ABSTRACT
FIGURE 4.1 Scanning electron microscopy (SEM) photomicrographs of very-low-density polyethylene (VLDPE)/styreneethylene butylene-graft-diethyl maleate (SEBS-g-DEM)/polyethylene terephthalate (PET) 40/40/20 blend cryogenic fracture. (A): after extraction with 1,1,1, 3,3,3 hexauoro 2 propanol (HFIP); (B): after the successive extraction with chloroform. (From M. B. Coltelli, I. Della Maggiore, S. Savi, M. Aglietto, and F. Ciardelli, Polym. Degrad. Stab. 90(2), 211-223, 2005; erratum 91, 987, 2006. With permission.)
12 kV ×550 20 µm
(B)
Aluminum
Teflon
20 24 SE I
FIGURE 4.2 SEM photomicrographs of the cryogenic fracture surface of a lm made of 90/10 polyethylene/copolyamide (PE/CPA) blend prepared via compression molding at 180°C and 125 bar for 10 min (A), 30 min (B), and 60 min (C). (From M. Bertoldo, M. B. Coltelli, L. Miraglia, P. Narducci, and S. Bronco, Polymer 46, 11311-11321, 2005. With permission.)
FIGURE 4.3 SEM photomicrograph of the smoothed and toluene-etched surface of a PET ultra-low-density polyethylene (ULDPE)-g-DEM blend obtained in a discontinuous mixer by adding Ti(OBu)4 as a transesterication catalyst. (From M. B. Coltelli, Catalysed Reactive Compatibilization of Polyolefin and Poly(ethylene terephthalate) Blends: Reactions Mechanisms and Phase Morphology Development, Ph.D. thesis, University of Pisa, Italy, 2005.)
12 kV ×700 20 µm
(C)
Aluminum
Teflon
20 24 SE I
FIGURE 4.2 (Continued)
FIGURE 4.4 SEM photomicrographs of PET/LDPE/SEBS-g-DEM 80/13.3/6.6 blends. Top images: before etching (left) and after etching (right). Bottom images: cryogenically broken surface in the center and near to the edge of the extruded strand. (From M. B. Coltelli, C. Harrats, M. Aglietto, and G. Groeninckx, EuroFillers and Polymer Blends Joint Meeting, Proceedings, p. 19, Brugge, Belgium, 2005.)
(A)
FIGURE 4.5
FIGURE 4.5 (Continued) SEM photomicrographs of the 70/30 PET/LDPE+diethyl maleate grafted ultra-low-density polyethylene (ULDPE-g-DEM) blends obtained with a mixing time of 20 min. (A) and (B): no copolymer, sample cut parallel to ow direction; (C): no copolymer, sample cut perpendicular to ow direction. (From M. B. Coltelli, Catalysed Reactive Compatibilization of Polyolefin and Poly(ethylene terephthalate) Blends: Reactions Mechanisms and Phase Morphology Development, Ph.D. thesis, University of Pisa, Italy, 2005.)
(A)
(B)
FIGURE 4.6 SEM photomicrographs of PET/LDPE+SEBS-g-DEM blends obtained using a mixing time of 20 min. (A): 80/16.7 PET/LDPE containing 3.3 wt% of SEBS-g-DEM sample cut parallel to ow direction; (B): 70/20 PET/LDPE blend containing 10 wt% of SEBS-g-DEM, sample cut parallel to ow direction. (From M. B. Coltelli, Catalysed Reactive Compatibilization of Polyolefin and Poly(ethylene terephthalate) Blends: Reactions Mechanisms and Phase Morphology Development, Ph.D. thesis, University of Pisa, Italy, 2005.)
FIGURE 4.7 Visualization of compatibilizer location in immiscible blends: SEM photomicrographs of a blend of thermoplastic polyurethane (TPU) with 20 wt% polypropylene compatibilized with different ethylenic co-and terpolymers (blend melt-mixed using ZSK-30 extruder). (A): TPU/propylene (PP) = 80/20 wt% blend; (B): added with 5 wt% Lucalen having 4% acrylic acid; (C): added with 5 wt% Lucalen without acrylic acid; (D): added with 5 wt% Luwax having 20% acrylic acid. The TPU matrix was selectively dissolved in dimethylformamide and the remaining PP particles without or with compatibilizer were separated on a membrane. (From K. Wallheinke, W. Heckmann, P. Pötschke, and H. Stutz, Polym. Test. 17(4), 247-255, 1998. With permission.)
(C)
(D)
FIGURE 4.7 (Continued)
(A)
(B)
FIGURE 4.8 SEM photomicrographs of blends based on hyperbranched polymers with a functionality of ca. 100 COOHgroups per molecule as reactive compatibilizers in blends based on oxazoline-terminated PP (PP-Ox) and oxazoline-terminated PS (PS-Ox). Distribution of 5 wt% hyperbranched polymer (HBP) in PP, PP-Ox, PS, and PS-Ox. (A): PP/HBP; (C): PS/HPB nonreactive; (B): PP-Ox/HPB; and (D): PS-Ox/HPB reactive, SEM on cryocuts, HBP etched with THF, frame size 240 × 180 mm. (From J. Pionteck, P. Pötschke, N. Proske, H. Zhao, H. Malz, D. Beyerlein, U. Schulze, and B. Voit, Macromol. Symp. 198, 209-220, 2003. With permission.)
(C)
(D)
FIGURE 4.8 (Continued)
190°C
(A)
200°C
(B)
SCA 200°C
(C)
SCA+Pt 200°C
(D)
FIGURE 4.9 Atomic force microscopy (AFM) images in phase-contrast mode of PS-COOH/polymethyl methacrylate (PMMA)-NH2 = 40/60 (vol.%) prepared at 190°C (A); (B) like (A), prepared at 200°C; (C) like (B), with SCA; (D) like (B), with SCA+Pt (frame size 10 × 10 µm). Inuence of silane-containing coupling agent (SCA) and processing conditions on morphology of PS-COOH/PMMA-NH2 = 40/60 (vol.%) blends. (From J. Pionteck, V. B. Sadhu, L. Jakisch, P. Pötschke, L. Häußler, and A. Janke, Polymer 46, 6563-6574, 2005. With permission.)
0 Data type 2 range
Height 100.0 nm
Data type 2 range
Phase 30.00*
4.00 µm 4.00 µm0
(A)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 15.00*
4.00 µm 4.00 µm0
(B)
FIGURE 4.10 AFM analysis of (A) PS-COOH/PMMA-NH2/SCA/Pt, 40/60/3, melt-mixed at 200°C for 30 min; (B) PS-COOH/ PMMA-NH2/SCA, 40/60/3 melt-mixed at 200°C for 10 min and annealed at 200°C for 30 min, without shear (left images: height prole; right images: stiffness contrast; frame size 4 × 4 µm). Inuence of silane-containing coupling agent (SCA) and processing conditions on morphology of PS-COOH/PMMA-NH2 = 40/60 (vol.%) blends. (From J. Pionteck, V. B. Sadhu, L. Jakisch, P. Pötschke, L. Häußler, and A. Janke, Polymer 46(17), 6563-6574, 2005. With permission.)
(A)
(B)
FIGURE 4.11 Porous structures are formed from Interpenetrating network (IPN) due to extraction in hot xylene after irradiation with an electron beam (doses in kGy), which destroys the polymethacrylate phase, cross-links the PE phase, and causes partial grafting between phases. The SEM images show cryofractures of different treated samples. MMA: methyl methacrylate; EMA: ethyl methacrylate; BMA: n-butyl methacrylate: DMA: n-dodecyl methacrylate; BDDM: 1,4-butanediol dimethacrylate; peroxide: 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane (Trigonox-101). (A): Porous structure of the cross section of the PE/BMA-co-MMA IPN (polytetrauoroethylene [PTFE] reactor, BMA/MMA = 50:50, BDDM = 0.1 mol%, peroxide = 1 wt%, 800 kGy). A dense surface structure is visible in the right upper corner. Porous surface (A) and bulk morphology (B) of the PE/DMA-co-EMA IPN (PTFE reactor, no BDDM, peroxide = 3 wt%, 800 kGy). (B): porous (left) surface and (right) bulk morphology of the PE/DMA-co-EMA IPN (PTFE reactor, no BDDM, peroxide = 3 wt%, 800 kGy). (C): porous surface structure of the PE/BMA-co-MMA IPN (Alu reactor, BMA/MMA = 50:50, BDDM = 1 mol%, peroxide = 1 wt%, 800 kGy). (D): porous (left) surface and (right) bulk morphology of the PE/BMA-co-MMA IPN (Alu reactor, BMA/MMA = 60:40, BDDM = 1 mol%, peroxide = 1 wt%, 400 kGy). (E): porous surface structure of the PE/DMA-co-EMA IPN (Alu reactor, BDDM = 1 mol%, peroxide = 1 wt%, 800 kGy). (From J. Pionteck , J. Hu, and U. Schulze, J. Appl. Polym. Sci. 89, 1976-1982, 2003. With permission.)
(C)
(D)
(E)
FIGURE 4.11 (Continued)
0 Data type 2 range
Height 100.00 nm
Data type 2 range
Phase 30.00*
10.0 µm 10.0 µm0
(A)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 45.00*
4.00 µm 4.00 µm0
(B)
FIGURE 4.12 AFM images of blends of PS-COOH/PMMA-NH2 (PS/PM) compatibilized with an SCA. (A) and (B): PS/PM = 50/50 without compatibilizer. (C) and (D): PS/PM/SCA (50/50/3). (E) and (F): PS/PM/SCA (50/50/3) + catalyst. (G) and (H): PS/PM (40/60) without compatibilizer. (I) and (J): PS/PM (40/60) without compatibilizer after annealing 30 min at 200°C. (K) and (L): PS/PM/SCA (40/60/3). (M) and (N): PS/PM/SCA (40/60/3) after 30 min of annealing at 200°C. (O) and (P): PS/PM/SCA (40/60/3) + catalyst. (Q) and (R): PS/PM/SCA (40/60/3) + catalyst after annealing 30 min at 200°C. NanoScope IV-Dimension 3100 (Veeco) on smooth cut surfaces, tapping mode, topography (left), and phase images (right) detected simultaneously; some images are published in cited paper, composition in volume. For details concerning structure and chemistry, see the reference. (From J. Pionteck, V. B. Sadhu, L. Jakisch, P. Pötschke, L. Häußler, and A. Janke, Polymer 46, 6563-6574, 2005. With permission.)
0 Data type 2 range
Height 100.00 nm
Data type 2 range
Phase 15.00*
10.0 µm 10.0 µm0
(C)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 10,000*
4.00 µm 4.00 µm0
(D)
FIGURE 4.12 (Continued)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 30.00*
10.0 µm 10.0 µm0
(E)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 30.00*
4.00 µm 4.00 µm0
(F)
FIGURE 4.12 (Continued)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 10.00*
10.0 µm 10.0 µm0
(G)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 10.00*
4.00 µm 4.00 µm0
(H)
FIGURE 4.12 (Continued)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 45.00*
10.0 µm 10.0 µm0
(I)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 25*
4.00 µm 4.00 µm0
(J)
FIGURE 4.12 (Continued)
0 Data type 2 range
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Data type 2 range
Phase 10,000*
10.0 µm 10.0 µm0
(K)
0 Data type 2 range
Height 100.0 nm
Data type 2 range
Phase 8000*
4.00 µm 4.00 µm0
(L)
FIGURE 4.12 (Continued)
0 Data type 2 range
Height 100.00 nm
Data type 2 range
Phase 15.00*
10.0 µm 10.0 µm0
(M)
0 Data type 2 range
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Data type 2 range
Phase 15.00*
4.00 µm 4.00 µm0
(N)
FIGURE 4.12 (Continued)
0 Data type 2 range
Height 100.0 nm
Data type 2 range
Phase 8000*
10.0 µm 10.0 µm0
(O)
0 Data type 2 range
Height 50.00 nm
Data type 2 range
Phase 7000*
4.00 µm 4.00 µm0
(P)
FIGURE 4.12 (Continued)
0 Data type 2 range
Height 100.00 nm
Data type 2 range
Phase 15.00*
10.0 µm 10.0 µm0
(Q)
0 Data type 2 range
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Data type 2 range
Phase 20.00*
4.00 µm 4.00 µm0
(R)
FIGURE 4.12 (Continued)
(A)
(B)
FIGURE 4.13 Dispersion of PS-brils in spun PP/PS composite bers. SEM photomicrographs of cross sections. (A): PP/PS 98/2; (B): PP/PS 96/4; (C): PP/PS 94/6; (D): PP/PS 92/8. (PS phase is etched out with xylene at room temperature.) (From Q. Xing, M. Zhu, Y. Wang, Y. Chen, Y. Zhang, J. Pionteck, and H. J. Adler, Polymer 46(14), 5406-5416, 2005. With permission.)
(C)
(D)
FIGURE 4.13 (Continued)
FIGURE 4.14 Dispersion of PS-brils in as-spun PP/PS 92/8 composite bers, SEM photomicrographs in longitudinal section. PS phase is etched out with xylene at room temperature. (From Q. Xing, M. Zhu, Y. Wang, Y. Chen, Y. Zhang, J. Pionteck, and H. J. Adler, Polymer 46(14), 5406-5416, 2005. With permission.)
0 wt% (A)
5 wt%
(B)
FIGURE 4.15 SEM, smoothed cuts, PS phase etched with tetrahydrofuran (THF), bar = 20 µm. Inuence of concentration, tacticity, and side arm length on compatibilizing efciency of poly(propene-g-styrene) graft copolymers in PP/ PS = 2/1 (by wt.) blends. (A), (B), (C), and (D): inuence of the compatibilizer content on the PP/PS morphology. Polymer blends PP/PS = 2/1 (by wt.) with varied isotactic PP-PS copolymer (7.4 wt% PS side arms with Mn = 18.000 g/mol) content (SEM, smoothed cuts, PS etched with THF, scale bar = 20 µm). (E), (F), (G), (H), and (I): inuence of the copolymer structure on the blend morphology. Polymer blends PP/PS = 2/1 (by wt.) with 5 wt% isotactic copolymer (E), (F), and (G) or atactic copolymer (H and I). (From U. Schulze, T. Fonagy, H. Komber, G. Pompe, J. Pionteck, and B. Ivan, Macromolecules 36, 4719-4726, 2003. With permission.)
10 wt%
(C)
(E) (F)
(G) (H)
FIGURE 4.15 (Continued)
(A) (B)
FIGURE 4.16 Inuence of reactive group concentration on morphology of PP/PS = 2/1 blends. PP is nonreactive, PP-co-Ox3 is reactive to PS-COOH, the compositions and reactive group Ox3/COOH mol ratios are given below the SEM images (cryofractures, PS-phase etched with THF, frame size 233 × 187 m). (A): PP/PS-COOH (2/1 by wt., nonreactive); (B): PP/PP-co-Ox3/PS-COOH (60/6.7/33.3) reactive group ratio 0.5; (C): PP/PP-co-Ox3/PS-COOH (41.7/25/33.3) reactive group ratio 1.8; and (D): PP/PP-co-Ox3/PS-COOH (0.0/66.7/33.3) reactive group ratio 4.8. (From A. Kaya, G. Pompe, U. Schulze, B. Voit, and J. Pionteck, J. Appl. Polym. Sci. 86, 2174-2181, 2002. With permission.)
(I)
FIGURE 4.15 (Continued)
(A)
FIGURE 4.17 Morphology of a ternary system of PP-Ox/PS-Ox (2/1 by wt.) plus hyperbranched polymer (HBP, 5 wt%) obtained by simultaneous mixing for 5 min (A) or 30 min (B). The HBP enriches in the (bright) PS phase resulting in a salami-like phase in phase morphology. (DACA Micro Compounder; SEM, cryocut, HBP etched out with NaOH solution.) (From J. Pionteck, P. Pötschke, N. Proske, H. Zhao, H. Malz, D. Beyerlein, U. Schulze, and B. Voit, Macromol. Symp. 198, 209-220, 2003. With permission.)
(C) (D)
FIGURE 4.16 (Continued)
(B)
FIGURE 4.17 (Continued)
5 wt% ABS
(A)
FIGURE 4.18 SEM photomicrographs of cured epoxy-acrylobutadienestyrene (ABS) blends (scanning electron microscope XL 30 ESEM-FEG [Philips] on cut surfaces, etched with oxygen plasma, and sputtered with gold). (From Y. Müller, L. Häußler, and J. Pionteck, Macromol. Symp. 254, 267-273, 2007. With permission.)
10 wt% ABS
(B)
15 wt% ABS
(C)
FIGURE 4.18 (Continued)
20 wt% ABS
(D)
FIGURE 4.18 (Continued)
FIGURE 4.19 Inuence of reactive site concentration and viscosity ratio (lambda) on morphology of PP-g-Ox/PS-COOH = 70/30 (wt)-blends (PS was etched out with xylene at room temperature, cryocut). (A): PP-g-Ox/PS, lambda = 0.12, COOH: Ox = 0; (B): PP-g-Ox/PS-COOH 1, lambda = 0.11, COOH: Ox = 0.51; and (C): PP-g-Ox/PS-COOH 2, lambda = 1.03, COOH: Ox = 0.30. (From P. Pötschke, H. Malz, and J. Pionteck, Macromol. Symp. 149, 231-236, 2007. With permission.)
(B)
(C)
FIGURE 4.19 (Continued)
20 0n
m
(A )
(B )
20 0n
m
FI G
U R
E 4.
