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NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. 奈米化工與高分子材料 2003/11/8 報告人 : 吳逸謨.

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Presentation on theme: "NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. 奈米化工與高分子材料 2003/11/8 報告人 : 吳逸謨."— Presentation transcript:

1 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. 奈米化工與高分子材料 2003/11/8 報告人 : 吳逸謨

2 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ 原子彈 1960~70 - 太空登月 原子筆, 原子襪, 原子褲, 原子能 , etc 太空被,太空衣,太空鞋, 太空纖維 etc

3 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ – 奈米 奈米水,奈米電鍋,奈米冰箱,奈米冷氣機, 奈米 SARS 口罩,奈米塗料,奈米潤滑油,奈 米保養化妝品, 奈米 - 米 , etc… 奈米中藥,奈米顆粒,奈米管, etc… 奈米生化,奈米醫學, etc

4 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. 奈米福碳公司 奈米科技論壇 Dr. Alan MacDirmid – (2002 Chemistry Nobel-Prize Laureate for conducting polymers) He said Taiwan could someday become a 奈米島

5 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Analyses of Crystal Forms in Syndiotactic Polystyrene Intercalated with Layered Nano- Clays

6 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. 高分子 – 超奈米

7 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Introduction Over the last decade, polymer-layered silicate nanocomposites (PLSNs) with nano-scale reinforcements have been the focus of extensive study. Incorporation of the organo-layered silicates into the polymers results in enhanced mechanical strength, improved thermal stability and flame retardancy, increased solvent resistance and barrier properties, higher ionic conductivity, reduced thermal expansion coefficient, and controlled biodegradability. Dispersivity of the clay particles plays the pivotal role to influence the ultimate properties of the PLSNs. For a typical polymer, the key factors of the clay dispersion are the method of synthesis, structure of the intercalant (generally onium surfactants) and concentration of clay.

8 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. sPS is a semi-crystalline polymer exhibiting complex polymorphic behavior with multiple melting characteristics. The main objectives of the present investigation are: (1)to elucidate the multiple melting characteristics of sPS/clay nano- composites vs. conventional micro-composites by comprehensive thermal and X-ray diffraction evidence; (2)(2) to investigate the effect of T c on the relative ratio of the polymorphic sPS crystals in presence of pristine and organo- clays; and (3)(3) to depict the spherulitic morphology of sPS as affected by incorporation of different kind of clays. Objectives

9 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Experimental Syndiotactic polystyrene (sPS) Syndiotactic polystyrene (sPS) (Idemitsu Petrochemical Co., Ltd., Japan) M w =210 kg/mol Cloisite ® Na+ (Na-MMT) Cloisite ® Na+ (Na-MMT) (Southern Clay Product Inc., USA) CEC = 92.6meq/100g clay (d 001 = 11.7Å), sp.gr. = 2.86 Cloisite ® 10A (Clay-10A) (Southern Clay Product Inc., USA) Modifier : 2MBHT(dimethyl, benzyl, hydrogenatedtallow, quaternary ammonium salt) Modifier conc. = 125meq/100g clay (d 001 = 19.2Å), sp.gr. = 1.90 HT is Hydrogenated Tallow (~65% C18; ~30% C16; ~5% C14) 1,1,2,2-tetrachloroethane (TCE) (Showa Chemicals Inc., Japan) (  = 19.8 MPa ½, b.p. 145 o C,   1.6 g/cc) Materials Used

10 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Experimental (contd.) Differential Scanning Calorimetry (DSC): DSC-7 (Perkin-Elmer) attached with cooling accessory Intracooler 2 (Perkin-Elmer). Wide-Angle X-ray Diffraction (WAXD): Shimadzu XRD-6000 with Cu K α radiation (30 kV and 40 mA) and a wavelength of Å. The scanning 2θ angle ranged between 2° and 30° with a step scanning rate of 2°/min. Transmission Electron Microscopy (TEM): JEOL JEM 1200-EX TEM. Epoxy-mounted samples were ultra-microtomed with a diamond knife on a Leica Ultracut R microtme (nominal thickness of 50~70 nm). The sections were transferred from water to carbon coated 200-mesh Cu grids. Polarized Optical Microscopy (POM): Nikon Optiphot-2, POL equipped with UFX-DX automatic exposure. Linkam THMS-600 with TP-92 temperature programmer was used as microscopic heating stage. Instrumentation

11 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Solvent used - 1,1,2,2-tetrachloroethane (TCE) Solution was stirred for 1h at 130 o C to dissolve sPS (2-wt%) Clay (vacuum dried at 80 o C for 6h) was added into the polymer solution Clay suspension was vigorously stirred at 60 o C in oil bath for 24h The resultant solution was cast as thin film at 60 o C for 24h Residual solvent was removed by vacuum drying at 110 o C for 7 days Cast film was grounded to fine powder Powdered samples were further dried at 110 o C for 3 days for complete removal of solvent Solution Intercalation of sPS

12 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Composition T g (  C) T cc (  C) a T m (  C)  H m (J/g) b sPS (neat) sPS + Na-MMT (5%) sPS + C10A (5%) sPS + C10A (10%) All the samples were melted at 290  C for 10 min to remove all the crystalline forms and then quenched by liquid nitrogen to obtain the amorphous state (DSC scan rate = 20°C/min) a T cc : peak temperature of cold crystallization. b  H m : melting enthalpy. Thermal transitions of sPS/clay-Hybrids

13 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Dispersion of layered silicates in sPS No peak in the relevant range (2  = 3 ~ 8  ) for neat sPS. A broad peak around 2   9.2  indicates the existence of  -crystal form in this TCE-cast sPS matrix (Trace c) Peak at 2   6.1  in sPS/Na-MMT (5-wt%) composite indicates the presence of clay-induced  -crystals of TCE-cast sPS overlapped by the d 001 peak of the unintercalated Na-MMT (Trace d) No significant XRD peak in the region of 2  = 3-5  sPS/ C10A (5-wt%) nanocomposite, indicating successful intercalation of sPS into the silicate layers (Trace e) Small and broad peak at 2   6  for C10A (10- wt%) nanocomposite suggests the presence of  - crystal of sPS in the cast sample, still no peak in the region of 2  = 3-5  (Trace f) d 001  1.17 nm d 001  1.88 nm

14 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. TEM images of sPS/clay-Hybrids sPS/Na-MMT(5-wt%) microcomposite ` sPS/C10A (5-wt%) nanocomposite

15 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Polymorphism in sPS/clay nanocomposites melt crystallized at 240 o C t c = 30 min DSCXRD

16 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Characterization sPS/clay Nanocomposites Melt crystallized at 235 o C Characterization sPS/clay Nanocomposites Melt crystallized at 235 o C t c = 30 min DSC XRD

17 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Crystal forms in sPS/clay nanocomposites melt crystallized at 245 o C t c = 60 min DSCXRD

18 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Melt crystallization behavior of sPS/clay nanocomposites at 250 o C t c = 60 min DSCXRD

19 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. 800X 10μm sPS/Na-MMT(5-wt%) microcomposite sPS/C10A (5-wt%) nanocomposite sPS (neat) Effect of layered silicates in spherulitic dimension of sPS All the samples were melt crystallized at 240  C for 30 min (T max = 290  C, t max = 10 min) Average maximum diameter of spherulites ~40  m~25  m ~15  m

20 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Conclusions The sPS molecules were successfully intercalated into the organo-clay galleries. TEM analysis revealed a mixed morphology of an intercalated/exfoliated structure in the sPS/clay nanocomposites. A significant alteration of the polymorphism in the sPS matrix was observed by the inclusion of different nano-layered clays. The temperature regime of the  -crystal formation in sPS was found to expand considerably and the organo-clays favored the formation of  -phase in addition to the  -phase, even at high T c of 250  C. Pristine clay (Na-MMT) was dispersed in the sPS matrix more coarsely with aggregated structures, behaved differently in its nucleating action and only larger spherulites of  - form of sPS crystals were induced to grow at all the available T c ’s. the clay dispersibility in the sPS matrix is assumed to play a pivotal role in altering the crystalline structures. The inclusion of the organo-clay with nano-scale dispersibility promoted the rapid formation of  -forms, which developed spherulites of smaller dimension as compared the  -forms. However, the proportion of  -phase was decreased with higher loading (> 5-wt%) of organo-clay due to poor dispersion. The peak 2 (P2) for melt-crystallized sPS in DSC analysis was further confirmed to correspond to the  -phase, as it was almost absent in the sPS/Na-MMT composites.

21 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Polymorphic Crystal Forms and Melting Behavior of Poly(butylene adipate)

22 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Introduction Polymorphic structure of Poly(butylene adipate)(PBA) was reported by Minke and Blackwell in They have identified two types of polymorphic crystals exhibited in crystalline PBA samples.  -from crystal was characterized as a monoclinic unit cell, and  -form was packed as an orthorhombicunit cell. For PBA, in the previous paper, it was indicated that the formation of  - and  -form crystal was dependent on the melt crystallization temperatures. In this study, we attempted to explore the relationships between the polymorphic crystals and the multiple melting peaks.

23 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Experimental Material Used Poly(butylene adipate)(PBA) Poly(butylene adipate)(PBA) (Aldrich Chem. Co.) Mw=12,200 and Mn=9,540 with a polydispersity of Purification: PBA was reprecipitated from chloroform into cold methanol (ca. –10 o C). And then, the sample was dried in the vacuum oven at 40 o C for 7 days to remove the solvent.

24 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Complex Melting Peaks and Characterization of Crystal forms in PBA WAXD DSC

25 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PBA isothermally melt-crystallized at 29.5 o C for various times

26 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PBA (T c = 29.5 o C) and scanned at various rates (t c =30min)

27 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Dynamically cooled PBA at various rates (T c =29.5 o C) DSC WAXD

28 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PBA sample melt-crystallized at 28 o C was melted to 58 o C and then quenched to 31 o C

29 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PBA (T c =31 o C) melted to different T m and then quenched to 28 o C

30 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Comparison of the melting behaviors of  - form crystal melted to various temperatures

31 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. X-ray diffractograms for PBA (T c =31 o C) melted and annealed to various temperatures

32 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Comparison of the melting behaviors of  - form crystal melted to various temperature

33 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. X-ray diffractograms for PBA (T c =28 o C) melted to various temperaturesand annealed X-ray diffractograms for PBA (T c =28 o C) melted to various temperatures and annealed

34 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Conclusion The formation of  -form crystal can be favored in the crystallization of PBA under these two conditions: (1) slow cooling from the molten state, (2) melt crystallization at high temperatures. The  -form crystal can be formed under these two conditions: (1) melt crystallization at lower temperatures, (2) at fast cooling rates from the melt. The  -form crystal which was heated to melt produced two endothermic peaks (P1 and P3). P2 and P4 appeared when  -from crystal was melted. As  - and  -form crystals coexisted, the melting behaviors for the crystals showed four peaks (P1-P4) on the DSC trace.

35 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Miscibility in Ternary Blends: PVAc/PVPh/PMMA Part 1

36 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PVPh Mw = 22,000 g/mol Tg = o C Polysciences, Inc. PMMA Mw=100,000 g/mol (GPC) Tg = 87.1 o C Polysciences, Inc. PVAc Mw = 260,000 g/mol (GPC) Tg = 35.4 o C Scientific Polymer Products, Inc. THF b.p=66 o C MEK b.p=79.6 o C Cyclohexanone b.p=156.7 o C Materials Experimental Part Solvent

37 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Experimental Part (Contd.) Sample Preparation The blend samples were prepared by solvent-casting (THF, MEK and cyclohexanone). When completely mixing that The blend samples were cast at 45 o C for 24 hr. Samples were subjected to vacuum degassing at 80 o C for one week Apparatus Optical light microscope (Nikon Optiphot-2, POL) Different scanning calorimeter (Perkin-Elmer DSC-7) Scanning electron microscope (SEM, JEOL JXA840)

38 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Results and Discussion POM for ternary PVAc/PVPh/PMMA phase diagram : THF cyclohexanone MEK

39 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. POM for ternary PVAc/PVPh/PMMA MEK casting phase diagram : Results and Discussion (Contd.)

40 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Results and Discussion (Contd.) LCST Behavior :

41 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. DSC thermograms for PVAc/PVPh/PMMA ternary blends heated at 20 o C/min Results and Discussion (Contd.)

42 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. DSC traces of the physical-aged PVAc/PVPh/PMMA blends (ageas at 70 o C for different time) DSC traces of the physical-aged PVAc/PVPh/PMMA blends (ageas at 70 o C for various composition) Results and Discussion (Contd.)

43 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Results and Discussion (Contd.) T g value for ternary PVAc/PVPh/PMMA phase diagram :

44 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. THE observed Tg data by DSC vs the Tg Values calculate by Fox equation This finding might imply that interactions among the components are weak. Results and Discussion (Contd.)

45 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. SEM micrographs of PVAc/PVPh/PMMA ternary blends of virious compositions. 5/90/5 8000X 10/80/ X 15/70/ X 20/60/ X 10/60/ X 30/60/ X 40/50/ X 80/10/ X 35/50/ X

46 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. SEM micrographs of PVAc/PVPh/PMMA ternary blends of virious compositions. 5/70/ X 25/70/5 5000X 90/5/5 5000X

47 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. LPVAc/PVPh/LPMMA Part 2

48 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PVPh Mw = 22,000 g/mol Tg = o C Polysciences, Inc. LPMMA Mw=15,000 g/mol (GPC) Tg = 75.8 o C Aldrich Chemical Company, Inc. LPVAc Mw = 12,800 g/mol (GPC) Tg = 31.3 o C Aldrich Chemical Company, Inc. solvent MEK b.p=79.6 o C Materials Experimental Part

49 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Results and Discussion POM for ternary LPVAc/PVPh/LPMMA phase diagram :

50 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. DSC thermograms for LPVAc/PVPh/LPMMA ternary blends heated at 20 o C/min Results and Discussion (Contd.)

51 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Results and Discussion (Contd.) DSC thermograms for LPVAc/PVPh/LPMMA ternary blends heated at 20 o C/min

52 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Results and Discussion (Contd.) T g value for ternary LPVAc/PVPh/LPMMA phase diagram :

53 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. THE observed Tg data by DSC vs the Tg Values calculate by Fox equation This finding might imply that interactions among the components are weak. Results and Discussion (Contd.)

54 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Results and Discussion (Contd.) Effect of Mw on Tg values. (  HMW PVAc/PVPh/PMMA ) ( 。 LMW LPVAc/PVPh/LPMMA )

55 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. LPVAc/PVPh/LPMMA Cyclohexanone solvent and co-precipitated Part 3

56 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Experimental Part Sample Preparation The blend samples were prepared by solvent-casting (cyclohexanone). When completely mixing that the blend samples were cast at 50 o C and 90 o C for 24 hr. Samples were subjected to vacuum degassing at 80 o C for one week Apparatus Optical light microscope (Nikon Optiphot-2, POL)

57 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. POM for ternary LPVAc/PVPh/LPMMA cyclohexanone casting at 50 o C sample : Results and Discussion (Contd.)

58 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Results and Discussion (Contd.) POM for ternary LPVAc/PVPh/LPMMA cyclohexanone casting at 90 o C sample :

59 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. DSC thermograms for LPVAc/PVPh/LPMMA ternary blends heated at 20 o C/min Results and Discussion DSC for ternary LPVAc/PVPh/LPMMA phase diagram.

60 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Conclusion In this ternary blend of PVAc/PVPh/PMMA where PVPh is miscible with each of the other component, more than 50wt% PVPh was required to cause miscibility between PVAc and PMMA. Phase boundary of LPVAc/PVPh/LPMMA ternary blend investigated by DSC shows that miscibility window was increased obviously. Furthermore, the Tg value of LPVAc/PVPh/LPMMA was less than PVAc/PVPh/PMMA system. Blend prepared by cyclohexanone solvent casting and co-precipitated (MEK-hexane) were found to be immiscible.

61 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Chiang Chih Pei

62 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. System 1. The blend of Poly(p-vinylphenol) (PVPh) / Poly(1,6-hexamethylene adipate)(PHA) 2. The blend of Poly(p-vinylphenol) (PVPh) / Poly(ethylene azelate)(PEAz) 3. The blend of Poly(p-vinylphenol) (PVPh) / Poly(hexamethylene sebacate)(PHS)

63 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. 2. Poly(1,6-hexamethylene adipate)(PHA) T m :55~65°C M n : 3,800 (by GPC M w : 13000) Aldrich Inc. 1. Poly(p-vinylphenol) (PVPh) T g :148°C M w :22,000 Polysciences Inc. Part.1 The blend of PVPh/PHA

64 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Methods Sample preparation All polymers blends via solution-casting. Solutions were prepared in tetrahydrofuran (THF) at a concentration of 4 g polymer/ 100 mL solvent to obtain clear solution mixtures at room temperature; then mixtures were cast at 45°C onto hot stage for 24hr. The solution-cast films were dried for a week in 40°C vacuum oven. Apparatus Polarizing optical microscope, POM Differential scanning calorimeter, DSC

65 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. DSC traces of the PVPh/PHA blends (2nd run)

66 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PVPh/PHA=0/100 PVPh/PHA=10/90 PVPh/PHA=30/70 POM graphs of PVPh/PHA blends after melt- crystallized at 30 o C

67 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PVPh/PHA=0/100 PVPh/PHA=10/90 PVPh/PHA=30/70 POM graphs of PVPh/PHA blends after melt- crystallized at 35 o C

68 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PVPh/PHA=0/100 PVPh/PHA=10/90 PVPh/PHA=30/70 POM graphs of PVPh/PHA blends after melt- crystallized at 40 o C

69 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. PVPh/PHA=0/100 PVPh/PHA=10/90 PVPh/PHA=30/70 POM graphs of PVPh/PHA blends after melt- crystallized at 45 o C

70 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Part.2 The blend of PVPh/PEAz 2. Poly(ethylene azelate)(PEAz) T g :-50 °C T m :55°C M w :50,000 SP 2 Inc. 1. Poly(p-vinylphenol) (PVPh) T g :148°C M w :22,000 Polysciences Inc.

71 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Methods Sample preparation All polymers blends via solution-casting. Solutions were prepared in tetrahydrofuran (THF) at a concentration of 4 g polymer/ 100 mL solvent to obtain clear solution mixtures at room temperature; then mixtures were cast at 45°C onto hot stage for 24hr. The solution-cast films were dried for a week in 40°C vacuum oven. Apparatus Polarizing optical microscope, POM Differential scanning calorimeter, DSC

72 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Thermodynamic reversibility -2 o C/min PVPh/PEAz=90/10 -2 o C/min PVPh/PEAz=80/20 -2 o C/min PVPh/PEAz=70/30 heat to above UCST cool to r.t.

73 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Check the UCST behavior +2 o C/min (B) after melt-blending and casting (A) by melt-blending as -cast transiting heat to above UCST Using melt-blending to prepare PVPh/PEAz=70/30 binary blend sample, then dissolving in THF (4wt%); and casting at 45°C onto hot stage for 24hr. The solution-cast films were dried for 3days in 40°C vacuum oven.

74 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Clarity point of the PVPh/PEAz blends one phase phase separation UCST

75 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. DSC traces of the PVPh/PEAz blends casting at 45 o C

76 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. DSC traces of the PVPh/PEAz blends after quenching from 200 o C

77 NCKU-PRL Polym. Res. Lab. Nation Cheng Kung Univ. Clarity point temperature and T g in PVPh/PEAz binary blends PVPh/PEAzClarity point( o C) 1 st T g ( o C)2 nd T g ( o C) 0/100x /90x /80x /70x /60x /50x / , / , / , / ,


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