utilisation de la rhéologie pour controller les propriétés
TRANSCRIPT
Nicole R. Demarquette [email protected]
École de Technologie Supérieure
Université du Québec Montréal (Québec), CANADA
Utilisation de la rhéologie pour controller les propriétés de mélanges et nanocomposites à base de
thermoplastiques
Le 18 septembre 2018
1
• Fondée en 1974 • Fait partie du réseau de l’UQ • École de Génie 11000
étudiants (3000 aux études supérieures)
• Génie de la contruction, électrique, production automatisée, mécanique, logiciel, opérations et de la la logistique, technologies de l’information
2 École de Technologie Supérieure
2
ÉTS située au cœur de Montréal
L’été à Montréal – “Joie de vivre”
5
6
Les Plastiques
Polyethylene
Polypropylene PVC
ABS
PET
ABS
Nylon
Polycarbonate OLEDS
Polymères Intelligents
Coût de la recherche : une quinzaine de millions de dollars jusqu’à l’usine pilote
Nouveau matériau polymérique avec de meilleures propriétés
Nouvelle molécule ??
Que faire?
Polymère A Polymère B
• Synergisme de propriétés • Coût de développement plus faible • Donne des alternatives pour le recyclage
Mélanges
10 mícrons
80/20 HDPE/PP blend
Composites Constitué de plus d’un type de matériau Matrice: Polymère Phase dispersée Conçu pour bénéficier des propriétés des deux matériaux
Traditional
Carbon fibers in thermoplastic matrix
Echelle micro
• Propriétés exceptionnelles • Matériaux légers
Antibacterial thermoplastics
Nanocomposites
Echelle Nano
Souza, AMC; Demarquette,NR POLYMER Volume: 43 Issue: 14 Pages: 3959-3967
• Marché des mélanges de 40 milliards de dollars qui croît à 4,4% par an
• Marché des nanocomposites croît à 20% par an
• Nombre d’articles scientifiques qui croît exponentiellement
Importance de ces matériaux
Que faire ?
Il faut domestiquer leur morphologie pour contrôler leurs propriétés fonctionnelles
12
Control Polymer Blends,
Nanocomposites, Block Copolymers
Morphology to Taylor their Engineering
Properties
Blend Compatibilization
Microsphere for Filtration Using Polymer Blends
Improvement of Mechanical Properties of PHA
Blends Fibers with Controlled Surface Properties
Coaxial Electrospinning of PNVCL\PCL: Thermo-responsive polymers
Blending to control drug delivery
Configuration of Coaxial E lectrospinning setup used for preparing Core-Shell fibers
SE M image of PNV CL /PCL and PE G/ Ketoprofene Core-Shell nanofibers
2
MarwaSta
100nm
5 mm
TuyauBlends of Thermosensitive
Polymers for Drug Delivery Applications
SEBS Block Copolymer with Clays for DC Cables
SpiderWeb
Piezoelectric Membranes of Copolymers for Sensors
Rubber Blend with Optimized
Mechanical Properties For Tires
Control Polymer Blends,
Nanocomposites, Block Copolymers
Morphology to Taylor their Engineering
Properties
3 mm
Helal, Demarquette et al, Polymer2016, 2017 Carastan, Demarquette et al: EPJ, 2013 Rezageibi, Demarquette et al: JAPS, Macromolecules, 2018 Kurusu, Demarquette: Langmuir 2015, 2016 Genoyer, Demarquette et al: JOR, 2017 Bizi, Demarquette, JAPS, 2008 Valera, Demarquette, EPJ, 2008
Graphene CNT Composites For EMI Shielding
Blends, Block Copolymers and Nanocomposites
7
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[1] Eva Mårtensson, Modelling electrical properties of composite materials , Thesis submitted to Kungl Tekniska Högskolan Department of Electrical Engineering Division Electrotechnical Design Stockholm, Sweden, 2003.
http://www.magdahavas.com/microwave-radiation-affects-the-heart-are-the-results-real-or-are-they-due-to-interference/
http://www.spira-emi.com/theory.htm
http://sarveshie.blogspot.ca/2012_08_01_archive.html
Semi-conductive screen materials for power cables
Stress grading materials for HVDC applications
EMI shielding
Cable termination including a field grading material [1]
Conductive Composites
Conductive Nanocomposites: Graphene
14
• Single of few-layer Graphene sheet – Remarkable properties; – Difficult to produce in large-scale.
Source:https://www.sciencenews.org/article/%E2%80%98impermeable%E2%80%99-graphene-yields-protons
Source:http://www.mechscience.com/graphite-structure-crystallography/
graphene
graphite
• Graphene produced in large-scale – Mechanochemical exfoliation of graphite; – More layers (average thickness of 20
nm).
• Incorportation in polymers by melt mixing to obtain conductive composites
10
15
Helmut Münstedt, and Zdeněk Starý,.. Polymer, Volume 98, 19 August 2016, Pages 51-60
Percolation Threshold
Suitable morphology
Difficult by melt-mixing
16
Objective
Prepare conductive composites with the low percolation using a commercial
graphene grade and an industrial process.
17
Blending
• Mixing 2 polymers – Immiscible blends
Relative amount of polymer B in the immiscible blend
Polymer B
Polymer A
18
Materials
Commercial graphene grade (GN) heXo-G V20 (provided by NanoXplore) Average thickness: 20 nm. Average flake size: 50 µm. Ethyl vinyl acetate (EVA) Polar matrix. Better affinity to GN. Linear low density polyethylene (LLDPE) Low viscosity .
(Scale bar = 50 µm)
Selective location of GN in EVA/LLDPE blend
19
Based on surface energy, interfacial tension graphene (GN) has greater chemical affinity with EVA
PE EVA
GN
γ (mJ.m-2) γd (mJ.m-2) γp (mJ.m-2)
PE [3] 35.7 35.7 0
EVA [4] 27.4 20.8 6.6
Graphene [5, 6] 53 39.1 13.9
But processing sequence and kinetics can affect 15
Processing Twin screw extrusion ( 2 runs) Temperature: 160 °C Compression molding at 160 °C 50/50 blend
Order of processing
EVA master batch (EVAMB)
LLDPE master batch (LLDPEMB)
Polymer + + Graphene
PE EVA GN
PE EVA GN
16
21
Design of Blend Morphology
Condition for co-continuity: Φ1/ Φ2= η1/ η2
[ordhamo, G.M., Manson, J.A. and Sperling, L.H, Phase continuity and inversion in polymer blends and simultaneous interpenetrating networks, Polym. Eng. Sci., 1986, 26, pp. 517-524.
SEM image of unfilled LLDPE/EVA blend (50wt%/50wt%)
(scale bar = 100 µm, EVA dissolved by toluene)
Co-continuous morphology expected
100 µm
Co-continuous morphology for all blends
Results – Electrical conductivity
22
Materials prepared from LLDPE
masterbatch feature the lowest
percolation: More GN particles
located at the interface
1E-15
1E-14
1E-13
1E-12
1E-11
1E-10
1E-09
1E-08
1E-07
1E-06
1E-05
1E-04
1E-03
1E-02
1E-01
0 5 10 15 20 25
Con
duct
ivity
(S/m
)(σ'
at 1
0-2 H
z)
φ (%)
EVA/GN
LLDPE/GN
EVA/LLDPE/GN (EVA MB)
EVA/LLDPE/GN (LLDPE MB)
EVAMB
LLDPEMB
Results – Small Amplitude Oscillatory Shear
23
A plateau appears at 1.3 vol% GN and higher.
EVAMB
LLDPEMB
Is it the effect of formation of interfacial GN network or a change in blend’s morphology or both?
24
• From EVA masterbatch:
EVA/LLDPE EVA/LLDPE + 1.3 vol% GN
EVA/LLDPE + 2.2 vol% GN
EVA/LLDPE + 3.3 vol% GN
Results – Morphologies of blends
100 µm 100 µm
100 µm 100 µm
25
• From LLDPE masterbatch:
LLDPE/EVA LLDPE/EVA + 1.3 vol% GN
LLDPE/EVA + 2.2 vol% GN
LLDPE/EVA + 3.3 vol% GN
Results – Morphologies of blends
100 µm 100 µm
100 µm 100 µm
26
• Characteristic Domain Size ξ (ImageJ) – ξ = Total area / Interfacial length
Results – Morphologies of blends
100 µm 100 µm
27
0
1
2
3
4
5
6
7
8
9
0 1 2 3 4
Dom
ain
Siz
e ξ
(µm
)
φ % GN
EVA/LLDPE (EVA MB)EVA/LLDPE/GN (LLDPE MB)
Results – Morphologies of blends
8,6.10-6 S/m
1,2.10-4 S/m
EVA masterbatch
LLDPE masterbatch
28
• From LLDPE masterbatch:
10 µm 50 µm
10 µm
Results – Morphologies of blends
10 µm 50 µm
10 µm
29
• Electrical conductivity
Effect of Annealing at 160oC for 2 hours
30
100 µm
100 µm
100 µm
100 µm
100 µm
100 µm
100 µm
100 µm
100 µm
100 µm
100 µm
100 µm
Effect of Annealing at 160oC for 2 hours • Morphology
31
• LLDPE/EVA/1.3GN (EVAMB) (EVA phase dissolved by toluene):
0 min 28 min
95 min 75 min
Effect of Annealing at 160oC
100 µm 100 µm
100 µm 100 µm
32
• LLDPE/EVA/1.3GN (LLDPEMB) (EVA phase dissolved by toluene):
0 min 28 min
95 min
Effect of Annealing at 160oC
100 µm 100 µm
1 µm 1 µm
75 min
Conclusions
• Conductive composites with low percolation have been prepared using commercial GN grade and an industrial process.
• LLDPE/EVA (50 /50) and LLDPE/EVA/GN composites feature a co-continuous morphology.
• The addition of graphene results in a finer morphology.
• The processing sequence affects the location of GN and the electrical conductivity. When GN is added to LLDPE it is located at the interface and results in a reduction of percolation threshold is reduced in the blends (1.3 vol% GN, 10-8 S/m)
• Annealing of the blends results in an increase of conductivity due to a coarsening of co-continuous morphology and migration of graphene to interface when graphene was incorporated in LLDPE
33
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EMI Shielding Materials Charge Carriers Electric and/or Magnetic Dipoles
Metals are the most used materials for EMI shielding.
Metallic materials High Density Prone to Corrosion Shielding Mechanism only by Reflection
Disadvantages
. Lower Density Easier Processability Shielding Mechanism by Reflection and Absorption
Alternative:
Polymer-Carbon Composites
Advantages
Need to Tailor the Morphology ! 35
Nanocomposites for EMI shielding
35
Materials • Poly(styrene-b-(ethylene-co-butylene)-b-styrene)
• Styrene content = 30 wt%; cylindrical morphology; Melt flow index < 1g/10 min
• Expanded Graphite • Micrograf HC 30; Nacional de Grafite Ltda, Brazil • Surface area 26 m2.g-1; Bulk density 1.8 g.cm-3
• Carbon Black,
• Degussa Brazil • Surface area 1000 m2g-1,Bulk density 1.9 g cm-3
• Multiwalled Carbon Nanotube (MWCNT)
• Nanocyl NC 7000 • Surface area: 250-300 m2.g-1, Bulk density: 0.06 g.cm-3
• Carbon purity: 99.5%
• Graphene: • XG Science, • Surface area : 120-150 m2.g-1, Bulk density: 0.03-0.1 g.cm-3 • Carbon purity: 90%
Block Copolymers
Spherical Cylindrycal Lamellar
1. Amurin L.G, Carastan D.J, Demarquette N.R, Journal of Rheol ogy, 60(1), 175-189, 2016
Block Copolymers
Block A Block B
Thermoplastic Elastomers
36
Experimental Procedures
• Obtention of Composites by melt mixing
Post-Processing
Extrusion
Compression Molding
SEBS
Carastan D.J, Demarquette N.R et al: European Polymer Journal, 2014, Polymer 2017
37
SEBS/GP
(wt.%)
Low
frequency
slope of log
G’ vs. log ω
0 0.32
0.8 0.32
1 0.30
2 0.27
5 0.24 a
Similar behavior was obtained for the EG and CB composites
Kuester S.,et al, European Polymer Journal, 2016, 2017
Results – Small Amplitude Oscillatory Shear
SEBS/CNT
(wt.%)
Low
frequency
slope of
log G’ vs. log
ω
0 0.32
0.8 0.22
1 0.19
2 0.14
3 0.11
5 0.05
a
𝐺′𝛼 𝑚 −𝑚𝑐𝑡
G’: Storage modulus m: mass fraction of filler; mc: mass fraction at percolation threshold; t: critical exponent
Filler type mc (wt%)
CB 2.6
EG 7
GPn 7
CNT 0.8
Kuester S., Demarquette N.R. et al, European Polymer Journal, 2016, 2017 29
Results – Small Amplitude Oscillatory Shear
Carbon black
Graphene Carbon nanotube
1.2 wt. % CNT σ increase of 16 orders of magnitude
Expanded graphite
Kuester S., Demarquette N.R. et al, European Polymer Journal, 2016, 2017 36
Results – Electrical Conductivity
40
Filler type mc (wt%)
CB 2.6
EG 7
GPn 7
CNT 0.8
Filler type mc (wt%)
CB 5
EG 9
GPn 12
CNT 1.4
𝐺′𝛼 𝑚 −𝑚𝑐𝑡
G’: Storage modulus;
m: mass fraction of filler; mc: mass fraction at percolation threshold; t: critical exponent
𝜎 𝛼 𝑚 −𝑚𝑐𝑡
𝜎 : Electrical conductivity;
m: mass fraction of filler; mc: mass fraction at percolation threshold; t: critical exponent
Results – Percolation Threshold
𝐸𝑀𝐼 𝑆𝐸 = 𝑆𝐸𝑅 + 𝑆𝐸𝐴 (𝑑𝐵)
𝑆𝐸𝑅 = 10 𝑙𝑜𝑔𝐼
𝐼 − 𝑅
𝑆𝐸𝐴 = 10 𝑙𝑜𝑔𝐼 − 𝑅
𝑇 Expanded graphite Carbon black
0
5
10
15
20
25
30
0 5 10 15 20EG content (wt. %)
SEA (dB)SER (dB)
0
5
10
15
20
25
30
3 5 7 10 15
EMI S
E (d
B)
CB content (wt. %)
SEA (dB)
SER (dB)
Graphene Carbon nanotube
0
5
10
15
20
25
30
3 5 8 10 15
EMI S
E (d
B)
CNT content (wt. %)
SEA (dB)SER (dB)
0
5
10
15
20
25
30
2 5 7 10 15
Graphene Content (%wt)
SEA (dB)
SER (dB)
38
Results – EMI Shielding Efficiency
Hybrid composites
8/2 CNT/GR = 23.42 dB
10/5 CNT/GR = 36.47 dB 15 CNT = 30.07 dB
10 CNT = 20.78 dB
Same amount of single filler of higher efficiency
Kuester S., Demarquette N.R. et al, European Polymer Journal, 2016, 2017 39
Results – EMI Shielding Efficiency
43
Random
Oriented
0 1 2 3 4 5 6 7 8 91E-13
1E-11
1E-9
1E-7
1E-5
0.001
AC
ele
ctric
al c
ondu
ctiv
ity (S
.cm
-1)
CNT (wt%)
Compression SEBS/CNT Extrusion SEBS/CNT
Results – Results effect of post-processing
0 2 4 6 8
0
10
20
30
40
50
60
CNT (wt%)
EMI-S
E (d
B)
8
10
12
14
16
18
SEBS/CNT extrusion SEBS/CNT compression
Ten
sile
str
engt
h (M
Pa)
0
10
20
30
40
50
60
0 2 3 5 8
EMI S
E (d
B)
CNT content (wt. %)
SEA…SER…
0
10
20
30
40
50
60
0 2 3 5 8
EMI S
E (d
B)
CNT content (wt. %)
SE…SE…
44
Addition of CNT resulted in highest electrical conductivity, lower electrical percolation
threshold.
Addition of CNT resulted in the highest EMI shielding effectiveness
With CNT wt% > 5, absorption was the main shielding mechanism.
Hybrid composites of SEBS/CNT/GR presented synergistic effect on SE.
Nanocomposites prepared by compression presented higher AC electrical conductivity,
lower percolation threshold and slightly higher EMI-SE.
SEBS/CNT with 5 wt% of CNT prepared compression molding presented an excellent
balance of EMI-SE and mechanical properties.
Conclusions
• Rhéologie : Étude de l’écoulement de la matière
• Équations Constitutives Contrainte = f (Déformation, Interface, Fraction en
volume, Morphologie)
Déformation Contrainte
Études Théoriques : Comment la morphologie se forme ?
Études rhéologiques
Polymers are Viscoelastic
19/09/2018
t
g
t
s
t
s
t
s
Études Théoriques : Comment la morphologie se forme ?
Études rhéologiques
• Viscoélasticité linéaire – Petites déformations lentes – On peut l’utiliser pour caractériser la morphologie
• Viscoélasticité non linéaire
– Déformations larges et rapides – Utiles pour étudier l’évolution de la morphologie au cours de la mise en forme
Études théoriques : Comment la morphologie se forme ?
Études rhéologiques
Viscoélasticité linéaire : Petites déformations lentes
t
g
t
g
t
s Phase dispersée dans un mélange de polymères
Nanoparticules
dhg
0 G
d
d: diamètre des gouttes de la phase dispersée, η: viscosité; γ: vitesse de cisaillement; Γ: tension interfaciale
Déformation
Contrainte
)sin()( tt o gg
)cos()(' g
s
o
oG
)sin()(" g
s
o
oG
´G´´GTan
)sin( ss to
Viscoélasticité linéaire : Petites déformations lentes
50
Polymer A + Polymer B
≈1
≈2
ω (rad/s) t (s)
H(t
).t
(Pa.
s)
Small Angle Oscillatory Shear
Linear viscoelasticity
Constitutive equations Stress = f (Deformation, Interface, Volume Fraction, Morphology)
Viscoélasticité linéaire : Petites déformations lentes
0 5 10 15 200,0
0,1
0,4
0,5
Vol
ume
Ave
rage
Rad
ius
(mm
)
Compatibilizer (wt%)
Blend 90/10 Blend 80/20
PMMA+ PS + Random Copolymer
M. Yee, Calvao P. N.R. Demarquette, RA 2007. 50
Effect of Blend Concentration
0,01 0,1 1 10 1001
10
100
1000
10000
100000
Sto
rage
Mod
ulus
(Pa)
Frequency (rad/s)
PS PMMA PMMA/PS 70/30 PMMA/PS 80/20 PMMA/PS 90/10
P.S. Calvão, M. Yee, N.R. Demarquette, Polymer, 2005, 2610-2620
Effect of Blend Concentration
47
τf: Relaxation time of the dispersed phase; Γ: Interfacial Tension; K: Viscosity Ratio; Rv: Radius of dispersed phase;
)(Φ)(
))(Φ)(((
Γ 2521101321619
KK
KKKR mvη
1E-3 0,01 0,1 1 10 100
0
1000
2000
3000
4000
5000PMMA
PS
90/10 80/20
H (
). (
) (P
a.s)
Time (1) (s)
P.S. Calvão, M. Yee, N.R. Demarquette, Polymer, 2005, 2610-2620 48
Effect of Blend Concentration
Blend Composition
Rv (μm) Rheology
Rv (μm) Microscopy
90/10 0.12 0.13
85/15 0.23 0.24
80/20 0.33 0.35
75/25 1.1 1.0
70/30 1.5 1.6
P.S. Calvão, M. Yee, N.R. Demarquette, Polymer, 2005, 2610-2620 49
Effect of Blend Concentration
Polyamide: Nylon Polivynil butiral
0200400600800
1000120014001600
Poliamida:PA
PA + 20%PVB
PA + 40%PVBR
esis
tên
cia
ao Im
pac
to (
J/m
)
Valera T.S., Demarquette N. R“Polymer Toughening Using Residue of Recycled Windshields: PVB film as impact modifier”,, European Polymer Journal, 44, 3, pg 755-768, 2008
19/09/2018
Recycling
Polyvinyl butiral
Polyamide
All the blends presented a dispersed droplet type morphology 19/09/2018
Recycling
57
0.1
200
400
600
800
1000
1200
1400
1600Im
pa
ct S
tre
ng
th (
J/m
)
Interparticular distance (mm)
60/40 Blend
70/30 Blend
80/20 Blend
90/10 Blend
Valera T.S., Demarquette N. R“Polymer Toughening Using Residue of Recycled Windshields: PVB film as impact modifier”, Eurpean Polymer Journal, 44, 3, pg 755-768, 2008
Recycling
• Improvement of properties • Better distribution • Morphology more uniform • More stable morphology
8
10 mícrons
Block copolymer
Nanoparticles
42
Compatibilization of Polymer Blends
• Improvement of properties • Better distribution • Morphology more uniform • More stable morphology
8
10 mícrons
• Reduction of size of dispersed phase
• Improves adhesion between the phases
• Reduce interfacial tension • Prevents coalescence
– What are the phenomena?
HOW TO EVALUATE • Microscopy • Spectroscopy • Interfacial tension • Rheology
46
Compatibilization of Polymer Blends
60
Polymer A + Polymer B
≈1
≈2
ω (rad/s) t (s)
H(t
).t
(Pa.
s)
Small Angle Oscillatory Shear
Linear viscoelasticity
Constitutive equations Stress = f (Deformation, Interface, Volume Fraction, Morphology)
Blends Rheology
10-2 10-1 100 101 10210-2
10-1
100
101
102
103
104
105
106
10-2 10-1
10-1
100
101
102
103
Sto
rage
Mod
ulus
(Pa)
Frequency (rad/s)
PS PMMA 80/20 80/20/04 80/20/10
S
tora
ge M
odul
us (P
a)
Frequency (rad/s)
PS PMMA 80/20 80/20/04 80/20/10
M. Yee, P.S. Calvão, N.R. Demarquette, Rheologica Acta, 46, 5, 653-664 2007 51
Effect of Compatibilization
0,01 0,1 1 10 100
101
102
103
104
PMMA/PS (95/05)
F
H
().(
)(P
a.s)
Time () (s)
PS PMMA 95/05 95/05/08 95/05/10
M. Yee, P.S. Calvão, N.R. Demarquette, Rheologica Acta, 46, 5, 653-664 2007 51
Results: Effect of Compatibilization
Interface is not totally covered by compatibilizer
Relaxation of the Shape of the Droplets f
Relaxation of Marangoni Stresses
52
Results: Effect of Compatibilization
64
Polymer grade supplier Viscosity (0)
(Pa.s) at 200
°C PMMA1 DHAF Metacrill 24 000
PMMA2 PLEXIGLASS 6N Evonik 12 000
PS1 N1841 InNova 3 200
PS2 EMPERA 350N INEOS
Styrenics 9 800
Organomodified by
dimethyl dihydrogenated
tallow ammonium
Polystyrene Poly(methyl methacrylate)
Polymer A + Polymer B
Clay Acronym Shape Size Surface Area
(m²/g)
Surfactant Concentration
(mg/m²)
Cloisite Na MMT
150-250 nm 750
0
Cloisite Na modifiée mMMT 0,46
Cloisite 20A C20A 0,95
+ Compatibilizer
Block copolymer Name Mn (g/mol) Mw/Mn
PS-b-PMMA BC1 30 000 <1,2
BC2 104 000 <1,2
n
Materials
0.01 0.1 1 10 10010-1
100
101
102
103
104
0.01 0.1 1 10 10010-1
100
101
102
103
104H
().
(Pa.
s)
(s)
Pure PMMA PS BC1 0.2% BC1 0.5% BC1 1%
H(
). (P
a.s)
(s)
Pure BC2 0.2% BC2 0.5% BC2 1%
54
PMMA2+ PS2 + CB
No change of morphology Decrease of Interfacial Tension Marangoni Stresses
0.0 0.2 0.4 0.6 0.8 1.00
1
2
3
4
5
6
Pure BC1 BC2
a (m
N/m
)
% of BC
0.0 0.2 0.4 0.6 0.8 1.00.0
0.2
0.4
0.6
Pure BC1 BC2
Rv (
µm)
% of BC
0.01 0.1 1 10 100102
103
104
105H
().
(Pa.
s)
(s)
Pure BC1 0.2 % BC1 0.5 % BC1 1 % 200 °C
170 °C PMMA & PS
τF τβ τβ
𝜏𝛽 𝐵𝐶1 < 𝜏𝛽(𝐵𝐶2)
𝑴𝒏 𝑩𝑪𝟏 < 𝑴𝒏(𝑩𝑪𝟐)
Results: Effect of Compatibilization
0.01 0.1 1 10 100100
101
102
103
104
105
G' (
Pa)
(rad/s)
strain=0
Pure
0.01 0.1 1 10 100100
101
102
103
104
105
G' (
Pa)
(rad/s)
strain=0 strain=10 % (3)
Pure
0.01 0.1 1 10 100100
101
102
103
104
105
G' (
Pa)
(rad/s)
strain=0 strain=10 strain=25
Pure
0.01 0.1 1 10 100100
101
102
103
104
105
G' (
Pa)
(rad/s)
strain=0 strain=10 strain=25 strain=100
Pure
0.01 0.1 1 10 100100
101
102
103
104
105
G' (
Pa)
(rad/s)
strain=0 strain=10 strain=25 strain=100 strain=250Pure
0.01 0.1 1 10 100100
101
102
103
104
105
G' (
Pa)
(rad/s)
strain=0 strain=10 strain=25 strain=100 strain=250 strain=1000Pure
66
Shear sequence 200 °C
+300 s +200 s +1500 s +3000 s +15000 s
time (h) 0 1 2 3,3 5 10
strain 10 25 100 250 1000
shea
r
0.05 s-1
0.01 0.1 1 10 100100
101
102
103
104
H(
). (P
a.s)
(s)
strain =0
Pure
0.01 0.1 1 10 100100
101
102
103
104
H(
). (P
a.s)
(s)
strain =0 strain=10
Pure
0.01 0.1 1 10 100100
101
102
103
104
H(
). (P
a.s)
(s)
strain =0 strain=10 strain=25
Pure
0.01 0.1 1 10 100100
101
102
103
104
H(
). (P
a.s)
(s)
strain =0 strain=10 strain=25 strain=100
Pure
0.01 0.1 1 10 100100
101
102
103
104
H(
). (P
a.s)
(s)
strain =0 strain=10 strain=25 strain=100 strain=250
Pure
0.01 0.1 1 10 100100
101
102
103
104
H(
). (P
a.s)
(s)
strain =0 strain=10 strain=25 strain=100 strain=250 strain=1000 Pure
PMMA & PS
τF
Coalescence tests PMMA2+ PS2
0.01 0.1 1 10 100100
101
102
103
104
H(
). (P
a.s)
(s)
strain =0 strain=10 strain=25 strain=100 strain=250 strain=1000 Pure
0.01 0.1 1 10 100100
101
102
103
104
H(
). (P
a.s)
(s)
strain =0 strain=10 strain=25 strain=100 strain=250 strain=1000 Pure
PMMA & PS
τF 0.01 0.1 1 10 100
100
101
102
103
104
0.01 0.1 1 10 100100
101
102
103
104
0.01 0.1 1 10 100100
101
102
103
104
0.01 0.1 1 10 100100
101
102
103
104
dc
ba
H(
). (P
a.s)
(s)
strain =0 strain=10 strain=25 strain=100 strain=250 strain=1000 Pure
H(
). (P
a.s)
(s)
strain =0 strain=10 strain=25 strain=100 strain=250 strain=1000 BC1 0.2 %
H(
). (P
a.s)
(s)
strain =0 strain=10 strain=25 strain=100 strain=250 strain=1000 BC1 0.5 %
H(t)
*t (P
a.s)
time (s)
strain =0 strain=10 strain=25 strain=100 strain=250 strain=1000 BC1 1 %
67
PMMA & PS
τF τF
τF τF
τF
? ? τβ τβ
τF = 𝑓(η𝑀, 𝑝, Φ𝐼 , α , 𝑅𝑣)
Rv is evaluated at each step
Coalescence tests PMMA2+ PS2 + CB 𝑴𝒏 𝑩𝑪𝟏 < 𝑴𝒏(𝑩𝑪𝟐)
68
BC2 more efficient
=𝛷𝐵𝐶𝛷𝑃𝑆
𝑅𝑣𝜌𝐵𝐶𝑁𝐴6𝑀𝑤𝐵𝐶
A. Adedeji, S. Lyu, and C. W. Macosko, “Block copolymers in homopolymer blends: interface vs micelles,” Macromolecules, vol. 34, no. 25, pp. 8663–8668, 2001.
BC2 is more efficient for same surface coverage
1 10 100 10000.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0 Pure
BC2 1 %
BC1 1 %
Rv (
mm
)
strain
%BC ∑
(chain/nm²)
Covered interface
(%)
BC1 0.2 0.0023 13 0.5 0.0032 18 1 0.0075 43
BC2 0.2 0.0006 11 0.5 0.0009 19 1 0.0030 60
Coalescence tests
𝑴𝒏 𝑩𝑪𝟏 < 𝑴𝒏(𝑩𝑪𝟐)
PMMA2+ PS2 + CB
=𝛷𝐵𝐶𝛷𝑃𝑆
𝑅𝑣𝜌𝐵𝐶𝑁𝐴6𝑀𝑤𝐵𝐶
%BC ∑
(chain/nm²)
Covered interface
(%)
BC1 0.2 0.0023 13 0.5 0.0032 18 1 0.0075 43
BC2 0.2 0.0006 11 0.5 0.0009 19 1 0.0030 60
69
BC2 more efficient
A. Adedeji, S. Lyu, and C. W. Macosko, “Block copolymers in homopolymer blends: interface vs micelles,” Macromolecules, vol. 34, no. 25, pp. 8663–8668, 2001.
Coalescence is prevented by steric hindrance + Marangoni stresses
Coalescence tests
𝑴𝒏 𝑩𝑪𝟏 < 𝑴𝒏(𝑩𝑪𝟐)
PMMA2+ PS2 + CB
0.0 0.2 0.4 0.6 0.8 1.00.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Pure C20A
a (m
N/m
)
% of BC
70 J. Genoyer, M. Yee, J. Soulestin, and N. R. Demarquette, “Compatibilization mechanism induced by organoclay in PMMA/PS blends,” J. Rheol. , vol. 61, no. 4, 2017.
90/10 blend (a) without and (b) with 0,8 % C20A
90/10/0,8
-35 %
Rv decreases Clay at interface Decrease of interfacial
tension
PMMA1+ PS1 + C20A
-52 %
Results: Compatibibilization with Clay
10-2 10-1 100 101 102
0.01 0.1 1 10 100
10-2
10-1
100
101
102
103
104
H(
). (P
a.s)
(s)
90/10/0 90/10/1
10-2 10-1 100 101 102
0.01 0.1 1 10 100
10-2
10-1
100
101
102
103
104
H(
). (P
a.s)
(s)
90/10/0 90/10/1 90/10/4
10-2 10-1 100 101 102
0.01 0.1 1 10 100
10-2
10-1
100
101
102
103
104
H(
). (P
a.s)
(s)
90/10/0 90/10/1 90/10/4 90/10/8
71 J. Genoyer, M. Yee, J. Soulestin, and N. R. Demarquette, “Compatibilization mechanism induced by organoclay in PMMA/PS blends,” J. Rheol. , vol. 61, no. 4, 2017.
200 °C
Marangoni stresses with clays
+20 °C
PMMA & PS
τF τF τβ
𝜏𝛽 Concentration en C20A ,
Results: Compatibibilization with Clay PMMA1+ PS1 + C20A
1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
0.01 0.1 1 10 100 1000ω (rad/s)
G' (
Pa)
G' - PS+C15A - solution
G' - PS+C15A - masterbatch
G' - PS+C15A - melt mixing
G' - PS
D.J. Carastan , A. Vermogen, K. Masenelli-Varlot, N. R. Demarquette, Polymer Engineering and Science, 2010, pp 257-267
Déformations larges et rapides
Tout peut arriver !!!
Études théoriques: Comment la morphologie se forme ??
Études rhéologiques
VISCOÉLASTICITÉ NON LINÉAIRE
Coalescence
Breakup
Shape Recovery
Viscoélasticité non linéaire : Déformations larges
Viscoélasticité non linéaire : Déformations larges
0 5 10 15 20 25
0
5
10
15
20
25
30
PP/PS 90/10 PP/PS/SEBS 90/10/5
5 s -1
10 s -1
te
nsão
de
cisa
lham
ento
, kP
a
tempo (t), s
Time, s
She
ar ra
te s-1
5
10
Macaubas P.H.P, Demarquette N.R, Dealy J.M Rheol Acta, vol 44, pp 295-312, 2005
Déformation Contrainte
ijij
ml
kjijijmij PqQ
qqQCq
H
Hags
2
2
.2
322
15.11
Q: Interfacial area; qij: interface tensor, sij: stress tensor ; H: Function of viscosity of both Phases, gij ou ij Strain tensor; m: Matrix viscosity, C2, , m, d Model parameters
mm
m
j,iij
2
jiij
ijijijkmkm
jiijlklkijjkkiikkjij
q)1(QdQqqdtdQ
)qQ(qQqqQ
q)(3Qq
32qq
dtdq
dSV
Q1
dS)ij31
jnin(V1
ijq
Équations constitutives pour prévoir l’évolution de morphologie
t2 Time to t1
Rest (to)
θ2
deformation and re-orientation
(t2) 1
.s10 g
θ1
x
y
z
First shear step
Second shear step
Deformation and orientation
(t1) 1
.s5 g
Paulo H. P. Macaúbas, Nicole R. Demarquette, John M. Dealy, 44, Rheologica Acta 295-312, 2005
5
10
Shea
r ra
te s-1
Time, s
Strain
Stress
Viscoélasticité non linéaire : Déformations larges
Nanodiélectriques
Anhydride maléique
Effet des nanoparticules sur la croissance d’arborescence électrique
Michael G. Danikas, Toshikatsu Tanaka, Nanocomposites―A Review of Electrical Treeing and Breakdown, IEEE Dielectrics &
Electrical Insulation Society.
Anhydride maléique
Argile (améliore la résistance au claquage)
Copolymères Block
SEBS
Sphérique Cylindrique Lamellar
Nanodiélectriques
Extrusion +
soufflage de film
Bi-orienté
Agitation magnétique
Ultra sonication
Évaporation de solvent
Procédé chimique
Isotropique
+ + Nanoparticules SEBS or
SEBS_MA Extrusion
Sheet die Orienté
Nanodiélectriques
SEBS-30+20A (Cylinders)
SEBS-30-MA+20A (Lamellar/Cylinders)
Anhydride maléique
SEBS
Nanodiélectriques
83
La résistance au claquage est améliorée grâce aux argiles orientées.
E. Helal, N.R. Demarquette, L.G. Amurin, E. David, D.J. Carastan, M. Fréchette: Styrenic block copolymer-based nanocomposites: Implications of nanostructuration and nanofiller tailored dispersion on the dielectric properties Polymer, Volume 64, 1 May 2015, Pages 139-152.
Nanodiélectriques
Morphologie
Champs de claquage (kV/mm)
Pertes diélectriques
(à 1 kHz)
Isotropique Orienté Bi-orienté
Pure 60
Composite (5%)
63.6
Pure 56
Composite (5%)
63
Pure 60
Composite (5%)
78
Pure 2.5*10-3
Composite (5%)
2.6*10-2
Pure 2*10-3
Composite (5%)
1.9*10-2
Pure 9.7*10-4
Composite (5%)
4.5*10-3
Champs de claquage plus élevé
Pertes diélectriques plus faibles
Nanodiélectriques
Acknowledgments
85
Collaborators
Guilherme Barra UFSC, Brazil
Michel Fréchette China
Amilton dos Santos USP, Brazil
Danilo Carastan UFABC, Brazil
Ricardo Zednik ÉTS, Canada
Éric David ÉTS, Canada
Jérémie Soulestin École des Mines, France
Jean-Marc Chenal INSA, Lyon,
France
Ram Sharma Chem Eng
Bath University UK
86
Aldo Craievich USP, Brazil
Students
Dr Emna Helal
Dr Scheyla Kuester
Dr Julie Genoyer
87
Dr Rafael Kurusu
Dr Leice Amurin
لكشكرا
Thank you Obrigada
Merci