Rheology and Processing of Polymer Nanocomposites E-Book
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- Herausgeber: John Wiley & Sons
- Kategorie: Fachliteratur
- Sprache: Englisch
Rheology and Processing of Polymer Nanocomposites examines the current state of the art and new challenges in the characterization of nanofiller/polymer interactions, nanofiller dispersion, distribution, filler-filler interactions and interfaces in polymer nanocomposites.
A one-stop reference resource for important research accomplishments in this area, it benefits academics, researchers, scientists, and engineers in the field of polymer nanocomposites in their daily work.
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Seitenzahl: 1139
Veröffentlichungsjahr: 2016
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Table of Contents
Cover
Title Page
Copyright
List of Contributors
Chapter 1: Materials for Polymer Nanocomposites
1.1 Introduction
1.2 Nanocomposite Framework
1.3 Recent Developments and Opportunities in the Area of Polymer Nanocomposites
1.4 Challenges in the Area of Polymer Nanocomposites
1.5 Relationships of Macroscopic Rheological Properties to Nanoscale Structural Variables
1.6 Conclusion
Acknowledgments
References
Chapter 2: Manufacturing Polymer Nanocomposites
2.1 Introduction
2.2 Nanofillers
2.3 Polymer Matrices
2.4 Preparation of Nanocomposites
2.5 Characterization
2.6 Conclusions
References
Chapter 3: Rheology and Processing of Polymer Nanocomposites: Theory, Practice, and New Challenges
3.1 Introduction
3.2 Viscoelasticity of Nanocomposites
3.3 Flow Properties of Nanocomposites
3.4 Theory and Modeling of Nanocomposites Rheology
3.5 Processing of Nanocomposites
3.6 Conclusion and Futures Challenges
Acknowledgments
References
Chapter 4: Mixing of Polymers Using the Elongational Flow Mixer (RMX®)
4.1 Introduction
4.2 Polymer Blends
4.3 Polymer Nanocomposites
4.4 Elongational Flow Mixer (RMX®)
4.5 RMX® Mixing of Polymer Blends
4.6 Mixing of Polymer Nanocomposites
4.7 Concluding Remarks
References
Chapter 5: Rheology and Processing of Polymer/Layered Silicate Nanocomposites
5.1 Introduction
5.2 Nanostructure Development
5.3 Novel Compounding Methods for Delamination of OMLFs
5.4 Nanostructure and Rheological Properties
5.5 Nanocomposite Foams
5.6 Future Prospects
References
Chapter 6: Processing and Rheological Behaviors of Cnt/Polymer Nanocomposites
6.1 Introduction
6.2 Processing Techniques of Polymer/CNT Nanocomposites
6.3 Rheological Properties of Polymer/Carbon Nanotube Composites
6.4 Summary
Acknowledgment
References
Chapter 7: Unusual Phase Separation in PS Rich Blends with PVME in Presence of MWNTs
7.1 Introduction
7.2 Experimental Methods
7.3 Theory Background
7.4 Results and Discussion
7.5 Conclusions
Acknowledgements
References
Chapter 8: Rheology and Processing of Polymer/POSS Nanocomposites
8.1 Introduction
8.2 Polyhedral Oligomeric Silsesquioxanes
8.3 Processing of Polymer/POSS Nanocomposites
8.4 Rheological Behavior of POSS-Based Polymer Nanocomposites
8.5 Conclusions
Acknowledgments
References
Chapter 9: Polymer and Composite Nanofiber: Electrospinning Parameters and Rheology Properties
9.1 Introduction
9.2 Electrospinning
9.3 Electrospinning Process Parameters
9.4 Polymer-Based Nanofiber and its Rheology
9.5 Nanofiber and its Polymer Composites
9.6 Conclusion
References
Chapter 10: Rheology and Processing of Inorganic Nanomaterials and Quantum Dots/Polymer Nanocomposites
10.1 Inorganic Nanoparticle Filled Polymer Nanocomposites
10.2 Fabrication of Inorganic Nanoparticle Filled Polymer Nanocomposites
10.3 Why Rheological Study is Important for Polymer Nanocomposites
10.4 Rheology of Quantum Dot Based Polymer Nanocomposites
10.5 Metal Oxide Nanoparticle-Based Polymer Nanocomposites
10.6 Conclusion
References
Chapter 11: Rheology and Processing of Laponite/Polymer Nanocomposites
11.1 Introduction
11.2 Rheology
11.3 Processing
11.4 Conclusions and Outlook
Acknowledgement
References
Chapter 12: Graphene-Based Nanocomposites: Mechanical, Thermal, Electrical, and Rheological Properties
12.1 Introduction
12.2 Graphene
12.3 The Use of Graphene in Nanocomposite Materials
12.4 Nanocomposite Characterization
12.5 Conclusion
12.6 Future Perspective
References
Chapter 13: Processing, Rheology, and Electrical Properties of Polymer/Nanocarbon Black Composites
13.1 Introduction
13.2 Experimental
13.3 Electrical Properties of Carbon Black Composites and Applications
13.4 Conclusion
References
Chapter 14: Rheology and Processing of Nanocellulose, Nanochitin, and Nanostarch/Polymer Bionanocomposites
14.1 Introduction
14.2 Biopolymers as Nanofillers for Polymer/Nanocomposites
14.3 Potential Applications of Polysaccharide Nanofillers/Polymer Nanocomposites
14.4 Conclusions and Future Perspectives
References
Chapter 15: Rheology And Processing of Nanoparticle Filled Polymer Blend Nanocomposites
15.1 Rheology of Polymer Blends
15.2 Effect of Nanoparticles on the Morphology of Polymer Blend
15.3 Rheology of Nanoparticles Filled Polymer Blend
15.4 Summary
References
Chapter 16: Rheology as a Tool for Studying in Situ Polymerized Carbon Nanotube Nanocomposites
16.1 Introduction
16.2 Basic Principles of Rheokinetics
16.3 Rheokinetics of in Situ Polymerization of Carbon Nanotube/Monomer Systems
16.4 Rheological Percolation Threshold of Carbon Nanotube-Based Nanocomposites
16.5 Concluding Remarks
References
Index
End User License Agreement
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Guide
Cover
Table of Contents
Begin Reading
List of Illustrations
Chapter 1: Materials for Polymer Nanocomposites
Figure 1.1 Classification of nanoscale fillers: (a–c) 1D, 2D, and 3D nanomaterials.
Figure 1.2 Structures of silsesquioxanes [14]: (a) random structure, (b) ladder structure, (c–e) cage structures, and (d) partial cage structure.
Figure 1.3 TEM images of the nanoscale structure of carbon nanofibers showing (a) disordered bamboo-like structures, reproduced from Merkulov et al. [33] with permission of AIP Publishing; (b) highly graphitized sidewall of a cup-stacked nanofibers showing the shell tilt angle, reproduced from Endo et al. [34] with permission of AIP Publishing; and (c) a nesting of the stacked layers (insets: molecular models), reproduced from Endo et al. [44] with permission of AIP Publishing.
Figure 1.4 HRTEM images of MWNTs: (a) 18-nm-diameter nanotube produced at 675 °C and (b) 180-nm-diameter nanotube produced at 775 °C. The insets are the corresponding nanodiffraction patterns showing both tubes well graphitized at low synthesis temperatures. Reproduced from Andrews et al. [55] with permission of American Chemical Society.
Figure 1.5 Schematic illustration of topochemical synthesis and exfoliation of Co
2+
–Fe
3+
LDH. Reproduced from Renzhi et al. [71] with permission of American Chemical Society.
Figure 1.6 Pathway of nanocomposite preparation by (a) monomer exchange and in situ polymerization, (b) direct polymer exchange, and (c) restacking of the exfoliated layers over the polymer. Reproduced from Leroux and Besse [74] with permission of American Chemical Society.
Figure 1.7 Properties of graphene.
Figure 1.8 Classification of polymers.
Chapter 2: Manufacturing Polymer Nanocomposites
Figure 2.1 Structure of 2 : 1 layered silicate. Reproduced from Song et al. [11] with permission of Elsevier.
Figure 2.2 Schematic diagrams of (a) a single-walled carbon nanotube, (b) a multi-walled carbon nanotube, and (c) a double-walled carbon nanotube. Reproduced from Dresselhaus et al. [25] with permission of Elsevier.
Figure 2.3 Schematic illustrations of the carbon nanotube structures of (a) armchair and (b) zigzag. Reproduced from Thostenson et al. [26] with permission of Elsevier.
Figure 2.4 Representative XRD pattern of PS35–organosilicate hybrid heated to 165 °C at different times. The asterisks indicate the positions of the basal reflections from the pristine organosilicate (
d
001
= 2.52 nm and
d
002
= 1.27 nm). After 25 h, the X-ray reflection corresponding to the predominant hybrid is observed (
d
001
= 3.2 nm,
d
002
= 1.58 nm, and
d
003
= 1.06 nm). The reaction kinetics depends on the sample preparation parameters such as the particle size of the constituent powders and the degree of mixing. Therefore, the reaction times may vary slightly depending on the processing conditions. Reproduced from Vaia et al. [97] with permission of American Chemical Society.
Figure 2.5 Morphological analysis of the nanocomposites based on HMW nylon-6 and the organoclays M
3
(HT)
1
and M
2
(HT)
2
-95. (a) WAXD scans and TEM images of (b) M
3
(HT)
1
and (c) M
2
(HT)
2
-95 based composites. Concentrations of MMT in the M
3
(HT)
1
and M
2
(HT)
2
-95 nanocomposites are 2.9 and 3.0 wt%, respectively. Reproduced from Fornes et al. [101] with permission of Elsevier.
Figure 2.6 XRD patterns of pristine and modified clay, neat PA6, and PA6/clay nanocomposites with different clay loadings. Reproduced from Liu et al. [105] with permission of John Wiley and Sons.
Figure 2.7 (a) XRD data of hexadecyl-MMT/PET nanocomposites that were melt-blended at 285 °C for 2, 5, and 7 min at screw speeds of 21 and 31 rad/s; (b) TEM images of CD 12 showing high levels of dispersion and exfoliation; and (c) average tactoids of four sheets per stack. Reproduced from Davis et al. [56] with permission of John Wiley and Sons.
Figure 2.8 TEM images of samples prepared with and without coupling agent: (a) PP/15A and (b) PP/15A/MA330k. Reproduced from Ton-That et al. [123] with permission of John Wiley and Sons.
Figure 2.9 Variation of Young's modulus and yield strength as a function of SWCNT content in PP/SWCNT composites. Reproduced from Manchado et al. [154] with permission of Elsevier.
Figure 2.10 Generic pressure–temperature diagram. Reproduced from Canelas and DeSimone [178] with permission of Springer.
Figure 2.11 TEM images of 10 wt% MMT/PP nanocomposites processed by (a) conventional melt blending, (b) scCO
2
-aided melt blending, (c) direct blending with sequential mixing, and (d) scCO
2
-aided melt blending with sequential mixing method. Reproduced from Chen et al. [191] with permission of Elsevier.
Chapter 3: Rheology and Processing of Polymer Nanocomposites: Theory, Practice, and New Challenges
Figure 3.1 Variation of the complex shear modulus of nanocomposites at different nanofiller concentrations. (a) Storage modulus curves of LLDPE filled with
x
vol% of nanosilica A200 (
T
= 190 °C) () LLDPE, ()
x
= 1 vol%, (⊗)
x
= 2 vol%, (∇)
x
= 3 vol%, and ()
x
= 4 vol%. Reproduced from Dorigato et al. [13] with permission of Express Polymer Letters. (b) LLDPE filled with layer organoclays (Storage modulus variation). Inset: MA-× means × phr of organoclay. Reproduced from Durmus et al. [14] with permission of Elsevier. (c) Polycarbonate filled with multi-walled carbon nanotube (storage modulus variation). Reproduced from Potschke et al. [15] with permission of Elsevier.
Figure 3.2 Transmission electronic microscopy on the nanocomposite filled with 6.6% v/v (a) and with 15.7% v/v (b) of silica particles. Observations at medium (left) and low (right) magnification are shown. The black zone corresponds to the silica and the gray to the polymer. Reproduced from Jouault et al. [20] with permission of American Chemical Society.
Figure 3.3 Variation of storage modulus versus frequency of PS nanocomposite filled with 5 vol% of silica and PS-grated silica. References 1, 2, and 3 correspond to hydrodynamic diameter of PS-grated silica, respectively, 316, 144, and 181 nm (determined by dynamic light scattering). Master curve at
T
= 160 °C. Reproduced from Bartholome et al. [32] with permission of Elsevier.
Figure 3.4 Time variations of storage modulus
G
′ (a) and loss modulus
G
″ (b) of nanocomposite PP/PP-g-MA/MMT (85/10/5) at 200 °C. The time increases from bottom to top. Reproduced from Zouari et al. [56] with permission of AIP Publishing.
Figure 3.5 Curves obtained by TTS shift of the storage modulus
G
′ with frequency for three temperatures (: 220 °C, •: 200 °C, and : 180 °C, reference taken at 180 °C) at the same annealing time (a) and the corresponding curves at same yield stress (b). Reproduced from Zouari et al. [56] with permission of AIP Publishing.
Figure 3.6 The schematic representation of the speculated rheological response to the increase in the volume fraction of fillers. Reproduced from Zhao et al. [66].
Figure 3.8 Different contributions to the complex shear modulus versus strain for polymers filled with filler at two levels of dispersion. Reproduced from Frohlich et al. [83].
Figure 3.7 (a) Dynamic moduli at a fixed frequency (
ω
= 0.5 rad/s
1
) as a function of strain amplitude for a colloidal suspension of silanized silica nanoparticles (SiO
2
) at 35 wt% after preshearing at 5 s
−1
and a recovery for 7200 s. (b) Rescaled ratio
G
′
0
/
G
″
max
as a function of
G
″
max
for the suspensions prepared at 35 wt% with particles from batch 2. Solid and dotted lines are the linear fits to the slope and to the plateau, respectively. The marker US, U, S, and H corresponds to the sample preparation method, namely ultrasonic disperser (US), high shear Ultraturrax mixer (U), magnetic stirrer (S), and mixing by hand (H). Reproduced from Galindo-Rosales et al. [80] with permission of John Wiley and Sons.
Figure 3.9 Payne effect in fumed silica composites: limit of linearity. (a) Variation of the storage modulus versus deformation at different silica concentrations in a copolymer of ethylene and vinyl acetate.
ω
= 10 rad/s,
T
= 140 °C. Reproduced from Cassagnau et al. [37] with permission of Elsevier. (b) Power law on the limit of linearity
γ
c
.
Figure 3.10 Steady shear viscosity as a function of shear rate at (•) 0%, () 0.25%, () 0.5%, () 0.75%, () 1%. Reproduced from Aubry et al. [16] with permission of AIP Publishing.
Figure 3.11 Steady shear stress as a function of shear rate at (•) 0%, () 0.25%, () 1%, () 1.5%, () 2.5%, (Δ) 5%, () 10%. Reproduced from Aubry et al. [16] with permission of AIP Publishing.
Figure 3.12 Normalized polymer matrix viscosity as a function of specific interfacial area σ
c
. (
η
m
and
η
0
are polymer matrix viscosities in polymer nanocomposites and in pure polymer, respectively). Open and filled symbols are for
N
b
= 10 and
N
b
= 20 chains, respectively. The solid line is the expected behavior for conventional composites. The dashed lines serve to guide the eye. Estimated ±10% error bars for viscosities are shown. Reproduced from Smith et al. [112] with permission of AIP Publishing.
Figure 3.13 The different mass fractal dimensions as a function of the elongation ratio resulting from the three different
q
-ranges: full range,
d
m
, that is, from the minimum
q
visible to approximately 0.2 nm
−1
,
d
m1
from the range on the right-hand side of the minimum up to approximately 0.2 nm
−1
, and
d
m2
from the range on the left-hand side of the minimum. Reproduced from Schneider and Göritz [129] with permission of AIP Publishing. (b) Comparison of the evolution of
S
(
q
) at low
q
with the stress evolution of organophilic silica-hexadecane at
φ
= 0.035 at 3 s
−1
. Reproduced from Varadan et al. [130] with permission of American Chemical Society.
Figure 3.14 Steady-state Trouton ratio
η
E,∞
/
η
o
( ) and extensional relaxation time
λ
E
(▸) as a function of fumed silica nanoparticle concentration in 0.6 wt.% aqueous PEO solution (
M
w
= 6 × 10
5
g/mol). Reproduced from Khandavalli and Rothstein [136] with permission of AIP Publishing.
Figure 3.15 Extensional viscosity profiles as a function of time for EVA28 (28% VA) and EVA28 nanocomposites at 130 °C and at different elongation rates. Nanofiller is organomodified bentonite, contents are in wt%. For clarity purposes, the viscosities of EVA28 with 2.5% and 5.0% nanofillers were multiplied by 10 and 50, respectively. Reproduced from Gupta et al. [117] with permission of Elsevier.
Figure 3.16 (a) The internal chain-scale structure of the system. G, H, I, J, and K represent attachment points of a chain to two particles. Chain segments such as HI bridge fillers. A large number of polydisperse loops (e.g., GH, IJ, and JK) and dangling ends (e.g., GF) are attached to each filler. (b) Prediction of Sarvestani's model for the storage modulus
G
′ of nanofilled polymer systems at different filler volume fraction (
φ
= 6%, 12%) with constant energetic polymer–nanoparticle interaction. Reproduced from Sarvestani and Picu [151] with permission of Elsevier.
Figure 3.17 Comparison of theoretical prediction and experimental data of the complex shear modulus at
σ
= 1 rad/s for volume fraction of 0.252 (filled symbols) and 0.335 (open symbols) as a function of strain. The full line represents Equation (3.44a). Reproduced from Majeste et al. [87] with permission of John Wiley and Sons.
Figure 3.18 Different regimes for the dissipation in strongly reinforced polymers. At low deformations, the regime A is dominated by dissipation in the polymer matrix and dissipation in polymer close to the glass transition. Regime B is dominated by rupture and rebirth of glassy bridges. Regime C is dominated by the addition of the same mechanisms as in regime A again. Reproduced from Merabia et al. [94] with permission of American Chemical Society.
Figure 3.19 Percentage of extrudate swell as a function of wall shear stress for neat and iPP filled with (a) uncoated and (b) stearic acid-coated CaCO
3
nanoparticles of various filler loadings, ranging from 5 to 25 wt%. Reproduced from Dangtungee et el. [207] with permission of Elsevier.
Figure 3.20 Illustration of the supercritical carbon dioxide process. Polymer and clay are mixed together followed by a soaking period in scCO
2
. The system is depressurized, and the expanding CO
2
delaminates platelets. Reproduced from Manitiu et al. [213].
Chapter 4: Mixing of Polymers Using the Elongational Flow Mixer (RMX®)
Figure 4.1 Images from atomic force microscopy (AFM) of HDPE (50)/PP (40)/PS (10) wt/wt blends: (a) HDPE (dark domains) and PS (rounded clear particles) dispersed within PP (clear) matrix; and (b) co-continuos phases of HDPE and PP (PS rounded particle remains within the PP). Blends prepared by the elongational flow mixer, RMX®. Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.2 Depiction of the evolution of Rayleigh's disturbances for a Newtonian thread in a quiescent Newtonian matrix as interfacial stresses and shear stresses.
Figure 4.3 Depiction of the critical capillary number for droplet breakup as a function of viscosity ratio in simple shear and planar elongational flow.
Figure 4.4 Depictions of the efficiency coefficients,
e
f
, for (a) elongational and (b) simple shear flows.
Figure 4.5 Typical mixing heads for SSE: (a) Maddock Courtesy of James Frankland and (b) CRD. Adapted from http://www.google.com/patents/US6709147.
Figure 4.6 Modular adaptability of a TSE. Distributive and dispersive efficiencies depend on both the number of mixing segments and the particular design.
Figure 4.7 Three-dimensional view of the RMX®: (a) chamber, (b) piston with seal, (c) mixing element, (d) feeding unit for melts, (e) feeding channel for liquids, and (f) optional mold. Reproduced from Bouquey et al. [43] with permission of John Wiley and Sons.
Figure 4.8 Schematic operation of the RMX® mixer: (a) feeding, (b) mixing, and (c) discharge. Reproduced from Bouquey et al. [43] with permission of John Wiley and Sons.
Figure 4.9 Maximum pressure reached by cycle in an RMX® mixing sequence for an HDPE/PP/PS blend at
N
= 10 and
v
= 10 mm/s, employing mixing elements of (a)
L
/
D
= 14 and (b)
L
/
D
= 7. Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.10 Pressure trajectory as a function of piston displacement in an RMX® mixing sequence for an HDPE/PP/PS blend at
N
= 10,
v
= 10 mm/s, and mixing element
L
/
D
= 14. The total displacement in millimeters depends on the volume of material (in the example, 40 g). Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.11 Mapping of the flow by Astarita's parameter. Reproduced from Bouquey et al. [43] with permission of John Wiley and Sons.
Figure 4.12 Elongational strain rate
dv
/
dx
(s
−1
) along the
x
-symmetry axis. Reproduced from Bouquey et al. [43] with permission of John Wiley and Sons.
Figure 4.13 Estimation of elongation strain rate in the RMX® using capillary data obtained at similar convergence ratio of capillary die for a blend HDPE/PP/PS. Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.14 TEM images at two different values of
N
for 10/90 PS/PMMA blends (
v
= 10 mm/s),
L
/
D
= 5: (a) 10 and (b) 40. Reproduced from Bouquey et al. [43] with permission of John Wiley and Sons.
Figure 4.15
D
n
and
D
v
(µm) versus
N
for 90/10 PS/PMMA blends (
v
= 10 mm/s, temperature = 210 °C): ()
L
/
D
= 5 (long die),
D
n
; (▵)
L
/
D
= 1.5 (short die),
D
n
; ()
L
/
D
= 5,
D
v
; and ()
L
/
D
= 1.5,
D
v
. Reproduced from Bouquey et al. [43] with permission of John Wiley and Sons.
Figure 4.16
D
n
and
D
v
(µm) as a function of
N
in the RMX® (
T
= 200 °C and
Q
= 21 cm
3
/s) for PP/EPDM 80/20 (wt/wt%) blends: (Δ)
D
n
(
L/D
= 7), ()
D
v
(
L/D
= 7), ()
D
n
(
L/D
= 14), and ()
D
v
(
L/D
= 14). Reproduced from Rondin et al. [52] with permission of John Wiley and Sons.
Figure 4.17 AFM images of an HDPE/PP/PS-50/40/10 (wt/wt%) blend obtained by RMX® at 200° C,
v
= 3 mm/s, and
N
= 5: (a)
L
/
D
= 7 (Φ = 4 mm) and (b)
L
/
D
= 14 (Φ = 2 mm). Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.18
D
n
and
D
v
(µm) of PMMA/PS blends versus
N
at different
v
/
Q
values, temperature = 210 °C: (▵)
D
n
at 5 mm/s, ()
D
v
at 5 mm/s, ()
D
n
at 10 mm/s, ()
D
v
at 10 mm/s, ()
D
n
at 20 mm/s, and (•)
D
v
at 20 mm/s. Reproduced from Bouquey et al. [43] with permission of John Wiley and Sons.
Figure 4.19 AFM images of an HDPE/PP/PS-50/40/10 (wt/wt %) blend obtained by RMX® at 200 °C,
v
= 3 mm/s,
N
=
5
,
L
/
D
= 7. (a) 3 mm/s, (b) 10 mm/s, and (c) 30 mm/s. Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.20 AFM images of an HDPE/PP/PS-50/40/10 (wt/wt %) blend obtained by RMX® at 200 °C,
v
= 3 mm/s,
N
= 5,
L
/
D
= 14. (a) 3 mm/s, (b) 10 mm/s, and (c) 30 mm/s. Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.21 (a, b) Complex viscosity
η
* and storage modulus
G
′ of PP with two different melt flow index, MFI, and EPDM at 200 °C: () PP (MFI:2), () PP (MFI:12), and () plasticized EPDM. Guided lines are for the Carreau-Yasuda fitting. Reproduced from Rondin et al. [52] with permission of John Wiley and Sons.
Figure 4.22 (a)
D
v
as a function of the number of cycles and (b) PDI as a function of the number of cycles done in the RMX®. (
T
= 200 °C and
Q
= 21 cm
3
/s) for PP/EPDM 80/20 (wt/wt%) blends at different viscosity ratios and
L
/
D.
Reproduced from Rondin et al. [52] with permission of John Wiley and Sons.
Figure 4.23 Viscosity of pristine polymer to be mixed into a blend HDPE/PP/PS by RMX® mixing. Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.24 AFM images of HDPE/PP/PS systems: (a) extruded and compression molded and (b) after RMX® mixing. Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.25 SEM images at equivalent specific mixing energies. (a) PP (MFI = 2)/EPDM-60/40 (wt/wt%) blends: (a1) Haake Rheomix 600 (
v
= 50 rpm,
t
= 6 min, SMEI = 405 J/g) and (a2) RMX® (
L/D
= 14,
N
= 10,
t
= 1 min, SMEI = 408 J/g); (b) PP (MFI = 12)/EPDM-P 60/40 (wt/wt%) blends: (b1) Haake Rheomix 600 (
v
= 50 rpm,
t
= 6 min, SMEI = 260 J/g) and (b2) RMX® (
L/D
= 14,
N
= 10,
t
= 1 min, SMEI = 272 J/g). Reproduced from Rondin et al. [52] with permission of John Wiley and Sons.
Figure 4.26 Temperature increment at three different piston speeds and
L
/
D
ratio for blends HDPE/PP/PS obtained by RMX®. Reproduced from Mani et al. [13] with permission of Ecoindustry.
Figure 4.27 Morphology comparison between (a) Haake internal mixer and (b) RMX® at the same mixing energy for PBT/PP compatibilized blends. Top photographs, without maleic anhydride; bottom, 5 wt/wt% maleic anhydride. Reproduced from Bouquey et al. [57] with permission of MIXPLAST.
Figure 4.28
G
′ (white symbols) and
G″
(black symbols) for a PP(FMI = 2)/EPDM 80/20 (wt/wt%) blend elaborated in the Haake Rheomix 600 (
v
= 50 rpm,
t
= 6 min) and in the RMX® (
L/D
= 14,
N
= 10). Gray and black lines correspond to the moduli fitting of the respective Palierne model, and dash lines represent the matrix moduli. Reproduced from Rondin et al. [52] with permission of John Wiley and Sons.
Figure 4.29
G
′ (white symbols) and
G
″ (black symbols) for a PP(FMI=2)/EPDM 60/40 (wt/wt%) blend elaborated in the Haake Rheomix 600 (
v
= 50 rpm,
t
= 6 min) and in the RMX® (
L/D
= 14,
N
= 10). Gray and black lines correspond to the moduli fitting of the respective Palierne model, and dash lines represent the matrix moduli. Reproduced from Rondin et al. [52] with permission of John Wiley and Sons.
Figure 4.30 Optical microscopy images of morphologies resulting from different manufacturing methods: (a) Brabender mixing chamber, (b) Haake microcompounder, (c) RMX compounder, and (d) solvent-based preparation. A 5 wt% GNP was used in all cases. Reproduced from Oxfall et al. [60] with permission of John Wiley and Sons.
Figure 4.31 Histogram representing various manufacturing methods employed to prepare the 5 wt% composition: (1) mixing chamber, (2) roll milling, (3) microcompounder, (4) elongational flow, (5) solvent processing. Reproduced from Oxfall et al. [60] with permission of John Wiley and Sons.
Figure 4.32
G
′ versus frequency of materials processed using various manufacturing methods. (a) 5 wt% and (b) 10 wt%: () mixing chamber, () roll milling, () microcompounder, (•) elongational flow, and (x) solvent processing. Reproduced from Oxfall et al. [60] with permission of John Wiley and Sons.
Figure 4.33 Complex viscosity as a function of frequency for processed samples of neat PLA at different RMX mixing conditions. Reproduced from Ibarra-Gómez et al. [68] with permission of John Wiley and Sons.
Figure 4.34 RMX® pressure trajectory during the mixing sequence of neat PLA at 40 mm/s and 10 cycles. Reproduced from Ibarra-Gómez et al. [68] with permission of John Wiley and Sons.
Figure 4.35 TEM images of (a) reference sample, (b) 10/20, (c) 10/30, and (d) 10/40. 10,000× (bar = 2 µm). Reproduced from Ibarra-Gómez et al. [68] with permission of John Wiley and Sons.
Figure 4.36 TEM characterization: (a, b) photographs of internal mixer sample and RMX sample 10/10, respectively, at 62 J/g. (c, d) photographs of internal mixer sample and RMX 10/40, respectively, at 246 J/g. 10,000× (bar = 2 µm). Reproduced from Ibarra-Gómez et al. [68] with permission of John Wiley and Sons.
Figure 4.37 XRD diffractograms showing the graphite characteristic peak for PLA/EG samples at different RMX® mixing conditions. The inset shows the general pattern of all samples, in order to point out that the amorphous character of the PLA matrix was preserved. Reproduced from Ibarra-Gómez et al. [68] with permission of John Wiley and Sons.
Chapter 5: Rheology and Processing of Polymer/Layered Silicate Nanocomposites
Figure 5.1 Selected articles based on Web of Science™ (accessed February 07, 2014) using keywords:
polymer
,
clay
, and
nanocomposites
.
Figure 5.2 Molecular dimensions of intercalants: (a) octadecylammonium (C
18
H
3
N
+
); (b) octadecyltrimethylammonium (C
18
(CH
3
)
3
N
+
); (c) dioctadecyldimethylammonium (2C
18
(CH
3
)
2
N
+
); and (d)
N
-(cocoalkyl)-
N
,
N
-[bis(2-hydroxyethyl)]-
N
-methylammonium cations (qC
14
(OH)). Reproduced from Yoshida and Okamoto [23] with permission of John Wiley and Sons.
Figure 5.3 WAXD patterns of HTO,
syn
-FH, and MMT intercalated with qC
14
(OH)
+
. Reproduced from Yoshida and Okamoto [23] with permission of John Wiley and Sons.
Figure 5.4 Illustration of a model of the interlayer structure of intercalant
N
-(cocoalkyl)-
N
,
N
-[bis(2-hydroxyethyl)]-
N
-methylammonium cation (qC
14
(OH)) in gallery space of layer titanate (HTO). The average distance between exchange sites is 0.888 nm calculated by surface charge density of 1.26 e
−
/nm
2
. For qC
14
(OH), the obtained molecular length, thickness, and width are 2.09, 0.881, and 0.374 nm, respectively (see Figure 5.2). The tilt angle
α
of the intercalants can be estimated by the combination of the interlayer spacing, molecular dimensions, and loading amount of intercalants when the alkyl chains are adopted all-
trans
conformation. Reproduced from Yoshida and Okamoto [23] with permission of John Wiley and Sons.
Figure 5.5 Bright field TEM images of PLA-based nanocomposites prepared with (a) MMT-C
18
H
3
N
+
, (b) MMT-C
18
(CH
3
)
3
N
+
, and (c) MMT-2C
18
(CH
3
)
2
N
+
. The dark entities are the cross section and/or face of intercalated-and-stacked silicate layers and the bright areas are the matrix. Reproduced from Yoshida and Okamoto [23] with permission of John Wiley and Sons.
Figure 5.6 Molecular dimensions of PLA backbone using the molecular dynamics program (MM2 in Quantum CAChe) in consideration with van der Waals' radii. Optimization of structure is based on the minimization of the total energy of the molecular system.
Figure 5.7 Three-component model used for basal spacing simulations, consisting of two layers of MMT with K
+
cations (stick model), four molecules of trimethylammonium cation (a) or dimethylstearylammonium cation (b) (stick and ball model), and one molecule of maleated PP (PP-MA) (ball model). Reproduced from Toth et al. [58] with permission of Elsevier.
Figure 5.8 POM images of the mixture: (a) unprocessed sample and (b) after solid-state processing for 8 h. Both micrographs were taken at 180 °C just after annealing for 30 s. The insets in each image are a computed FFT spectra of the micrograph. Reproduced from Saito and Okamoto [57] with permission of Elsevier.
Figure 5.9 Bright field TEM images of (a) unprocessed sample, (b) and (c) sample prepared by solid-state processing for 8 h. The dark entities are the cross section and/or face of intercalated-and-stacked silicate layers, and the bright areas are the matrix. The insets in (a) and (c) are a computed FFT spectrum of the micrograph. Reproduced from Saito and Okamoto [57] with permission of Elsevier.
Figure 5.10 Plots of versus vol% of MMT for various nanocomposites. The Einstein coefficient
k
E
is shown with the number in the box. The lines show the calculated results from Halpin and Tai's theory with various
k
E
.
Figure 5.11 Reduced frequency dependence of storage modulus, loss modulus, and complex viscosity of neat PLA and various PLACNs under dynamic oscillatory shear measurement. Reproduced from Ray et al. [44] with permission of Elsevier.
Figure 5.12 Percolation of hydrodynamic volumes of silicate layers at a low concentration. A schematic representation of stacked silicate layers and their interaction with each other, resulting in complete relaxation of the nanocomposite melts. Reproduced from Ren et al. [36] with permission of American Chemical Society.
Figure 5.13 (a) Frequency shift factors
a
T
and (b) modulus shift factor
b
T
as a function of temperature. Reproduced from Ray et al. [44] with permission of Elsevier.
Figure 5.14 Reduced frequency dependence of (a) tan
δ
, storage modulus
G
′(
ω
), and loss modulus
G
″(
ω
) of (b) neat nylon-6, (c) N6C1.6, and (d) N6C3.7 at
T
r
= 225 °C. The solid line was drawn by the power law of
G
′(
ω
) ∼
G
″(
ω
) ∼
ω
0.8
in the low
ω
region for N6C1.6. Reproduced from Mizuno et al. [21] with permission of John Wiley and Sons.
Figure 5.15 Temperature dependence of characteristic relaxation rates (
ω
rel
and 1/
t
d
) and crystallization rate (1/
t
1/2
) of N6C3.7. Reproduced from Katoh and Okamoto [20] with permission of Elsevier.
Figure 5.16 Onset of stress overshoot in the start-up of steady shear depends on the strain applied to the PP-based nanocomposite at 180 °C. Reproduced from Solomon et al. [39] with permission of American Chemical Society.
Figure 5.17 Schematic representation of (a) repulsive colloidal glass, (b) attractive glass, and (c) gel. Each thick line represents a Laponite disk, while a white ellipsoid indicates the range of electrostatic repulsions. For (a), long-range electrostatic repulsions dominate. In (b), attractive interactions affect the spatial distribution but repulsive interaction still plays the predominant role in the slow dynamics of the system. In (c), attractive interactions play a dominant role, percolated network forms, which gives the system its elasticity. Reproduced from Tanaka et al. [79] with permission of American Physical Society.
Figure 5.18 Time variation of shear viscosity for organo-Hectorite/styrene (3.5/96.5 vol/vol) suspension with four shear rates. Reproduced from Okamoto et al. [81] with permission of The Society of Rheology, Japan.
Figure 5.19 Time variation of <
η
2
> and <
δ
2
> upon imposition/cessation of steady shear under low (=0.5 s
−1
) and high (=60 s
−1
) conditions. Debye–Bueche equation is applicable in anisotropic shear flow field for dense suspension [83]. Reproduced from Okamoto et al. [81] with permission of The Society of Rheology, Japan.
Figure 5.20 TEM image in the
x–z
plane showing N6CN (clay loading = 3.7 wt%) sheared at 225 °C with = 0.0006 s
−1
for 1000 s. The
x
-,
y
-, and
z
-axes correspond to flow, shear gradient, and neutral direction, respectively. Reproduced from Okamoto [90] with permission of Rapra Technology.
Figure 5.21 Time variation of elongational viscosity for (a) N6CN3.7 melt at 225 °C and for (b) PPCN4 at 150 °C. The solid line shows three times the shear viscosity, , taken at a low shear rate = 0.001 s
−1
on a cone–plate rheometer. Reproduced from Okamoto [90] with permission of Rapra Technology.
Figure 5.22 Couette-type shear cell for SANS and the model for real-space orientation of the oriented clay platelets in the cell. The reference coordinate frame is anchored in the tangential beam. Reproduced from Scmidt [77] with permission of American Chemical Society.
Figure 5.23 SEM images for PP-MA and various PPCNs foamed at different temperatures. Reproduced from Nam et al. [106] with permission of John Wiley and Sons.
Figure 5.24 A schematic diagram of the visual observation apparatus for batch physical foaming. Reproduced from Taki et al. [107] with permission of John Wiley and Sons.
Figure 5.25 Representative average growth rates for PP-MA and nanocomposite foaming. Reproduced from Taki et al. [107] with permission of John Wiley and Sons.
Figure 5.26 The relation of relative modulus (
K
f
/
K
p
) against relative density (
ρ
f
/
ρ
p
) of neat PLA and PLA-based nanocomposite foams, taken in the directions parallel (a) and perpendicular (b) to the flow.
Figure 5.27 Typical results of FE-SEM images of the fracture surfaces of the structural foams processed at two different conditions under FIM process. (a)–(g) are skin layers enclosing the foamed core, and (a′)–(g′) are center areas of the foamed core. Reproduced from Hayashi et al. [115] with permission of Elsevier.
Figure 5.28 (a) Specific dynamic storage modulus () at –50 °C and (b) specific thermal expansion coefficient (
α
) in the temperature range of –150 to 0 °C of solids and foams. Reproduced from Hayashi et al. [115] with permission of Elsevier.
Chapter 6: Processing and Rheological Behaviors of Cnt/Polymer Nanocomposites
Figure 6.1 Schematic representations of (a) single-wall carbon nanotubes (SWCNTs); (b) multi-wall carbon nanotubes (MWCNTs); transmission electron micrographs of (c) SWCNTs and (d) MWCNTs. Reproduced from Eatemadi et al. [7] with permission of Open Access.
Figure 6.2 Schematic representations on various processing types of polymer–CNTs composites: (a) solution mixing; (b) melt mixing; (c) in situ polymerization.
Figure 6.3 (a) Scanning electron microscopy (SEM) image of MWCNT-PVOH nanocomposites. Reproduced from Shaffer et al. [18] with permission of John Wiley and Sons. (b and c) TEM images of the undrawn 1 wt% MWCNT-UHMWPE nanocomposites. (b) A global view showing the macroscopic distribution of the embedded CNTs and their effects on PE crystallization. No staining was applied but the PE phase displays a clear lamellar structure radiating from the clustered CNTs. (c) A magnified view of one of the clustered CNT regions displaying the dispersion of CNTs as individual tubes. Some clusters on the nanoscale show local entanglements between CNTs. Reproduced from Ruan et al. [19] with permission of Elsevier.
Figure 6.4 Schematic representations of various process models. Reproduced from Balogun and Buchanan [29a] with permission of Elsevier.
Figure 6.5 Scanning electron micrographs (SEM) of SWCNT-UHMWPE with 5% filler: (a) and (b) represent the same sample imaged at different magnifications. Reproduced from Grady et al. [29b] with permission of John Wiley and Sons.
Figure 6.6 (a) Reaction scheme of polymer-grafted MWCNTs via free radical graft polymerization (FRGP); scanning electron microscopy (SEM) images of (b) pristine MWCNTs; (c) MWCNTs-PS; and (d) HR-TEM images of MWCNT-PS. Reproduced from Park et al. [36] with permission of Elsevier.
Figure 6.7 Transmission electron microscopy (TEM) images of (a) polystyrene (PS) wrapped MWCNTs and (b) poly(methyl methacrylate) (PMMA) wrapped MWCNTs. Reproduced from Wu et al. [37] with permission of Elsevier.
Figure 6.8 Schematic (not to scale) of carbanion formation and subsequent initiation of polymerization: (a) section of SWCNT sidewall showing
sec
-butyl lithium addition to a double bond (gray arrow indicates the bond to which it adds) and formation of anion via transfer of charge, (b) the carbanion attacks the double bond in styrene, which in turn transfers the negative charge to the monomer. Successive addition of styrene results in the formation of living polymer chain. (c) Tapping mode atomic force microscopy (TMAFM) image of a polystyrene-grafted SWCNT/polystyrene film. (d) AFM height profile of an individual nanotube of diameter ∼0.8 nm. Reproduced from Viswanathan et al. [38] with permission of American Chemical Society.
Figure 6.9 (a) Schematic representation of surface-initiated atom transfer radical polymerization (SI-ATRP) of polymer brushes on MWCNT surfaces; TEM images of pristine MWCNT (b) PMMA-grafted MWCNTs (c and d) [c, monomer: MWCNT-Br 1:1; monomer: CuBr:
N
,
N
,
N′
,
N″
,
N″
-pentamethylene diethylenetriamine ratio, 5:1:1; temperature, 60 °C; time, 20 h; d, monomer: MWCNT-Br 10:1; monomer: CuBr:
N
,
N
,
N
′,
N″
,
N″
-pentamethylene diethylenetriamine ratio: 50:1:1; temperature, 60 °C; time: 30 h]. Reproduced from Kong et al. [43] with permission of American Chemical Society.
Figure 6.10 (a) Functionalization of pristine SWNTs and ATRP of
n
-butyl acrylate from such functionalized SWCNTs and (b) TMAFM height images of SWCNT-BA-1 (DP of BA = 218): (a) original height; inset: phase image. Image size: 830 × 830 nm
2
. Pixel size: 1.62 × 1.62 nm
2
. (b) Image after reconstruction (grafting densities of regions A: 1.6, 2.1, and 1.2 chains/nm
2
). Reproduced from Wu et al. [44] with permission of John Wiley and Sons.
Figure 6.11 (a) Synthesis of nylon-6 SWCNT composite by ring-opening polymerization of caprolactam in the presence of SWCNTs. (b) Schematic of the fiber spinneret setup. (c) Photograph of the spinneret setup. (d) Photograph of the composite fiber. (e) SEM image of cross-sectional fracture of the composite fiber. Reproduced from Gao et al. [54] with permission of American Chemical Society.
Figure 6.12 (a) Synthesis of polyamide/functionalized carbon nanotube (FCNT) composite (PA–FCNT), FCNT–
short-chain
PA and FCNT–
long-chain
PA, TEM images of (a) polyamide-pristine CNT composites and (b) polyamide-ethylene diamine-g-CNT composites. Reproduced from Shabanian et al. [55] with permission of Royal Society of Chemistry.
Figure 6.13 Tapping mode atomic force microscopy (TMAFM) images of (a, b) PC with 15 wt% MWCNT (Masterbatch); (c, d) PC with 1 wt% MWCNT; (e, f) PC with 2.0 wt% MWCNT. Reproduced from Poetschke et al. [65] with permission of Taylor & Francis.
Figure 6.14 SEM images of the nanocomposite fibers containing (a) 10 wt% carbon nanofibers (CNF), (b) 10 wt% entangled catalytically grown nanotubes (eCGCNT), (c) 5 wt% aligned catalytically grown nanotubes (aCGCNT), and (d) 5 wt% arc-grown carbon nanotubes (AGCNT). Reproduced from Sandler et al. [71] with permission of Elsevier.
Figure 6.15 (a) Storage modulus
G
′ of nanotube-filled polycarbonate at 260 °C. (b) Complex viscosity versus nanotube content at different frequencies (inset). Schematic of (left) isolated nanotube dispersion below the percolation threshold, (center) onset of percolation, the matrix spanning
backbone connectivity
is marked white, and (right) fully grown network. (c) Schematic of CNTs–polymer nanocomposites in which the nanotube bundles have isotropic orientation. (Top) At low nanotube concentrations, the rheological and electrical properties of the composite are comparable to those of the host polymer. (Bottom) The onset of solid-like viscoelastic behavior occurs when the size of the polymer chain is somewhat large to the separation between the nanotube bundles. Reproduced from Chatterjee and Krishnamoorti [75] with permission of Royal Society of Chemistry.
Figure 6.16 (a) Frequency dependence of storage (
G′
) and loss modulus (
G
″) of epoxy-MWCNT suspension (0.5 wt%) prepared by magnetic mixing (sample A) and ultrasonication (sample B), TEM images of MWCNT in epoxy using (b) ultrasonication and (c) magnetic stirring. Reproduced from Ran et al. [89] with permission of AIP Publishing.
Figure 6.17 Schematic of two types of network structures: I, continuous network between aggregates connected by separated individual MWCNTs; II, continuous network between separated MWCNT fibers. Reproduced from Ran et al. [89] with permission of AIP Publishing.
Figure 6.18 (a) A schematic of the hierarchical network structure showing different length scales. The major characteristic length scales are the floc size (
R
) and mesh size (
ζ
). (b) A representative model fit (solid red line) to the smeared scattering data. The solid vertical lines represent scattering vector
q
values associated with different network length scales (=2π/
q
). The intensity mismatch is due to instrument smearing. (c) Optical microscopic image of a representative SWCNT network (
φ
/
φ
c
= 4.0, in PEO) verifies the presence of micron-sized flocs as obtained from scattering data fitting. Reproduced from Chatterjee and Krishnamoorti [93] with permission of American chemical Society.
Figure 6.19 (a) Frequency dependence of the phase angle, tan
δ
, from linear dynamic oscillatory shear measurements for carbon nanotubes with 0.1–1.0 vol% CNTs. For
φ
≥ 0.3 vol%, a composition invariant behavior is observed at low frequencies. (b) Time–temperature–composition superposed master curves for different linear dynamic rheological properties for PEO-based nanocomposites with CNT loading range from 0.3 to 1.0 vol%. Reproduced from Chatterjee and Krishnamoorti [75] with permission of Royal Society of Chemistry.
Figure 6.20 (a) Representative stress relaxation behavior for CNTs loading
φ
= 0.7 vol% in PEO (
M
w
= 8000 Da) as a function of the applied bulk strain amplitude. For low-amplitude strain (
γ
≤ 0.003 where
γ
critical
= 0.003), linear behavior is observed followed by a time–strain superposable zone (gray curves, 0.003 ≤
γ
≤ 0.03). At higher strain amplitude (
γ
> 0.03), time–strain superposability is violated (black curves). (b) Damping function
h
(
γ
) required for the time–strain superposition for different nanocomposites is plotted against the applied or bulk strain (
γ
bulk
). Deviation from
h
(
γ
) = 1.0 marks the onset of nonlinearity. With increasing nanotube loading, an earlier onset of nonlinear response (i.e., lower
γ
critical
) is observed. (c) The local strain dependence of
h
(
γ
). The onset of the shear thinning is observed at
γ
local
∼ 0.1 and is similar to other nanocomposite systems with short-range interactions. Therefore, at and around 10% deformations, the nanocomposite network starts to flow. Reproduced from Chatterjee and Krishnamoorti [75] with permission of Royal Society of Chemistry.
Figure 6.21 TEM images of different MWCNT arrangements in a polycarbonate matrix: (a) initial agglomerates; (b) well-dispersed MWCNTs; and (c) secondary agglomerates. (d, e) Time-dependent conductivity for initially agglomerated and well-dispersed composites of MWCNT (0.6 vol%) in PC under steady shear deformation (
dγ
/
dt
= 0.02 s
−1
for 1 h) and during quiescent annealing after shear at 230 °C (inset: schematics show the state of nanotube dispersion and the measuring cell with the sample). (f) Schematic representation of the differences between the conductivity (“electrical network”) and rheological properties (mechanical active filler network): The shaped nanotubes are represented by black lines and the polymer chains by gray lines. To symbolize the contact resistance, an “electrical equivalent circuit” was taken, whereas the viscoelastic coupling between CNTs via polymer chains is represented by a “dash pot” for local friction and an “entropic spring.” Reproduced from Alig et al. [101] with permission of Elsevier.
Figure 6.22 (a) Representative transient shear stress response obtained during start-up of steady shear measurements for an SWCNT–PEO dispersion (
φ
/
φ
c
= 5.0). For all shear rates, the stress data exhibit an initial overshoot arising from the shear-induced cluster aggregation, and in the long time, the network breaks to reach a steady state. Solid lines are model fits to the experimental data as described in Ref. [101]. Reproduced from Chatterjee and Krishnamoorti [102] with permission of American Chemical Society. (b) Comparison of the complex and steady shear viscosities as a test for the Cox–Merz rule. The nanocomposites fail to obey the Cox–Merz rule presumably because of an alteration in the mesoscale structure during steady flow. Reproduced from Chatterjee and Krishnamoorti [102] with permission of American Chemical Society.
Figure 6.23 (a) Flow curve for PE-LCB and its composites with high amount of MWCNTs measured at 190 °C (arrows indicate the onset of the spurt instability); (b–e) SEM images showing the effect of MWCNTs on the surface morphology of PE-SCB composites processed at a shear rate of 472 s
−1
(under these conditions, the samples develop sharkskin instability); (f–i) SEM images showing the effect of MWCNTs amount on the surface morphology of PE-SCB composites processed at a shear rate of 1054 s
−1
(under these conditions, the samples develop gross melt fracture. Insets in (b) and (d) demonstrate detailed morphological changes occurring with increasing MWCNTs amount). Reproduced from Palza et al. [107] with permission of Elsevier.
Figure 6.24 (i) Schematic representation of hyperbranched poly(urea-urethane) (HPU)-grafted MWCNT. (ii) TEM image of HPU-grafted MWCNT. (iii) Solution rheology of HPU-grafted MWCNT at two different temperatures (20 and 80 °C). (iv) Rheological mechanism of the HPU-functionalized MWCNTs in their solutions. Reproduced from Yang et al. [115] with permission of American Chemical Society.
Figure 6.25 (i) The formation of cylindrical flocs aligned along the vorticity direction. The micrograph was collected for shear rate = 0.5 s
−1
, gap = 180 µm, and time = 600 s. Direction of flow is vertical as indicated. For this optical micrograph, vorticity alignment of CNT flocs is clearly visible. (ii) Schematic diagram of the growth mechanism. A nucleus rotates within the steady shear and captures initially isotropic aggregates of nanotubes. The nanotubes are then wound helically to form a cylinder with long axis perpendicular to the direction of flow. Reproduced from Ma et al. [108] with permission of Springer. (iii) Photos of extrudates of pure iPP and CNT/iPP melt (7.4% mass fraction) at 210 °C under different shear rates. The diameter and length of capillary die were 1 and 32 mm, respectively. iPP at 100 s
−1
, mean diameter of 1.34 mm (a); iPP at 500 s
−1
, mean diameter of 1.46 mm (b); iPP at 1000 s
−1
, mean diameter of 1.67 mm (c); iPP at 2000 s
−1
, mean diameter of 1.82 mm (d); 7.4% mass fraction CNT/iPP at 100 s
−1
, mean diameter of 1.18 mm (e); 7.4% mass fraction CNT/iPP at 500 s
−1
, mean diameter of 1.38 mm (f); 7.4% mass fraction CNT/iPP at 1000 s
−1
, mean diameter of 1.54 mm (g); 7.4% mass fraction CNT/iPP at 2000 s
−1
, mean diameter of 1.66 mm (h). The gray circle in the Figure shows the size of the capillary die for comparison. The minimum scale of the ruler at the downside of the Figure is 1 mm. The relative measurement uncertainty of the extrudate diameter was estimated to be about 1%. Reproduced from Xu et al. [116] with permission of American Chemical Society. (iv) Models about deformations of low aspect ratio CNT/iPP and high aspect ratio CNT/iPP networks under steady shear. Reproduced from Xu et al. [116] with permission of American Chemical Society.
Chapter 7: Unusual Phase Separation in PS Rich Blends with PVME in Presence of MWNTs
Figure 7.1 Isochronal dynamic temperature ramp performed at
ω
= 0.1 rad/s, 1% strain with 0.5 °C/min heating rate for (a) 90/10 PS/PVME neat blends and blend with (b) 0.25 wt% MWNT and (c) 0.5% MWNT.
Figure 7.2 Variation of correlation length as a function of temperature for (a) 90/10 PS/PVME blend with (b) 0.25 wt% MWNT and (c) 0.5% MWNT.
Figure 7.3 Reciprocal square correlation length versus 1000/
T
for (a) 90/10 PS/PVME neat blends and blend with (b) 0.25 wt% MWNT and (c) 0.5% MWNT.
Figure 7.4 POM images for 90/10 PS/PVME blend with and without MWNTs during early (a
1
, b
1
, c
1
); intermediate (a
2
, b
2
, c
2
), and late (a
3
, b
3
, c
3
) stages of phase separation. The top row is for neat 90/10 PS/PVME blends. The middle and the bottom rows are for 90/10 PS/PVME blends with 0.25 and 0.5 wt% MWNTs, respectively. (The darker phase represents PS and the brighter phase corresponds to the PVME phase; scale bar corresponds to 20 µm).
Chapter 8: Rheology and Processing of Polymer/POSS Nanocomposites
Figure 8.1 Structures of POSS. (a) Random structure, (b) ladder structure, (c–e) cage structures, and (f) partial cage structure. Reproduced from Kuo et al. [78] with permission of Elsevier.
Figure 8.2 General polymer/POSS architectures. Reproduced from Kuo et al. [78] with permission of Elsevier.
Figure 8.3 Schematic presentation of polymer/POSS composites melt blending using (a) internal mixer and (b) screw extruder.
Figure 8.4 SEM images of PP/POSS composites: (a) physical blending composites; (b) reactive blending composites; and (c) POSS-g-PP. Reproduced from Zhou et al. [131] with permission of Elsevier.
Figure 8.5 Polarizing optical micrographs of growing spherulites: (a) PP/OM
3
; (b) PP/IOB
10
molten samples during isothermal crystallization at
T
ic
= 130 °C. Reproduced from Pracella et al. [134] with permission of John Wiley and Sons.
Figure 8.6 Tensile strength curves of PE/POSS nanocomposites with different contents of POSS. PB – octaisobutyl–POSS; PM – octamethyl–POSS; PP – octaphenyl–POSS. Reproduced from Lim et al. [115] with permission os Elsevier.
Figure 8.7 tan
δ
value versus
ω
for EPI/POSS nanocomposite containing 20 wt% octaisobutyl-POSS molecules at 160 °C. The hypothesized dotted line represents the gel point. Reproduced from Fu et al. [206] with permission of Elsevier.
Figure 8.8 Schematic of the filled copolymer blend. At low loadings of untethered-POSS (black circles), most of the tethered-POSS groups are present in an unbound state (open circles). However, a kinetic exchange takes place whereby a particular chain (represented by the dashed line) may contain (a) an “active” tethered-POSS group (gray circle), which forms a thermodynamic association with a nanocrystallite of untethered-POSS. This temporary association may (b) break, thus allowing the chain to reptate freely before (c) a different tethered-POSS group on the same chain forms an association with the nanocrystallite. This kinetic exchange between an associated and a dissociated state leads to the dramatic slowdown in the relaxation processes in the copolymer matrix. Reproduced from Kopesky et al. [209] with permission of American Chemical Society.
Figure 8.9 Log–log plot of
η
ap
as a function of the POSS concentration as measured by the capillary rheometry of the Dp-POSS composites (PPSU – thermoplastic polyphenylsulfone; Dp-POSS – closed-cage dodecaphenyl polyhedral oligomeric silsesquioxane). Reproduced from Jones et al. [212] with permission of John Wiley and Sons.
Figure 8.10 Flow curves of polystyrene and polystyrene-POSS nanocomposites (PS – polystyrene; IB-PS and TSIB-PS –
i-butyl
-POSS-polystyrene; IO-PS and TSIO-PS –
i-octyl
-POSS-polystyrene; TSPH-PS –
phenyl
-POSS-polystyrene). Reproduced from Dintcheva et al. [214] with permission of Budapest University of Technology and Economics.
Chapter 9: Polymer and Composite Nanofiber: Electrospinning Parameters and Rheology Properties
Figure 9.1 Fundamental physical relationships of materials rheology.
Figure 9.2 Schematic image of typical electrospinning setup and its process parameters influencing the nanofiber morphology. Reproduced from Pelipenkp et al. [3] with permission of Elsevier. (b) Visual images of multiple parallel electrospinning jets and the resultant linear and whipping regions of the jets. Reproduced from Roman et al. [4] with permission of American Chemical Society.
Figure 9.3 Morphology of electrospun fibers at various PVAc concentrations: (a) 5 wt%, (b) 8 wt%, (c) 10 wt%, (d) 15 wt%, (e) 20 wt%, (f) 25 wt%, and (g) 30 wt% (applied voltage, 15 kV; flow rate, 100 µl/min; distance, 10 cm). Reproduced from Park et al. [13] with permission of Elsevier.
Figure 9.4 Schematic representation of electrospun jet development under various RH conditions. Reproduced from Pelipenkp et al. [3] with permission of Elsevier.
Figure 9.5 SEM images of polycaprolactone (PCL) fibers spun from a 15 wt% solution at different temperatures and relative humidity (RH). Reproduced from Putti et al. [14] with permission of Elsevier.
Figure 9.6 (a–f) Electrospun chitosan–PEO nanofibrous structures illustrating the effect of acetic acid concentration, chitosan–PEO ratio, and total polymer concentration. (g) Zero shear rate viscosity (
η
0
) of chitosan/PEO solutions measured as a function of time. Reproduced from Klossner et al. [23] with permission of American Chemical Society.
Figure 9.7 Interfacial viscosity, storage (
G
′), and loss (
G
″) moduli as a function of solution composition of (a) chitosan : PEO and (b) alginate : PEO blends. (c–e) Viscosity, electrical conductivity, and surface tension of low-viscosity alginate and PEO blends in the absence and presence of triton. Reproduced from Rošic et al. [25] with permission of Elsevier; Reproduced from Saquing et al. [26] with permission of American Chemical Society.
Figure 9.8 (a) Electrospun samples from PFSA/PVP/DMF solutions with different compositions (I – droplets region, II – beaded fibers region, III – fine fibers region) and (b) mixing the two endpoint solutions of the line using principles of balance. Reproduced from Zhao et al. [34] with permission of John Wiley and Sons.
Figure 9.9 (a) Influence of molar mass and concentration on the viscosity of PDMAEMA·HCl and (b) the corresponding FESEM images of electrospun PDMAEMA·HCl fibers. Reproduced from McKee et al. [37] with permission of American Chemical Society.
Figure 9.10 FESEM images of electrospun nylon-6 nanofibers mats at different voltages: (a) m12 (12 kV); (b and d) m22 (22 kV); and (c and e) m32 (32 kV); and (f) typical tensile stress–strain curves of electrospun nylon-6 mat. Reproduced from Pant et al. [38] with permission of Elsevier.
Figure 9.11 Viscosity versus shear rate graphs of (a) α-CD solutions and (b) β-CD solutions. Reproduced from Celebioglu et al. [40] with permission of Elsevier.
Figure 9.12 (a) SEM image of the polyimide morphology at different solution concentrations and (b) specific viscosity concentrations with the corresponding developed morphology. Reproduced from Chisca et al. [42] with permission of American Chemical Society.
Chapter 10: Rheology and Processing of Inorganic Nanomaterials and Quantum Dots/Polymer Nanocomposites
Figure 10.1 Linear melt-state rheological properties as a function of oscillatory frequency: (a) storage modulus,
G
′ and (b) loss modulus,
G
″. Reproduced from Wang et al. [8] with permission of Elsevier.
Figure 10.2 Size-tunable fluorescence spectra of CdSe quantum dots (a) and illustration of the relative particle sizes (b). From left to right, the particle diameters are 2.1, 2.5, 2.9, 4.7, and 7.5 nm. Reproduced from Smith and Nie [10] with permission of Royal Society of Chemistry.
Figure 10.3 (a) Shear stress versus shear rate and (b) viscosity versus shear rate of neat PVA solution and PVA/QDs dispersions and SEM images of 0% QDs, 1.0% QDs, and 5% QDs in PVA. Reproduced from Atabey et al. [21] with permission of SAGE.
Figure 10.4 Viscosity versus shear rate of the solutions (a) without IL and (b) with 1 wt% IL and shear stress versus shear rate of the solutions (c) without IL and (d) with 1 wt% IL. Reproduced from Zhu et al. [24] with permission of Elsevier.
Figure 10.5 (a) Viscosity and (b) shear stress versus shear rate of PMMA and PMMA-QDs solutions. Reproduced from Wei et al. [23] with permission of Elsevier.
Figure 10.6 Frequency-dependent viscoelastic properties of PP/EPDM/B-SiO
2
(80/20/3) composites at different mixing time: (a) one step; (b) two steps: (1) storage modulus (
G
0
) and (2) viscosity (
η
*). Reproduced from Yang et al. [25] with permission of Elsevier.
Figure 10.7 Surface tension at varying concentrations of QD's. Reproduced from [27] with permission of Amelia Elliott.
Figure 10.8 Viscosity of QD's + photopolymer. Reproduced from [27] with permission of Amelia Elliott.
Figure 10.9 Viscosity at a shear rate of 100 s
−1
versus volume fraction of nanoparticles. Lines represent the different theoretical models. Reproduced from Sheng et al. [37] with permission of John Wiley and Sons.
Figure 10.10 Viscosity versus temperature data from a series of SiO
2
/Epon862/W nanocomposite samples. The onset temperature is taken from the crossing of tangent lines representing the minimum viscosities and the trend at the steepest part of the curves (tangent lines not shown). The maximum temperature was taken as the maximum of the derivative of the viscosity profile,
η
*. Reproduced from Chen et al. [42] with permission of Elsevier.
Figure 10.11 Variation in storage modulus with strain rate. Reproduced from Cassagnau [47] with permission of Elsevier.
Figure 10.12 Elastic shear modulus
G
′ (a) and
G
″ (b) as a function of pulsation
ω
, using time–temperature superposition (T0) 143 °C) coefficient
aT
defined in the text, for different volume fractions of silica in the composite (0%, 1%, 2%, 3%, 4%, and 5% v/v). Reproduced from Jouault et al. [48] with permission of American Chemical Society.
Figure 10.13 Flow index versus shear rate with different composites and SEM image of TiO
2
nanoparticles dispersed randomly in LLDPE/LDPE/TiO
2
composite films. Reproduced from Wang et al. [51] with permission og John Wiley and Sons.
Figure 10.14 Flow curves for PANI/TN-1 (b, d) and PANI/TN-2 (a, c) based fluids under different electric field strengths. Reproduced from Cheng et al. [55] with permission of John Wiley and Sons.
Figure 10.15 Viscosity versus shear rate of epoxy resin suspensions filled with different loadings of (a) μ-Fe
3
O
4
NPs and (b) f-Fe
3
O
4
NPs at 25 °C; (c) effect of surface functionalization on the viscosity of Fe
3
O
4
/epoxy nanocomposite suspensions with different loadings under different shear rates at 25 °C; (d) Effect of temperature on the viscosity of epoxy resin suspensions with a Fe
3
O
4
particle loading of 15 wt%. Reproduced from Gu et al. [56] with permission of American Chemical Society.
Figure 10.16 Effect of ferrite content on the yield stress of PET. Reproduced from Chae et al. [59] with permission of Elsevier.
Figure 10.17 Complex viscosity versus shear rate at 220 °C for (a) PP, POE, and POE/nano-CaCO
3
, and (b) PP, POE, and PP/POE/nano-CaCO
3
. Logarithmic plots of
G
′ versus
G
″ for the PP and its binary and ternary composites at 220 °C. Reproduced from Ma et al [68] with permission of Elsevier.
Chapter 11: Rheology and Processing of Laponite/Polymer Nanocomposites
Figure 11.1 TEM images of neat PU, ex situ, and in situ prepared PU–clay nanocomposite [52]. (I3cAPL = TPU with 3% of cAPL prepared by in situ technique (cAPL: Laponite RD modified by CTAB followed by 3-aminopropyltriethoxysilane (AP); E3cAPL = TPU with 3% of cAPL prepared by ex situ technique; E3cOSL = TPU with 3% of cOSL prepared by ex situ technique (cOSL: Laponite RD modified by CTAB followed by OS); I3cOSL = TPU with 3% of cOSL prepared by in situ technique). Reproduced from Mishra et al. [52] with permission of Elsevier.
Figure 11.2 Schematic representation of a sheet of Laponite whose silanol groups have been reacted with alkoxy silanes. Reproduced from Wheeler et al. [65] with permission of American Chemical Society.
Figure 11.3 Hydrogelation by mixing Laponite (CNS as shown) and molecular binders in water. (a) Schematic representation of the mechanism of hydrogelation. (b, c) Pictures of supramolecular hydrogels. Reproduced from Tamesue et al. [89] with permission of American Chemical Society.
Figure 11.4 Schematic representations of the model structures for the reaction solution and the mechanism of forming organic/inorganic network structure in an NC gel. (a) Aqueous solution consisting of clay and NIPAm. Here, the formation of house-of-cards structure does not form. (b) Reaction solution consisting of clay, NIPAm, potassium persulfate (KPS), and
N
,
N
,
N
′,
N
′-tetramethylethylenediamine (TEMED). (c) Radical formation near the clay surface in the reaction solution. (d) Formation of clay–brush particles. (e) Formation of organic/inorganic networks. In the models, only a small number of monomer (polymer), KPS, and TEMED are depicted for simplicity. Reproduced from Haraguchi et al. [105] with permission of American Chemical Society.
Figure 11.5 Proposed mechanism for the ionic Laponite/poly(AMPS-
co
-AA) NC gels [14]. Reproduced from Chen et al. [14] with permission of Elsevier.
Figure 11.6 Possible mechanisms for the development of different types of structures [52]. (a) TPU; TPU/Laponite nanocomposites prepared by (b, c): solution blending (d, e) in situ technique. Reproduced from Mishra et al. [52] with permission of Elsevier.
Figure 11.7 Outline of the synthetic route toward the preparation of highly filled poly(St-
co
-BA)/Laponite hybrid latexes [34]. Reproduced from Zengeni et al. [34] with permission of Elsevier.
Chapter 12: Graphene-Based Nanocomposites: Mechanical, Thermal, Electrical, and Rheological Properties
Figure 12.1 (a, b) TEM images of polyurethane/graphene nanosheets; (c, d) SEM images of PVA/chemically reduced graphene.
Figure 12.2 XRD patterns of PVDF/GOs nanocomposites. From Ref. [21]. Reproduced with permission of Elsevier.
