Figure 1
Unit cyclic (a), linear (b), and associate (c) structures of MAO; red balls: oxygen; gray balls: aluminum and methyl groups. Reprinted with permission from reference 35. Copyright 2014 American Chemical Society
Figure 2
Structures of metallocenes used for the synthesis of PP and PE.33 Kaminsky, W.; Materials2014, 7, 1995.
Figure 3
Nanofiller families including molecules and inorganic nanoparticles. Adapted from reference 41.
Figure 4
Polymer activity as a function of polymerization temperature for the nanosized and the microsized catalysts with 2 h of polymerization time; (a) [Al]/[Zr] = 570 and (b) [Al]/[Zr] = 17. Adapted from reference 53.
Figure 5
Models for the interactions of metallocene Cp2ZrCl2 with species present in acidic silicate surfaces (A: acidic element). Reprinted from reference 57. Copyright 2014, with permission from Elsevier.
Figure 6
Interaction of MCM-41 with a metallocene, followed by MAO. Reprinted from reference 61. Copyright 2014, with permission from Elsevier.
Figure 7
(a) Proposed interaction between grafted metallocene species within larger and smaller diameter pores. (b) Correlation between Zr-C interatomic distance and catalyst activity. Adapted from reference 63.
Figure 8
Correlation between the mean Zr-O interatomic distance in the grafted species and the Mw of the resulting PE. Reprinted with permission from reference 63. Copyright (c) 2014 [John Wiley and Sons, Inc.].
Figure 9
(A to C) SEM images of freeze-dried PE at three different magnifications. From reference 74. Reprinted with permission from AAAS.
Figure 10
Conceptual scheme for the growth of crystalline fibers of PE by mesoporous silica-assisted extrusion polymerization. From reference 74. Reprinted with permission from AAAS.
Figure 11
Preparation of Cp2ZrCl2-MWCNT. Reprinted with permission from reference 79. Copyright (c) 2014 [John Wiley and Sons, Inc.].
Figure 12
(A) Scheme of homogeneous surface coating of MWCNTs caused by in situ polymerization. (B) TEM micrographs of MWNTs coated by in situ grown E-N copolymers (highlighted by the arrow) (45 wt.% E-N). Adapted from references 80 and 81.
Figure 13
Different routes for nanotubes’ functionalization: sidewall covalent functionalization (a); defect-group covalent functionalization (b); noncovalent polymer wrapping (c); noncovalent pi-stacking (d).8282 Beyou, E.; Akbar, S.; Chaumont, P.; Cassagnau, P. In Syntheses and Applications of Carbon Nanotubes and Their Composites; Suzuri, S., ed.; InTech: Cassagnau, 2013; pp. 77-115.
Figure 14
Structure of 2:1 phyllosilicates and schematically illustration of clay form factors of dispersed clay and the three different types of thermodynamically achievable polymer/layered silicate nanocomposites. Reprinted with permission from reference 86. Copyright 2014 American Chemical Society.
Figure 15
Scheme of the delamination of alkylammonium-exchanged layered clays (on the left) with alkoxides following a sol-gel process giving rise to intermediate organo-clay materials that after thermal treatment (> 450 °C) in the presence of oxygen leads in a second step to delaminated clay-nanoparticles (NPs) materials. Reproduced from reference 90 with permission from The Royal Society of Chemistry.
Figure 16
Surface modification of clay with quaternary and tertiary ammonium salts. Adapted from reference 93.
Figure 17
Proposed reactions during catalyst supporting on Cloisite 93A. Adapted from reference 93.
Figure 18
Schematic illustrations of the formation process of PE/P-MMTs nanocomposites during in situ ethylene polymerization in the presence of P-MMTs with different concentration. Reprinted with permission from reference 98. Copyright (c) 2014 [John Wiley and Sons, Inc.].
Figure 19
Schematic illustration of mechanism for formation of MT-Si and the PE/clay-silica nanocomposites. Adapted from reference 99.
Figure 4
Polymer activity as a function of polymerization temperature for the nanosized and the microsized catalysts with 2 h of polymerization time; (a) [Al]/[Zr] = 570 and (b) [Al]/[Zr] = 17. Adapted from reference 53.
Figure 5
Models for the interactions of metallocene Cp2ZrCl2 with species present in acidic silicate surfaces (A: acidic element). Reprinted from reference 57. Copyright 2014, with permission from Elsevier.
Figure 6
Interaction of MCM-41 with a metallocene, followed by MAO. Reprinted from reference 61. Copyright 2014, with permission from Elsevier.
Figure 7
(a) Proposed interaction between grafted metallocene species within larger and smaller diameter pores. (b) Correlation between Zr-C interatomic distance and catalyst activity. Adapted from reference 63.
Figure 8
Correlation between the mean Zr-O interatomic distance in the grafted species and the Mw of the resulting PE. Reprinted with permission from reference 63. Copyright (c) 2014 [John Wiley and Sons, Inc.].
Figure 9
(A to C) SEM images of freeze-dried PE at three different magnifications. From reference 74. Reprinted with permission from AAAS.
Figure 10
Conceptual scheme for the growth of crystalline fibers of PE by mesoporous silica-assisted extrusion polymerization. From reference 74. Reprinted with permission from AAAS.
Figure 11
Preparation of Cp2ZrCl2-MWCNT. Reprinted with permission from reference 79. Copyright (c) 2014 [John Wiley and Sons, Inc.].
Figure 12
(A) Scheme of homogeneous surface coating of MWCNTs caused by in situ polymerization. (B) TEM micrographs of MWNTs coated by in situ grown E-N copolymers (highlighted by the arrow) (45 wt.% E-N). Adapted from references 80 and 81.
Figure 13
Different routes for nanotubes’ functionalization: sidewall covalent functionalization (a); defect-group covalent functionalization (b); noncovalent polymer wrapping (c); noncovalent pi-stacking (d).8282 Beyou, E.; Akbar, S.; Chaumont, P.; Cassagnau, P. In Syntheses and Applications of Carbon Nanotubes and Their Composites; Suzuri, S., ed.; InTech: Cassagnau, 2013; pp. 77-115.
Figure 14
Structure of 2:1 phyllosilicates and schematically illustration of clay form factors of dispersed clay and the three different types of thermodynamically achievable polymer/layered silicate nanocomposites. Reprinted with permission from reference 86. Copyright 2014 American Chemical Society.
Figure 15
Scheme of the delamination of alkylammonium-exchanged layered clays (on the left) with alkoxides following a sol-gel process giving rise to intermediate organo-clay materials that after thermal treatment (> 450 °C) in the presence of oxygen leads in a second step to delaminated clay-nanoparticles (NPs) materials. Reproduced from reference 90 with permission from The Royal Society of Chemistry.
Figure 16
Surface modification of clay with quaternary and tertiary ammonium salts. Adapted from reference 93.
Figure 15
Scheme of the delamination of alkylammonium-exchanged layered clays (on the left) with alkoxides following a sol-gel process giving rise to intermediate organo-clay materials that after thermal treatment (> 450 °C) in the presence of oxygen leads in a second step to delaminated clay-nanoparticles (NPs) materials. Reproduced from reference 90 with permission from The Royal Society of Chemistry.
Figure 16
Surface modification of clay with quaternary and tertiary ammonium salts. Adapted from reference 93.
Figure 17
Proposed reactions during catalyst supporting on Cloisite 93A. Adapted from reference 93.
Figure 18
Schematic illustrations of the formation process of PE/P-MMTs nanocomposites during in situ ethylene polymerization in the presence of P-MMTs with different concentration. Reprinted with permission from reference 98. Copyright (c) 2014 [John Wiley and Sons, Inc.].
Figure 19
Schematic illustration of mechanism for formation of MT-Si and the PE/clay-silica nanocomposites. Adapted from reference 99.
Figure 20
Schematic illustration of two different types of thermodynamically achievable polymer/layered silicate nanocomposites. Reprinted from reference 101. Copyright 2014, with permission from Elsevier.
Figure 21
Schematic representation of PLS obtained by direct polymer melt intercalation of M2(HT)2 with LLDPE. Adapted from references 112 and 113.
Figure 22
Schematic representation of EVA/LLDPE/DS-LDH obtained by solution blending. Adapted from references 116 and 117.
Figure 23
(a) Phase separated and (b) randomly distributed morphology of graphene/polymer nanocomposites. Reprinted from reference 104, Copyright 2014, with permission from Elsevier
Figure 24
TEM images of 1 wt.% TRG with EG-8200-MA (a, b) prepared by melt compounding and (c, d) prepared by solvent blending. Adapted from reference 104.
Figure 25
Schematic representation nanocomposite production of PE/OMMT with rac-ethylene bis (4,5,6,7-tetra-hydro-1-indenyl) zirconium dichloride supported obtained by in situ polymerization. Adapted from reference 120.
Figure 26
Schematic representation of nanocomposite formation by ringopening reaction of cyclic oligomers in-between silicate layers. Reprinted from reference 121, Copyright 2014, with permission from Elsevier.
Figure 21
Schematic representation of PLS obtained by direct polymer melt intercalation of M2(HT)2 with LLDPE. Adapted from references 112 and 113.
Figure 22
Schematic representation of EVA/LLDPE/DS-LDH obtained by solution blending. Adapted from references 116 and 117.
Figure 23
(a) Phase separated and (b) randomly distributed morphology of graphene/polymer nanocomposites. Reprinted from reference 104, Copyright 2014, with permission from Elsevier
Figure 24
TEM images of 1 wt.% TRG with EG-8200-MA (a, b) prepared by melt compounding and (c, d) prepared by solvent blending. Adapted from reference 104.
Figure 25
Schematic representation nanocomposite production of PE/OMMT with rac-ethylene bis (4,5,6,7-tetra-hydro-1-indenyl) zirconium dichloride supported obtained by in situ polymerization. Adapted from reference 120.
Figure 26
Schematic representation of nanocomposite formation by ringopening reaction of cyclic oligomers in-between silicate layers. Reprinted from reference 121, Copyright 2014, with permission from Elsevier.
Figure 27
Micrographs of exfoliated nanocomposites composed by (A) PE-coated MWNTs with 12 wt.% by TEM; (B) silica (monospheres) in an isotactic PP matrix prepared with 50 wt.% by SEM; (C) silica (nanospheres) in PE with 7 wt.% by TEM and (D) MMT in a high Mw nylon-6 with 3 wt.% by TEM. Adapted from references 81, 3, 108 and 2, respectively.
Figure 28
Schematic representation of silicate intercalated by an initiator or catalyst that upon introduction of a monomer an intercalated or exfoliated polymer nanocomposite is formed. Reproduced from reference 125 with permission from The Royal Society of Chemistry.
Figure 29
Plot of powder X-ray diffraction intensity versus scattering angle: (a) 1-tetradecylammonium modified fluorohectorite (C14N-2); (b) C14N-2 after intercalation by the catalyst (Pd-2); (c) Pd-2 after exposure to ethylene for 135 min; (d) Pd-2 after exposure to ethylene for 24 h. Reproduced from reference 125 with permission from The Royal Society of Chemistry.
Figure 30
TEM images of the 2 wt.% C15A/PP nanocomposites: without a compatibilizer (A); with 1 wt.% OTMS (B) and with 1.5 wt.% PP‑g‑MA/0.5 wt.% OTMS (C). Adapted from reference 126.
Figure 31
TEM images (A) and XRD patterns (B) of PP nanocomposites with various organoclay contents (a): PPN-0.5; (b) PPN-1; (c) PPN-3; (d) PPN‑6. Adapted from reference 127.
Figure 32
Electron micrographs of a highly filled rhombic PE nanocomposite crystal (54 wt.% nanoparticles) (a) with homogeneous distribution of nanoparticles (b) and of spherical nanocomposite particles for a nanoparticle loading of 7.4 wt.% at low (c) and high (d) magnification. Reprinted with permission from reference 128. Copyright 2014 American Chemical Society
Figure 33
Structures of (A) DMN and (B) dimethylstearylbenzylammonium ions; (C) X-ray diffraction of high density PE nanocomposites: (a) bentonite modified with dimethylstearylbenzylammonium cations; (b) melt-compounded PE/DMSB composite; (c) in situ polymerized PE/DMSB nanocomposite; (d) high density PE. Adapted from reference 103.
Figure 34
TEM-images of PE/DMSB nanocomposites of high density PE: composite prepared by melt compounding (A) and prepared by in situ polymerization (B). Reprinted with permission from reference 103. Copyright (c) 2014 [John Wiley and Sons, Inc.].
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