Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark....
Transcript of Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark....
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Lecture 7 and 8: Extensional Rheology
Ole Hassager and Qian Huang
Nanjing, August , 2018
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2 DTU Chemical Engineering, Technical University of Denmark
Experimentalscience is the
foundation of all natural science.
National Museum of China, Beijing
A Chinese Nobel laureate:
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Do you know this feeling?
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4 DTU Chemical Engineering, Technical University of Denmark
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5 DTU Chemical Engineering, Technical University of Denmark
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6 DTU Chemical Engineering, Technical University of Denmark
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Perkins, Smith and Chu, Science, 27 June 1997, Volume 276, pp.2016-2021
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8 DTU Chemical Engineering, Technical University of Denmark
Injection Moulding:
Why study extensional rheology?
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9 DTU Chemical Engineering, Technical University of Denmark
Other Polymer processing operations with Extension:
Fibre spinning:
(draw down ratio)
Film blowing:
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10 DTU Chemical Engineering, Technical University of Denmark
"The World's Strongest FibreTM"
Dyneema® is an UHMwPE (Ultra High Molecular weight Polyethylene) fibredeveloped by DSM in the Netherlands
High Strength: On a weight for weight basis, Dyneema® is 15 times stronger than steel wire
Water resistant: Dyneema® is hydrophobic and does not absorb water.
Chemical resistance: Dyneema® is chemically inert.DSM Dyneema’s patent: EP1699954B1.
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Historical:Extensional Rheometer Designs
Meissner and Hostettler (1994), conveyor belt
Meissner (1969), (1971), rotary clamp
Sentmanat (2004): SER
TA: EVF
Münstedt and Laun (1979)
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12 DTU Chemical Engineering, Technical University of Denmark
All materials:
Mass: 𝛻𝛻 � 𝑣𝑣 = 0
Force: 𝜌𝜌 𝜕𝜕𝜕𝜕𝜕𝜕
+ 𝑣𝑣 � 𝛻𝛻 𝑣𝑣 = −𝛻𝛻𝑝𝑝 + 𝛻𝛻 � 𝜎𝜎
Newtonian liquids:
True Stress: 𝜎𝜎 𝑡𝑡 = 𝜇𝜇�̇�𝛾 𝑡𝑡
Viscosity: 𝜇𝜇
Rate-of-deformation tensor: �̇�𝛾 = [𝛻𝛻𝑣𝑣 + 𝛻𝛻𝑣𝑣 † ]
Polymeric liquids:
True Stress: 𝜎𝜎 𝑡𝑡 = 𝜎𝜎{𝑣𝑣 𝑡𝑡′ , 𝑡𝑡′ ∈ −∞; 𝑡𝑡 }
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13 DTU Chemical Engineering, Technical University of Denmark
Shear Flow:
𝑥𝑥1
𝑥𝑥2
Uniaxial Extensional flow:𝑣𝑣1 = − ̇𝜖𝜖𝑥𝑥1/2 𝜎𝜎33 − 𝜎𝜎11 = 𝜂𝜂𝐸𝐸( ̇𝜖𝜖) ̇𝜖𝜖𝑣𝑣2 = − ̇𝜖𝜖𝑥𝑥2/2 ̇𝜖𝜖 ≥ 0𝑣𝑣3 = ̇𝜖𝜖𝑥𝑥3
Shear rate 𝜅𝜅 [1/s]
Hencky strain rate ̇𝜖𝜖 [1/s]
Problem:In general no connection betweenrheometric functions in shear and extension
𝑥𝑥1
𝑥𝑥3
Two basic frequently studied classes of flow:
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14 DTU Chemical Engineering, Technical University of Denmark
Except in small deformations:
𝜎𝜎𝑖𝑖𝑖𝑖 𝑡𝑡 = �𝜕𝜕′=−∞
𝜕𝜕𝐺𝐺 𝑡𝑡 − 𝑡𝑡′ �̇�𝛾𝑖𝑖𝑖𝑖 𝑡𝑡′ 𝑑𝑑𝑡𝑡𝑑
𝐺𝐺(𝑡𝑡 − 𝑡𝑡𝑑): Linear Viscoelastic Relaxation modulus
But polymer processing operations does not involve small deformations!
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15 DTU Chemical Engineering, Technical University of Denmark
Fibre spinning:
(draw down ratio)
Find pressure, velocity, polymer conformation, crystallinity…
Mainlyextensional flow
Mainly shear flow
Rheometry: Determine rheometric functions 𝜂𝜂𝐸𝐸( ̇𝜖𝜖)…
If we can control flow locally and measure stress locally the flow field needs not be homogeneousglobally.
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16 DTU Chemical Engineering, Technical University of Denmark
Homogeneous Extensional Flow
For incompressible liquids, the local Hencky strain of a filament may be calculated from the diameter:
L0
D0
L(t)
D(t)
Hencky Strain:
0
( )L tL
λ =
Stretch Ratio:
Hencky Strain Rate:
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17 DTU Chemical Engineering, Technical University of Denmark
Sentmanat Extensional Rheomter (SER)
Filament Stretching Rheomter (FSR)
0
( )lnzL tL
ε =
0
( )2 ln D tD
ε = −
FSR locally homogeneousin mid-plane
Commercially available extensional rheometers
do not provide globally homogeneous flow :
Extensional Viscosity Fixture (EVF)
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18 DTU Chemical Engineering, Technical University of Denmark
Filament Stretching Rheomter (FSR)
Determination of stress:
𝐷𝐷0 𝐷𝐷0
𝐹𝐹(𝑡𝑡)
𝐹𝐹(𝑡𝑡)
Engineering stress at t: 𝜎𝜎𝐸𝐸 = 𝐹𝐹(𝑡𝑡)/(𝜋𝜋(𝐷𝐷02
)2)
(True) stress in yellow material at t: 𝜎𝜎 = 𝐹𝐹(𝑡𝑡)/(𝜋𝜋 𝐷𝐷 𝜕𝜕2
2)
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Force measured at bottom plate. (correction for gravity may be needed)
www.rheofilament.com
Versatile Accurate Deformation Extensional Rheometer (VADER) provides:
• Local diameter measurement by laser micrometer
• Fast feedback loop for controlled deformation
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20 DTU Chemical Engineering, Technical University of Denmark
Available protocols:
• Constant rate (start-up)
• True Stress Relaxation ̇𝜀𝜀 = 0
• Constant stress (creep)
• Small Amplitude Oscillation
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21 DTU Chemical Engineering, Technical University of Denmark
Filament Stretching
0
( )lnzL tL
ε =
0
( )2 ln D tD
ε = −
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22 DTU Chemical Engineering, Technical University of Denmark
𝜎𝜎(𝑡𝑡) = �−∞
𝜕𝜕𝑀𝑀 𝑡𝑡 − 𝑡𝑡′ 𝜙𝜙 𝐼𝐼1, 𝐼𝐼2 𝐵𝐵 𝑡𝑡, 𝑡𝑡′ 𝑑𝑑𝑡𝑡𝑑
𝜙𝜙 𝐼𝐼1, 𝐼𝐼2 =𝛼𝛼
𝛼𝛼 − 3 + 𝛽𝛽𝑖𝑖1 + (1 − 𝛽𝛽)𝐼𝐼2
What happens at constant stretch rate no feed-back control?
Hassager, Kolte and Renardy
J. Non-Newtonain Fluid Mech., 76, 137-151 (1998)
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23 DTU Chemical Engineering, Technical University of Denmark
What happens at constant stretch rate no feed-back control?
Hassager, Kolte and Renardy
J. Non-Newtonain Fluid Mech., 76, 137-151 (1998)
Hencky strain at failuredecreases with increasing rate
𝑅𝑅𝑠𝑠𝑅𝑅0
Material near plates recoils
𝜀𝜀𝑁𝑁 𝜀𝜀𝑁𝑁
𝐿𝐿 𝑡𝑡 − 𝐿𝐿𝑐𝑐(𝑡𝑡)𝐿𝐿 0 − 𝐿𝐿𝑐𝑐(𝑡𝑡)
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24 DTU Chemical Engineering, Technical University of Denmark
No feedback loop: Viscoelastic InstabilityBoth FSR and SER:
Zhu et al., J. Rheol. (2013) 57: 223
See also Malkin et al., Prog. Poly. Sci. (2014) 39: 959-978
Zhu et al., J. Rheol. (2013) 57: 223
Simulations by e.g. Hassager, Kolte Renardy
Molecularstretching.
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25 DTU Chemical Engineering, Technical University of Denmark
With feed-back control:Steady-state Extensional Flow
Bach et al., Macromolecules (2003) 34: 5174-6179
Nielsen et al., J. Rheol. (2006) 50: 453-476
Bhattacharjee et al., Macromolecules (2002) 35: 10131-10148
PS melts and solutions
Rolie-Poly and Doi-Edwards without stretch:𝜂𝜂𝐸𝐸~ ̇𝜀𝜀−1
Type equation here.
UCM and Gaussian dumbbells:
𝜂𝜂𝐸𝐸 → ∞ for ̇𝜀𝜀 → ∞
Wiest model: 𝜂𝜂𝐸𝐸~ ̇𝜀𝜀−1/2 for ̇𝜀𝜀 → ∞
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26 DTU Chemical Engineering, Technical University of Denmark
• Elongational viscosity of model linear polymers
• Elongational viscosity at processing (PE-A and PE-B)
• Elongational viscosity of model branched polymers
• Stress maximum in branched polymers (creep)
• Stress maximum in branched polymers (SAXS)
• Challenges of Stress Relaxation
• True stress relaxation (SANS)
• Transient free surface viscoelastic flow (FEM)
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27 DTU Chemical Engineering, Technical University of Denmark
Steady-state Extensional Flow
Tube model parameters:Number of entanglements per chain: Z
Number of Kuhn steps per entanglement: Ne
Entanglement Relaxation time: τe
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28 DTU Chemical Engineering, Technical University of Denmark
Steady-state Extensional Flow
10-5 10-4 10-3 10-2 10-1103
104
105
.
PS-285k (Z=21.4) PS-545k/4k-52 (Z=21.6) PS-900k/4k-33 (Z=22.5) PS-1760k/4k-18 (Z=22.8) PS-3280k/4k-13 (Z=22.2)
η E / (G
0 N τc)
ετc
Bhattacharjee et al.(2002)
Bach et al.(2003)
Wid = 1 WiR = 1
Number of entanglements per chain: Z
Entanglement Relaxation time: τe
Number of Kuhn steps per entanglement: Ne
0 1 2 3 4 5 6 7104
105
106
107
WiR=6.10
WiR=2.03
WiR=0.61
WiR=0.20
<σzz
−σrr>
[Pa]
ε
PS-285k, Z=21
0 1 2 3 4 5 6 7103
104
105
106
107PS-1760k/4k-17, Z=21
ε
<σzz
−σrr>
[Pa]
WiR=10.31
WiR=3.43
WiR=1.03
WiR=0.34
WiR=0.21
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29 DTU Chemical Engineering, Technical University of Denmark
Steady-state Extensional Flow
Number of entanglements per chain: Z
Entanglement Relaxation time: τe
Number of Kuhn steps per entanglement: Ne
Reduction of monomeric frictionIanniruberto et al.(2012) & Yaoita et al.(2012):
10-1 100 101100
101
102
Solution-4k Solution-2k Solution-1k
/ (G
0 N τ R)
− η stea
dy
τR
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30 DTU Chemical Engineering, Technical University of Denmark
Steady-state Extensional Flow
PS melts & PMMA solutions
Z
Ne
τe
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31 DTU Chemical Engineering, Technical University of Denmark
Steady-state Extensional Flow
PS melts & PMMA solutions
Z
Ne
τe
Similar monomeric friction
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32 DTU Chemical Engineering, Technical University of Denmark
Steady-state Fracture
Fracture occurs on a fast time scale to make direct visual observations impossible
10-1 100 101100
101
102
Solution-4k Solution-2k Solution-1k
/ (G
0 N τ R)
− η stea
dy
τR0 1 2 3 4 5 6
103
104
105
106
107
WiR=32.4 WiR=11.3
WiR=6.5
WiR=3.2
WiR=1.1
ε
<σzz
−σrr>
[Pa]
PS-900k/4k-33, Z=22
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33 DTU Chemical Engineering, Technical University of Denmark
• Elongational viscosity of model linear polymers
• Elongational viscosity at processing (PE-A and PE-B)
• Elongational viscosity of model branched polymers
• Stress maximum in branched polymers (creep)
• Stress maximum in branched polymers (SAXS)
• Challenges of Stress Relaxation
• True stress relaxation (SANS)
• Transient free surface viscoelastic flow (FEM)
![Page 34: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/34.jpg)
34 DTU Chemical Engineering, Technical University of Denmark
Q. Huang et al., Rheol. Acta (2016)
Comparison of two commercial polyethylene samples
(PE-A and PE-C) both at 150C.
Extensional stress growth coefficient as function of time. Strain rate (from left to right): 1.0, 0.6, 0.4, 0.25, 0.15, 0.1, 0.06, 0.04, 0.025, and 0.01 (1/s).
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35 DTU Chemical Engineering, Technical University of Denmark
Extensional stress as function of strain. Strain rate (top to bottom): 1.0, 0.6, 0.4, 0.25, 0.15, 0.1, 0.06, 0.04, 0.025, and 0.01 (1/s).
Q. Huang et al., Rheol. Acta (2016)
Comparison of two commercial polyethylene samples
(PE-A and PE-C) both at 150C.
![Page 36: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/36.jpg)
36 DTU Chemical Engineering, Technical University of Denmark
Q. Huang et al., Rheol. Acta (2016)
Steady extensional viscosity (𝜂𝜂𝐸𝐸) as function of strain rate ̇𝜖𝜖.
Comparison of two commercial polyethylene samples
(PE-A and PE-C) both at 150C.
![Page 37: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/37.jpg)
37 DTU Chemical Engineering, Technical University of Denmark
• Elongational viscosity of model linear polymers
• Elongational viscosity at processing (PE-A and PE-B)
• Elongational viscosity of model branched polymers
• Stress maximum in branched polymers (creep)
• Stress maximum in branched polymers (SAXS)
• Challenges of Stress Relaxation
• True stress relaxation (SANS)
• Transient free surface viscoelastic flow (FEM)
![Page 38: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/38.jpg)
38 DTU Chemical Engineering, Technical University of Denmark
Comparison of model branchedpolymers:
Lin180180k
90k 90k 90k 90k
90k20k
Star20 Star90
Agostini et al., European Polymer Journal 49, 2769-2784(2013)
Rouse time: 85s at 130
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39 DTU Chemical Engineering, Technical University of Denmark
Linear Viscoelasticity
180k
90k 90k
90k
10-4 10-3 10-2 10-1 100 101 102
103
104
105
106
PS-Lin180
PS-Star90
TTS at 130°C
G', G
'' [Pa
]
ω [rad/s]
![Page 40: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/40.jpg)
40 DTU Chemical Engineering, Technical University of Denmark
Linear Viscoelasticity
180k
90k 90k
20k
10-4 10-3 10-2 10-1 100 101 102
103
104
105
106
PS-Lin180 PS-Star20
TTS at 130°C
G', G
'' [Pa
]
ω [rad/s]
![Page 41: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/41.jpg)
41 DTU Chemical Engineering, Technical University of Denmark
Extensional Flow
100 101 102 103 104
106
107
108
109
0.2s-1
Uniaxial extension at 130°C
0.0003s-1
0.003s-1
0.01s-1
0.03s-1
Star90 LVE envelope
− η+ [Pa.
s]
t [s]
0.1s-1
11/ 0.012sRτ −≈
![Page 42: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/42.jpg)
42 DTU Chemical Engineering, Technical University of Denmark
Extensional Flow
100 101 102 103 104
106
107
108
109
0.2s-1
Uniaxial extension at 130°C
0.0003s-1
0.003s-1
0.01s-1
0.03s-1
Star20 Star90 LVE envelope
− η+ [Pa.
s]
t [s]
0.1s-1
11/ 0.012sRτ −≈
![Page 43: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/43.jpg)
43 DTU Chemical Engineering, Technical University of Denmark
Extensional Flow
100 101 102 103 104
106
107
108
109
0.2s-1
Uniaxial extension at 130°C
0.0003s-1
0.003s-1
0.01s-1
0.03s-1
Lin180
Star90 LVE envelope
− η+ [Pa.
s]
t [s]
0.1s-1
11/ 0.012sRτ −≈
![Page 44: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/44.jpg)
44 DTU Chemical Engineering, Technical University of Denmark
Steady state
10-3 10-2 10-1 100 101 102
108
109
3η0 of Star90
3η0 of Star20
− η stea
dy [P
a.s]
Lin180 Star20 Star90
τR
3η0 of Lin180
-0.5
Entangled star PS behave like linear PS in the steady state of fast elongational flow
![Page 45: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/45.jpg)
45 DTU Chemical Engineering, Technical University of Denmark
• Elongational viscosity of model linear polymers
• Elongational viscosity at processing (PE-A and PE-B)
• Elongational viscosity of model branched polymers
• Stress maximum in branched polymers (creep)
• Stress maximum in branched polymers (SAXS)
• Challenges of Stress Relaxation
• True stress relaxation (SANS)
• Transient free surface viscoelastic flow (FEM)
![Page 46: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/46.jpg)
46 DTU Chemical Engineering, Technical University of Denmark
Viscosity overshoot in the start-up of uniaxial elongation of low density polyethylene melts, by H.K. Rasmussen, Nielsen, Bach and Hassager, J. Rheol. (2005)
Stress growth coefficient for BASF Lupolen 1840D and 3020D observed with first feedback loop on plate motion:
![Page 47: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/47.jpg)
47 DTU Chemical Engineering, Technical University of Denmark
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48 DTU Chemical Engineering, Technical University of Denmark
Creep compliance: J(t) = є(t)/ơ
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49 DTU Chemical Engineering, Technical University of Denmark
Compliance: Comparison shear vs. extension:
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50 DTU Chemical Engineering, Technical University of Denmark
Comparison constant stress (creep) vs. constant strain rate:
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51 DTU Chemical Engineering, Technical University of Denmark
Comparison constant stress (creep) vs. constant strain rate:
Alvarez et al., Physical Review Letters, (2013).
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52 DTU Chemical Engineering, Technical University of Denmark
• Elongational viscosity of model linear polymers
• Elongational viscosity at processing (PE-A and PE-B)
• Elongational viscosity of model branched polymers
• Stress maximum in branched polymers (creep)
• Stress maximum in branched polymers (SAXS)
• Challenges of Stress Relaxation
• True stress relaxation (SANS)
• Transient free surface viscoelastic flow (FEM)
![Page 53: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/53.jpg)
53 DTU Chemical Engineering, Technical University of Denmark
www.rheofilament.com
Oven surroundingsample can be lifted up for rapid quenching of
sample
Knob for lifting oven
VADER 1000
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54 DTU Chemical Engineering, Technical University of Denmark
SAXS (top) and WAXD (bottom) patterns of LDPE filaments quenched at various stress (a) 30, (b) 126, (c) 262, and (d) 518 kPa. All filaments have been elongated at T = 130C, and flow direction is vertical.
Wingstrand et al., Macromolecules (2017)
Ex-Situ X-ray Measurements on quenched filaments:
Aligned lamellaeplanes perpendicular to flow (vertical) direction (kebabs) with some variation in spacing.
![Page 55: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/55.jpg)
55 DTU Chemical Engineering, Technical University of Denmark
Wingstrand et al., Macromolecules (2017)
Visual appearance of SAXS patterns suggest correlation with stress (before and after maximum).
The X-ray wavelength was 1.54 Å for both WAXD and SAXS while the distance to the detector was ∼118 mm for the WAXD measurements and either ∼1020 or ∼2240 mm for the SAXS measurements.
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56 DTU Chemical Engineering, Technical University of Denmark
Herman’s orientation factor vs stress at quench. All samples have been stretched at T = 130C except (green) which have been stretched at varying T from 110 to 130C.
Herman’s orientation factor vs average stretch of the backbone for the two highest Maxwell models. Vertical lines indicate regions of different morphologies.
Herman’s orientation factor for SAXS patterns confirm uniquerelation between stress before quench and crystalline orientation.
Wingstrand et al., Macromolecules (2017)
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57 DTU Chemical Engineering, Technical University of Denmark
• Elongational viscosity of model linear polymers
• Elongational viscosity at processing (PE-A and PE-B)
• Elongational viscosity of model branched polymers
• Stress maximum in branched polymers (creep)
• Stress maximum in branched polymers (SAXS)
• Challenges of Stress Relaxation
• True stress relaxation (SANS)
• Transient free surface viscoelastic flow (FEM)
![Page 58: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/58.jpg)
58 DTU Chemical Engineering, Technical University of Denmark
Evolution of filament diameter, D(t), and plate separation, L(t), for an elongationalrate of 0.03 s−1 at 120C, stretched for 100 s and then relaxed. D0=3.40 mm and L0=8.82 mm.
Failure by necking after about 60 s relaxation.
Nielsen et al., J. Rheol. (2008)
Sample: NMMD polystyrene
Mw = 145 kg/mol, 120C.
The incorrect stress relaxation experiment: ̇𝜖𝜖𝑁𝑁 = 0
No feed-back control
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59 DTU Chemical Engineering, Technical University of Denmark
Note: The true stress actually increases with time in (some) uncontrolledstress relaxation experiments!
How do you report stress in uncontrolled stress relaxation experiments?
• True stress?
• Engineering stress?
J. Rheol. 524, 885-899 July/August 2008 0148-6055
Stress relaxation after 𝜖𝜖 = 3
Total time 14400 s = 4 h
The incorrect stress relaxation experiment: ̇𝜖𝜖𝑁𝑁 = 0
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60 DTU Chemical Engineering, Technical University of Denmark
• Elongational viscosity of model linear polymers
• Elongational viscosity at processing (PE-A and PE-B)
• Elongational viscosity of model branched polymers
• Stress maximum in branched polymers (creep)
• Stress maximum in branched polymers (SAXS)
• Challenges of Stress Relaxation
• True stress relaxation (SANS)
• Transient free surface viscoelastic flow (FEM)
![Page 61: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/61.jpg)
61 DTU Chemical Engineering, Technical University of Denmark
Evolution of plate separation L(t) and mid-filament diameter D(t).
145 kg/mol polystyrene at 120 C.
Elongation rate 0.03 s-1 for 0 < t < 100 s.
For t > 100 s the plates are either held fixed (left) or controlled to keepmid-filament diameter constant (right)
D0=3.40 mm, L0=8.82mm
The correct stress relaxation experiment: ̇𝜖𝜖 = 0
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62 DTU Chemical Engineering, Technical University of Denmark
145 kg/mol polystyrene at 120 C. Elongation rate 0.03 s-1 for 100 s.
Samples quenched after [0, 7, 47, 126, 350, 3000, 7000] s of relaxation
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K.Mortensen, Q.Huang, O. Hassager, J. Kirkensgaard, K. Almdal, C. Garvey
Anine Borger, PhD student, Niels Bohr Institute.AERC 2018, Sorrento, April 18th
Star polymer relaxation after fast extensional flow using neutrons
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64 DTU Chemical Engineering, Technical University of Denmark
Filament stretch rheometer
Hencky strain
Control scheme:•Stretch at constant Hencky strain rate
•Stress relaxation at constant Hencky strain
21/08/201864
A. Bach et al, J. Rheol., 47(2), 429-441 (2003)
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65 DTU Chemical Engineering, Technical University of Denmark
Branched polymers behave like linear in steady state of fast extensional flow
21/08/201865
Q. Huang et al. Macromolecules 2016, 49, 6694-6699
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66 DTU Chemical Engineering, Technical University of Denmark
The relaxation of star and linear polymers differ at long time scales
21/08/201866
Q. Huang et al. Macromolecules 2016, 49, 6694-6699
I : < 15 sII: 15-500 s
III: >500 s
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67 DTU Chemical Engineering, Technical University of Denmark
Two model sample series for neutron scattering
21/08/201867
Random deuterated End-deuteratedArm length 100 kWiR 27Relaxation times (s) 0, 10, 100, 1000,
fully0, 5, 200, 4000, fully
I : < 15 sII: 15-500 s
III: >500 s
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68 DTU Chemical Engineering, Technical University of Denmark
Neutron scattering data: Setup
21/08/201868
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69 DTU Chemical Engineering, Technical University of Denmark
Neutron scattering: Correlations and sizes
21/08/201869
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70 DTU Chemical Engineering, Technical University of Denmark
Neutron scattering: Correlations and sizes
21/08/201870
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71 DTU Chemical Engineering, Technical University of Denmark
Neutron scattering: Correlations and sizes
21/08/201871
•Characteristic distances in the sample give peaks in intensity
•Scattering maps reciprocal space
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72 DTU Chemical Engineering, Technical University of Denmark
Neutron scattering: Correlations and sizes
21/08/201872
•Characteristic distances in the sample give peaks in intensity
•Scattering maps reciprocal space
•Scattering vector
![Page 73: Lecture 7 and 8: Extensional Rheology · DTU Chemical Engineering, Technical University of Denmark. Steady-state Extensional Flow. 10-5. 10-4. 10-3. 10-2. 10-1. 10. 3. 10. 4. 10.](https://reader036.fdocuments.in/reader036/viewer/2022071510/612e935c1ecc51586942e6ac/html5/thumbnails/73.jpg)
73 DTU Chemical Engineering, Technical University of Denmark
Random-deuterated stars
21/08/201873
0 s 10 s
100 s 1000 s
Fully relaxed
PSI: SANS-I
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74 DTU Chemical Engineering, Technical University of Denmark
End-deuterated stars: Expectation
21/08/201874
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75 DTU Chemical Engineering, Technical University of Denmark
End-deuterated stars
21/08/201875
0 s 5 s
200 s 4000 s
Fully relaxed
0s and fully relaxed: K. Mortensen et al., accepted for publication(2018) ANSTO: QUOKKA
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76 DTU Chemical Engineering, Technical University of Denmark
Polystyrene: 𝑎𝑎 = 85 Å
Total length: 2 𝑁𝑁𝑎𝑎𝑎𝑎𝑎𝑎𝑏𝑏 = 4960 Å
Length of oriented tubes: 2 𝑍𝑍𝑎𝑎𝑎𝑎𝑎𝑎 𝑎𝑎 = 1040 Å
Measured axial diatance: 1300 Å
Measured transverse distance: 100 Å
Conclusions:
Oriented tube elements with small stretching.
Arms more or less inside one tube section.
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• Elongational viscosity at processing (PE-A and PE-B)
• Molecular extensional rheology (model polymers)
• Stress maximum in branched polymers (creep)
• Stress maximum in branched polymers (SAXS)
• Challenges of Stress Relaxation
• True stress relaxation (SANS)
• Transient free surface viscoelastic flow (FEM)
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All materials:
Mass: 𝛻𝛻 � 𝑣𝑣 = 0
Force: 𝜌𝜌 𝜕𝜕𝜕𝜕𝜕𝜕
+ 𝑣𝑣 � 𝛻𝛻 𝑣𝑣 = −𝛻𝛻𝑝𝑝 + 𝛻𝛻 � 𝜎𝜎
Newtonian liquids:
True Stress: 𝜎𝜎 𝑡𝑡 = 𝜇𝜇�̇�𝛾 𝑡𝑡
Viscosity: 𝜇𝜇
Rate-of-deformation tensor: �̇�𝛾 = [𝛻𝛻𝑣𝑣 + 𝛻𝛻𝑣𝑣 † ]
Polymeric liquids:
True Stress: 𝜎𝜎 𝑡𝑡 = 𝜎𝜎{𝑣𝑣 𝑡𝑡′ , 𝑡𝑡′ ∈ −∞; 𝑡𝑡 }
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79 DTU Chemical Engineering, Technical University of Denmark
All materials:
Mass: 𝛻𝛻 � 𝑣𝑣 = 0
Force: 𝜌𝜌 𝜕𝜕𝜕𝜕𝜕𝜕
+ 𝑣𝑣 � 𝛻𝛻 𝑣𝑣 = −𝛻𝛻𝑝𝑝 + 𝛻𝛻 � 𝜎𝜎
Polymeric liquids:
True Stress: 𝜎𝜎 𝑡𝑡 = 𝜎𝜎{𝑣𝑣 𝑡𝑡′ , 𝑡𝑡′ ∈ −∞; 𝑡𝑡 }
Simulations of transient viscoelastic flow:
Lagrangian finite element method.
Yu, Marin, Rasmussen and Hassager,
J. Non-Newtonian Fluid Mech. 165 (2010)
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80 DTU Chemical Engineering, Technical University of Denmark
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Wang, Boukani, Wang and Wang, PRL 99, 237801 (2007)SER fixture coupled to an Anton Paar MCR 301 rotational rheometer.
Relaxation with ̇𝜖𝜖𝑁𝑁 = 0 constant nominal Hencky strain mayresult in highly inhomogeneous flow and necking.
2D planar simulation by
Lyhne, Rasmussen and Hassager
PRL 102, 138301 (2009)
Necking close to cylinder:
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3D simulation of inhomogeneous ”stress reaxation” by Yu, Marin, Rasmussen and Hassager, J. Non-Newtonian Fluid Mech. (2010).
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83 DTU Chemical Engineering, Technical University of Denmark
Yu, Marin, Rasmussen
3D simulation of inhomogeneous ”stress reaxation” by Yu, Marin, Rasmussen and Hassager, J. Non-Newtonian Fluid Mech. (2010).
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84 DTU Chemical Engineering, Technical University of Denmark
Influence of non-linear material behavior on inhomogeneous deformation in dual-drum wind-up apparatus.
Left: neo-Hookeanrubber material
Right: Doi-Edwards (independent alignment) tube model.
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The Danish Council for Independent Research
The Aage and Johanne Louis-Hansen Foundation
The European Science Foundation
The Otto Mønsted Foundation
The work was funded by:
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Nominal Hencky strain as function of true Henckystrain for constant rate experiment with LDPE.
Nominal Hencky strain as function of true Henckystrain for constant rate experiment with polystyrenesolution.
Nominal Hencky strain: 𝜀𝜀𝑧𝑧 = ln(𝐿𝐿(𝑡𝑡)/𝐿𝐿0)
True Hencky strain: 𝜖𝜖 = 2 ln 𝐷𝐷0/𝐷𝐷(𝑡𝑡)
(Similar difference between Engineering stress vs. true stress.)
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Historical:Extensional Rheometer Designs
Meissner and Hostettler (1994), conveyor belt
Meissner (1969), (1971), rotary clamp
Sentmanat (2004): SER
TA: EVF
Münstedt and Laun (1979)