reformulation, we obtain:

    Steps to arrive here:•Add information about past deformations•Make memory fade

    Fluids with Memory – Chapter 8

    Often we write in terms of a modulus parameter, 𝐺

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡′

    © Faith A. Morrison, Michigan Tech U.

    We’ve seen that including terms that invoke past deformations (fluid memory) can improve the constitutive predictions we make.

    This same class of models can be derived in differential form, beginning with the idea of combining viscous and elastic effects.

    20

    Fluids with Memory – Chapter 8

  • Generalized LVE CM4650 3/4/2020

    11

    Hooke’s Law for elastic solids

    © Faith A. Morrison, Michigan Tech U.21

    Newton’s Law for viscous liquids

    The Maxwell Models

    The basic Maxwell model is based on the observation that at long times viscoelastic

    materials behave like Newtonian liquids, while at short times they behave like elastic solids.

    Fluids with Memory – Maxwell Models

    𝜏 𝜂𝛾

    𝜏 𝐺𝛾

    f

    Dtotal

    initial stateno force

    final stateforce, f, resists

    displacement

    © Faith A. Morrison, Michigan Tech U.

    Maxwell’s model combines viscous and elastic responses in series

    dashpotspringtotal DDD

    Displacements are additive:

    Spring (elastic) and dashpot (viscous) in series:

    22

    Fluids with Memory – Maxwell Models

  • Generalized LVE CM4650 3/4/2020

    12

    © Faith A. Morrison, Michigan Tech U.

    In the spring:

    In the dashpot:

    dtdD

    dtdD

    dtdD

    DDD

    dashspringtotal

    dashspringtotal

    dtdDf

    DGf

    dash

    springsp

    dtdD

    dtdf

    Gf

    fdtdf

    G

    total

    sp

    sp

    11

    23

    Fluids with Memory – Maxwell Models

    (proportional to displacement)

    (proportional to rate)

    © Faith A. Morrison, Michigan Tech U.

    dtdD

    dtdf

    Gf total

    sp

    By analogy:shear

    all flows

    G0 Relaxation timeTwo parameter model:

    0 Viscosity

    24

    Fluids with Memory – Maxwell Models

    𝜏 𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

    𝜏 𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

    Also by analogy:(we’re taking a leap here)

  • Generalized LVE CM4650 3/4/2020

    13

    © Faith A. Morrison, Michigan Tech U.

    The Maxwell Model

    G0 Relaxation timeTwo parameter model:

    0 Viscosity

    25

    Fluids with Memory – Maxwell Models

    𝜏 𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

    © Faith A. Morrison, Michigan Tech U.

    How does the Maxwell model behave at steady state? For short time deformations?

    26

    Fluids with Memory – Maxwell Models

    𝜏 𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

    The Maxwell Model

  • Generalized LVE CM4650 3/4/2020

    14

    Example: Solve the Maxwell Model for an expression explicit in the stress tensor

    Fluids with Memory – Maxwell Models

    𝜏 𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

    To solve first-order, linear differential equations:

    Use an integrating function, 𝑢 𝑥

    xdxaexu )()(

    Fluids with Memory – Maxwell Models

    Recall:

    𝑑𝒚𝑑𝑥 𝑎 𝑥 𝒚 𝑏 𝑥 0

  • Generalized LVE CM4650 3/4/2020

    15

    Example: Solve the Maxwell Model for an expression explicit in the stress tensor

    Fluids with Memory – Maxwell Models

    Let’s try.

    𝜏 𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

    © Faith A. Morrison, Michigan Tech U.

    Maxwell Model (integral version)

    30

    We arrived at this equation following two different paths:

    •Add up fading contributions of past deformations•Add viscous and elastic effects in series

    Fluids with Memory – Maxwell Models

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡′

    This is the same equation we “made up” when starting from the simple memory model!

  • Generalized LVE CM4650 3/4/2020

    16

    © Faith A. Morrison, Michigan Tech U.

    What are the predictions of the Maxwell model?

    Need to check the predictions to see if what we have done is worth keeping.

    Predictions:

    •Steady shear

    •Steady elongation

    •Start-up of steady shear

    •Step shear strain

    •Small-amplitude oscillatory shear

    31

    Fluids with Memory – Maxwell Models

    What now?

    © Faith A. Morrison, Michigan Tech U.

    What are the predictions of the Maxwell model?

    Need to check the predictions to see if what we have done is worth keeping.

    Predictions:

    32

    Fluids with Memory – Maxwell Models

    What now?

    Let’s get to work.

    •Steady shear

    •Steady elongation

    •Start-up of steady shear

    •Step shear strain

    •Small-amplitude oscillatory shear

  • Generalized LVE CM4650 3/4/2020

    17

    Imposed Kinematics:

    𝑣 ≡𝜍 𝑡 𝑥

    00

    Steady Shear Flow Material Functions

    Material Functions:

    Viscosity

    © Faith A. Morrison, Michigan Tech U.33

    𝜍 𝑡 𝛾 constant

    𝜂 𝛾 ≡ �̃�𝛾𝜏𝛾

    Ψ 𝛾 ≡

    Ψ 𝛾 ≡

    Material Stress Response: 𝜏 𝑡

    �̃�

    𝑡0

    𝑡0

    𝛾

    𝜍 𝑡

    𝑡0

    𝛾

    𝛾 0, 𝑡

    𝑁 𝑡

    𝑁 ,𝑡0

    First normal-stress coefficient

    Second normal-stress coefficient

    Predictions of the (single-mode) Maxwell Model

    © Faith A. Morrison, Michigan Tech U.

    Steady shear

    0210

    Fails to predict shear normal

    stresses.

    Fails to predict shear-thinning.

    Steady elongation

    Trouton’s rule

    34

    �̅� 3𝜂

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡𝜏𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

  • Generalized LVE CM4650 3/4/2020

    18

    Steady shear viscosity and first normal stress coefficient

    0.1

    1

    10

    100

    0.1 1 10 100

    stress, Pa

    1, sFigure 6.5, p. 173 Binnington and Boger; PIB soln

    sPa ,

    21, sPa

    © Faith A. Morrison, Michigan Tech U.

    There are some systems with a constant viscosity but still start-up effects.

    BOGER FLUIDS

    35

    Fluids with Memory – Chapter 8

    𝛾, 𝑠

    0.1

    1

    10

    100

    1000

    0.01 0.1 1 10 100

    stea

    dy s

    hear

    mat

    eria

    l fun

    ctio

    ns

    1 (Pa s2)

    (Pa)

    2 (Pa s2)

    PS/TCP squaresPS/DOP circles

    1, s

    Steady shear viscosity and first and secondnormal stress coefficient

    Figure 6.6, p. 174 Magda et al.; PS solns

    © Faith A. Morrison, Michigan Tech U.

    BOGER FLUIDS

    36

    Fluids with Memory – Chapter 8

    𝛾, 𝑠

  • Generalized LVE CM4650 3/4/2020

    19

    Step Strain Shear Flow Material Functions

    Relaxation modulus

    © Faith A. Morrison, Michigan Tech U.37

    𝑣 ≡𝜍 𝑡 𝑥

    00

    𝜍 𝑡 lim→0 𝑡 0

    𝛾 /𝜀 0 𝑡 𝜀0 𝑡 𝜀

    𝐺 𝑡, 𝛾 ≡ �̃� 𝑡, 𝛾𝛾𝜏 𝑡, 𝛾𝛾

    𝐺 𝑡, 𝛾 ≡

    𝐺 𝑡, 𝛾 ≡

    𝑡0

    𝛾 0, 𝑡

    𝜏 𝑡

    𝑡0

    𝑁 𝑡

    𝑡0

    First normal-stress relaxation modulus

    Second normal-stress relaxation modulus

    𝛾 ,𝛾 ,𝛾 ,

    𝛾 ,𝛾 ,𝛾 ,

    𝛾𝜀

    𝜀

    .

    .

    .

    𝜀

    𝑡0

    𝜍 𝑡

    𝜀

    Imposed Kinematics:

    Material Functions:

    Material Stress Response:

    𝛾 𝛾𝜀

    Predictions of the (single-mode) Maxwell Model

    © Faith A. Morrison, Michigan Tech U.

    Shear start-up

    0)()(

    1)(

    21

    /0

    ttet t Does predict a gradual

    build-up of stresses on start-up.

    Step shear strain

    0

    )(

    21

    /0

    GG

    etG t Does predict a reasonable

    relaxation function in step strain (but no normal stresses again).

    38

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡𝜏𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

  • Generalized LVE CM4650 3/4/2020

    20

    0.0

    0.2

    0.4

    0.6

    0.8

    1.0

    1.2

    0 2 4 6 8 10

    o

    tG

    t

    0.001

    0.01

    0.1

    1

    0.01 0.1 1 10

    o

    tG

    t

    © Faith A. Morrison, Michigan Tech U.

    Step-Shear-Strain Material Function G(t) for Maxwell Model

    39

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    10

    100

    1,000

    10,000

    1 10 100 1,000 10,000time, s

    G(t), Pa

    © Faith A. Morrison, Michigan Tech U.

    Comparison to experimental data

    Figure 8.4, p. 274 data from Einaga et al., PS 20% soln in chlorinated diphenyl

    s

    Pg

    150

    25000

    Pa

    40

    Fluids with Memory – Chapter 8

  • Generalized LVE CM4650 3/4/2020

    21

    © Faith A. Morrison, Michigan Tech U.

    We can improve this fit by adjusting the Maxwell model to allow multiple relaxation modes

    Generalized Maxwell

    Model

    2𝑁 parameters (can fit anything)41

    Fluids with Memory – Chapter 8

    2𝑁 model parameters: 𝑔 , 𝜆 (constants)

    𝜂 𝑔 𝜆

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    𝜏 𝜂𝜆 𝑒/ 𝛾 𝑡′ 𝑑𝑡′

    𝜏 𝑡 𝜏

    © Faith A. Morrison, Michigan Tech U.

    Generalized Maxwell

    Model

    42

    Fluids with Memory – Chapter 8

    •Steady shear

    •Steady elongation

    •Start-up of steady shear

    •Step shear strain

    •Small-amplitude oscillatory shear

    Let’s try.

    What are the predictions of the Generalized Maxwell model?

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

  • Generalized LVE CM4650 3/4/2020

    22

    © Faith A. Morrison, Michigan Tech U.

    Generalized Maxwell

    Model

    43

    Fluids with Memory – Chapter 8

    What are the predictions of the Generalized Maxwell model?

    •Steady shear

    •Steady elongation

    •Start-up of steady shear

    •Step shear strain

    •Small-amplitude oscillatory shear

    Let’s try.

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    Imposed Kinematics:

    𝑣 ≡𝜍 𝑡 𝑥

    00

    Steady Shear Flow Material Functions

    Material Functions:

    Viscosity

    © Faith A. Morrison, Michigan Tech U.44

    𝜍 𝑡 𝛾 constant

    𝜂 𝛾 ≡ �̃�𝛾𝜏𝛾

    Ψ 𝛾 ≡

    Ψ 𝛾 ≡

    Material Stress Response: 𝜏 𝑡

    �̃�

    𝑡0

    𝑡0

    𝛾

    𝜍 𝑡

    𝑡0

    𝛾

    𝛾 0, 𝑡

    𝑁 𝑡

    𝑁 ,𝑡0

    First normal-stress coefficient

    Second normal-stress coefficient

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    23

    Step Strain Shear Flow Material Functions

    Relaxation modulus

    © Faith A. Morrison, Michigan Tech U.45

    𝑣 ≡𝜍 𝑡 𝑥

    00

    𝜍 𝑡 lim→0 𝑡 0

    𝛾 /𝜀 0 𝑡 𝜀0 𝑡 𝜀

    𝐺 𝑡, 𝛾 ≡ �̃� 𝑡, 𝛾𝛾𝜏 𝑡, 𝛾𝛾

    𝐺 𝑡, 𝛾 ≡

    𝐺 𝑡, 𝛾 ≡

    𝑡0

    𝛾 0, 𝑡

    𝜏 𝑡

    𝑡0

    𝑁 𝑡

    𝑡0

    First normal-stress relaxation modulus

    Second normal-stress relaxation modulus

    𝛾 ,𝛾 ,𝛾 ,

    𝛾 ,𝛾 ,𝛾 ,

    𝛾𝜀

    𝜀

    .

    .

    .

    𝜀

    𝑡0

    𝜍 𝑡

    𝜀

    Imposed Kinematics:

    Material Functions:

    Material Stress Response:

    𝛾 𝛾𝜀

    Predictions of the Generalized Maxwell Model

    © Faith A. Morrison, Michigan Tech U.

    Steady shear

    0211

    N

    kk

    Fails to predict shear normal stresses

    Fails to predict shear-thinning

    Step shear strain

    0

    )(

    21

    1

    /

    GG

    etGN

    k

    t

    k

    k k

    This function can fit anyobserved data (we show how)

    Note that the GMM does not predict shear normal stresses.

    46

    Fluids with Memory – Chapter 8

    2𝑁 model parameters: 𝑔 , 𝜆 (constants)

    𝜂 𝑔 𝜆𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

  • Generalized LVE CM4650 3/4/2020

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    10

    100

    1,000

    10,000

    1 10 100 1000 10000time, t

    G(t), Pak k gk1 450 5002 100 9003 30 13004 5.0 1600

    k=4 k=3 k=2

    k=1

    4

    1k

    tk

    keg

    © Faith A. Morrison, Michigan Tech U.

    Fitting 𝐺 𝑡 to Generalized Maxwell Model

    Figure 8.4, p. 274 data from Einaga et al., PS 20% soln in chlorinated diphenyl

    (s) (Pa)

    47

    Fluids with Memory – Chapter 8

    2𝑁 model parameters: 𝑔 , 𝜆 (constants)

    𝜂 𝑔 𝜆

    © Faith A. Morrison, Michigan Tech U.

    The Linear-Viscoelastic Models

    Differential Maxwell (one mode):

    Integral Maxwell (one mode):

    Generalized Maxwell model (N modes):

    48

    Fluids with Memory – Chapter 8

    2𝑁 model parameters: 𝑔 , 𝜆 (constants)

    𝜂 𝑔 𝜆

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    𝜏 𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

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    25

    Predictions of the Generalized Maxwell Model

    © Faith A. Morrison, Michigan Tech U.

    Step shear strain

    0

    )(

    21

    1

    /

    GG

    etGN

    k

    t

    k

    k k

    49

    Fluids with Memory – Chapter 8

    Note: The time-dependent function in the integral of the GMM is the same form as the step strain result:

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    © Faith A. Morrison, Michigan Tech U.

    The Linear-Viscoelastic Models

    Differential Maxwell (one mode):

    Integral Maxwell (one mode):

    Generalized Maxwell model (N modes):

    50

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    Since the term in brackets is just the predicted relaxation modulus G(t), we can write an even more general linear viscoelastic modelby leaving this function unspecified.

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    𝜏 𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

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    © Faith A. Morrison, Michigan Tech U.

    The Linear-Viscoelastic Models

    Differential Maxwell (one mode):

    Integral Maxwell (one mode):

    Generalized Maxwell model (N modes):

    Generalized Linear-Viscoelastic Model:

    51

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    𝜏 𝜂𝐺𝜕𝜏𝜕𝑡 𝜂 𝛾

    © Faith A. Morrison, Michigan Tech U.

    Generalized Maxwell Model

    52

    Fluids with Memory – Chapter 8

    What are the predictions of these models?

    •Steady shear

    •Steady elongation

    •Start-up of steady shear

    •Step shear strain

    •Small-amplitude oscillatory shear

    Let’s try.

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    Generalized Linear-Viscoelastic Model 𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡

  • Generalized LVE CM4650 3/4/2020

    27

    𝛿

    Small-Amplitude Oscillatory Shear Material Functions

    SAOS stress

    © Faith A. Morrison, Michigan Tech U.53

    𝑣 ≡𝜍 𝑡 𝑥

    00

    𝜍 𝑡 𝛾 cos 𝜔𝑡𝛾 𝛾𝜔

    , , �̃� sin 𝜔𝑡 𝛿 𝐺 sin 𝜔𝑡 𝐺 cos 𝜔𝑡𝐺′ 𝜔 ≡ cos 𝛿 𝐺′′ 𝜔 ≡ sin 𝛿

    𝑡0

    𝛾 0, 𝑡

    𝜏 𝑡

    𝑡0

    𝑁 𝑡 𝑁 𝑡 0(linear viscoelastic regime)

    Storage modulus

    Loss modulus

    𝑡0

    𝜍 𝑡

    𝛾 cos 𝜔𝑡 𝛾 sin 𝜔𝑡

    𝜏 sin 𝜔𝑡 𝛿

    𝛿 phase difference between stress and strain waves

    Imposed Kinematics:

    Material Functions:

    Material Stress Response:

    Predictions of the Generalized Maxwell Model (GMM) and Generalized Linear-Viscoelastic Model (GLVE)

    © Faith A. Morrison, Michigan Tech U.

    Small-amplitude oscillatory shear

    GMM

    N

    k k

    k

    N

    k k

    kk

    G

    G

    12

    12

    2

    )(1)(

    )(1)(

    GLVE

    0

    0

    sin)()(

    cos)()(

    dsssGG

    dsssGG

    54

    Fluids with Memory – Chapter 8

    2𝑁 model parameters: 𝑔 , 𝜆 (constants)

    𝜂 𝑔 𝜆

    𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡 𝜏 𝑡𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

  • Generalized LVE CM4650 3/4/2020

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    0.00001

    0.0001

    0.001

    0.01

    0.1

    1

    10

    0.001 0.01 0.1 1 10 100 1000

    1

    1'

    G

    1

    1"

    G

    10-5

    10-4

    © Faith A. Morrison, Michigan Tech U.

    Predictions of (single-mode) Maxwell Model in SAOS

    21

    12

    1

    11

    21

    211

    21

    2211

    )(1)(1)(

    )(1)(1)(

    gG

    gG

    55

    Fluids with Memory – Chapter 8

    Two model parameters: 𝑔 , 𝜆 (constants)

    𝜂 𝑔 𝜆

    𝜏 𝑡 𝜂𝜆 𝑒 𝛾 𝑡 𝑑𝑡

    SAO

    S m

    ater

    ial f

    unct

    ions

    © Faith A. Morrison, Michigan Tech U.

    Predictions of (multi-mode) Maxwell Model in SAOS

    Figure 8.8, p. 284 data from Vinogradov, PS melt

    1.E+01

    1.E+02

    1.E+03

    1.E+04

    1.E+05

    1.E+06

    1.E+07

    1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07

    aT, rad/s

    G' (Pa)G'' (Pa)

    k k (s) gk(kPa) 1 2.3E-3 16 2 3.0E-4 140 3 3.0E-5 90 4 3.0E-6 400 5 3.0E-7 4000

    N

    k k

    k

    N

    k k

    kk

    G

    G

    12

    12

    2

    )(1)(

    )(1)(

    k 𝜆 (s) gk(kPa)

    56

    Fluids with Memory – Chapter 8

  • Generalized LVE CM4650 3/4/2020

    29

    © Faith A. Morrison, Michigan Tech U.

    Predictions of (multi-mode) Maxwell Model in SAOS

    Figure 8.10, p. 286 data from Laun, PE melt

    1.E-01

    1.E+00

    1.E+01

    1.E+02

    1.E+03

    1.E+04

    1.E+05

    1.E+06

    1.E-04 1.E-02 1.E+00 1.E+02 1.E+04 1.E+06

    aTrad/s

    mod

    uli

    G' (Pa)G" Pa

    k gk50 4.42E+025 3.62E+031 4.47E+030.5 3.28E+030.2 9.36E+030.1 1.03E+040.05 1.71E+030.02 1.18E+020.02 2.55E+040.01 3.33E+040.0007 1.83E+05

    N

    k k

    k

    N

    k k

    kk

    G

    G

    12

    12

    2

    )(1)(

    )(1)(

    57

    Fluids with Memory – Chapter 8

    © Faith A. Morrison, Michigan Tech U.58

    Fluids with Memory – Chapter 8

    http://pages.mtu.edu/~fmorriso/cm4650/PredictionsGLVE.pdf

    Predictions of the Generalized Linear Viscoelastic Model (the “report card”)

  • Generalized LVE CM4650 3/4/2020

    30

    0.1

    1

    10

    100

    1000

    0.01 0.1 1 10 100

    stea

    dy s

    hear

    mat

    eria

    l fun

    ctio

    ns

    1 (Pa s2)

    (Pa)

    2 (Pa s2)

    PS/TCP squaresPS/DOP circles

    1, s

    Steady shear viscosity and first and secondnormal stress coefficient

    Figure 6.6, p. 174 Magda et al.; PS solns

    © Faith A. Morrison, Michigan Tech U.

    BOGER FLUIDS

    59

    Fluids with Memory – Chapter 8

    𝛾, 𝑠

    x1

    x2

    x3

    H

    W V

    v1(x2)

    EXAMPLE: Drag flow of a Generalized Linear-Viscoelastic fluid between infinite parallel plates•steady state•incompressible fluid•infinitely wide, long

    60

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡

  • Generalized LVE CM4650 3/4/2020

    31

    © Faith A. Morrison, Michigan Tech U.

    Limitations of the GLVE Models

    •Predicts constant shear viscosity

    •Only valid in regime where strain is additive (small-strain, low rates)

    •All stresses are proportional to the deformation-rate tensor; thus shear normal stresses cannot be predicted

    •Cannot describe flows with a superposed rigid rotation (as we will now discuss; see Morrison p296)

    61

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡

    What else can we try?

    © Faith A. Morrison, Michigan Tech U.

    Jeffreys Model - Mechanical Analog

    Maxwell Model - Mechanical Analog

    62

    Advanced Constitutive Modeling – Chapter 9

    𝜏 𝑡 𝜆 𝜕𝜏𝜕𝑡 𝜂 𝛾

    𝜏 𝑡 𝜆 𝜕𝜏𝜕𝑡 𝜂 𝛾 𝜆𝜕𝛾𝜕𝑡

  • Generalized LVE CM4650 3/4/2020

    32

    © Faith A. Morrison, Michigan Tech U.

    Jeffreys Model

    Now, solving for 𝜏 explicitly we obtain,

    Other modifications of the Maxwell model motivated by springs and dashpots in series and

    parallel modify 𝐺 𝑡 𝑡’ but do not otherwise introduce new behavior.

    (Might as well use the Generalized Maxwell model)

    63

    Advanced Constitutive Modeling – Chapter 9

    𝜏 𝜆 𝜕𝜏𝜕𝑡 𝜂 𝛾 𝜆𝜕𝛾𝜕𝑡

    𝜏 𝑡 𝜂𝜆 1𝜆𝜆 𝑒

    2𝜂 𝜆𝜆 𝛿 𝑡 𝑡 𝛾 𝑡 𝑑𝑡

    Unfortunately, this change only modifies 𝐺 𝑡 𝑡 ;the Jeffreys Model is a GLVE model

    © Faith A. Morrison, Michigan Tech U.64

    Advanced Constitutive Modeling – Chapter 9

    Limitations of the GLVE Models

    •Predicts constant shear viscosity

    •Only valid in regime where strain is additive (small-strain, low rates)

    •All stresses are proportional to the deformation-rate tensor; thus shear normal stresses cannot be predicted

    •Cannot describe flows with a superposed rigid rotation (as we will now discuss; see Morrison p296)

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡

    What else can we try?

    Where do we go from here?

  • Generalized LVE CM4650 3/4/2020

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    © Faith A. Morrison, Michigan Tech U.65

    Advanced Constitutive Modeling – Chapter 9

    Limitations of the GLVE Models

    •Predicts constant shear viscosity

    •Only valid in regime where strain is additive (small-strain, low rates)

    •All stresses are proportional to the deformation-rate tensor; thus shear normal stresses cannot be predicted

    •Cannot describe flows with a superposed rigid rotation (as we will now discuss; see Morrison p296)

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡

    What else can we try?

    Where do we go from here?

    Let’s talk about this

    issue.

    © Faith A. Morrison, Michigan Tech U.

    fluid x

    y

    zyx ,,

    zyx ,,

    Shear flow in a rotating frame of reference

    66

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡GLVE:

  • Generalized LVE CM4650 3/4/2020

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    © Faith A. Morrison, Michigan Tech U.67

    fluid x

    y

    zyx ,,

    zyx ,,

    Shear flow in a rotating frame of reference

    Fluids with Memory – Chapter 8

    GLVE:

    𝑥,𝑦, 𝑧 coordinate system stationary�̅�,𝑦, 𝑧̅ coordinate system rotating at Ω

    The choice of coordinate system should make no difference. Let’s check.

    Predict: 𝜂

    © Faith A. Morrison, Michigan Tech U.68

    fluid x

    y

    zyx ,,

    zyx ,,

    Shear flow in a rotating frame of reference

    Fluids with Memory – Chapter 8

    GLVE:

    𝑥,𝑦, 𝑧 coordinate system stationary�̅�,𝑦, 𝑧̅ coordinate system rotating at Ω

    𝑣 𝑣 𝑣

    𝛾 𝑦�̂� ̅ 𝑣

    We write the fluid velocity two ways:

    Both ways we should get the same answer for 𝜏 𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡

    GLVE:

  • Generalized LVE CM4650 3/4/2020

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    © Faith A. Morrison, Michigan Tech U.

    Shear flow in a rotating frame of reference

    tyybdtyyctxxbtxxa

    o

    o

    o

    o

    cossinsincos

    oyy

    t

    P

    x

    y

    x

    y

    oxx

    ab

    d

    c

    69

    Fluids with Memory – Chapter 8

    .P

    © Faith A. Morrison, Michigan Tech U.

    Shear flow in a rotating frame of reference

    tyybdtyyctxxbtxxa

    o

    o

    o

    o

    cossinsincos

    oyy

    t

    P

    x

    y

    x

    y

    oxx

    ab

    d

    c

    70

    Fluids with Memory – Chapter 8

    𝑦 𝑦𝑥 𝑥

    Location of P: 𝑥 𝑥 ,𝑦 𝑦

    .

  • Generalized LVE CM4650 3/4/2020

    36

    © Faith A. Morrison, Michigan Tech U.

    Shear flow in a rotating frame of reference

    tyybdtyyctxxbtxxa

    o

    o

    o

    o

    cossinsincos

    oyy

    t

    P

    x

    y

    x

    y

    oxx

    ab

    d

    c

    71

    Fluids with Memory – Chapter 8

    𝑦 𝑦𝑥 𝑥

    Location of P: 𝑥 𝑥 ,𝑦 𝑦 𝑦 𝑑 𝑑 𝑏 𝑏

    .

    © Faith A. Morrison, Michigan Tech U.

    Summary: Generalized Linear-Viscoelastic (GLVE) Constitutive Equations

    •A first constitutive equation with memory

    •Can match SAOS, step-strain data very well

    •Captures start-up/cessation effects

    •Simple to calculate with

    •Can be used to calculate the LVE spectrum

    •Fails to predict shear normal stresses

    •Fails to predict shear-thinning/thickening

    •Only valid at small strains, small rates

    •Not frame-invariant

    PRO:

    CON:

    72

    Fluids with Memory – Chapter 8

    𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡GLVE:

  • Generalized LVE CM4650 3/4/2020

    37

    73

    Find the recipe card (has kinematics, 

    definitions of material functions; 𝑣(t) is known)

    Predict a material function for a constitutive equation

    For the given kinematics, calc. needed 

    stresses from the constitutive equation

    From stresses, calculate the material function(s) from the 

    definition on the recipe card

    Sketch the situation and choose an appropriate 

    coordinate system

    Calculate a flow field or stress 

    field for a fluid in a situation

    Solve the differential equations  (Solve EOM, continuity, and constitutive 

    equation for 𝑣 and 𝑝 and apply the boundary conditions)

    Model the flowby asking yourself questions about the velocity field (are some components and derivatives zero?  The constitutive 

    equationmust be known)

    x1

    x2

    x3

    H

    W V

    v1(x2)

    EXAMPLE: Drag flow between infinite parallel plates

    •Newtonian•steady state•incompressible fluid•very wide, long•uniform pressure

    2

    Step Shear Strain Material Functions

    00

    00

    constant

    00

    0

    0lim)(

    t

    tt

    t

    Kinematics:

    123

    2

    00)(

    xtv

    Material Functions:

    0

    0210

    ),(),(

    ttG

    20

    22111

    G

    20

    33222

    GRelaxation

    modulus

    First normal-stress relaxation modulus

    Second normal-stress relaxation

    modulus

    © Faith A. Morrison, Michigan Tech U.4

    What kind of rheology calculation am I considering?

    𝜏 𝑡 𝑓 𝑣constitutive equation

    © Faith A. Morrison, Michigan Tech U.74

    Done with GLVE.Let’s move on to Advanced Constitutive Equations

    𝜏 𝑡 𝐺 𝑡 𝑡′ 𝛾 𝑡 𝑑𝑡

  • Generalized LVE CM4650 3/4/2020

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    Chapter 9: Advanced Constitutive Models

    © Faith A. Morrison, Michigan Tech U.75

    CM4650 Polymer Rheology

    Professor Faith A. Morrison

    Department of Chemical EngineeringMichigan Technological University