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TITLE
CERTIFICATE
DECLARATION
ACKNOWLEDGEMENT
PREFACE
GLOSSARY OF TERMS
CONTENTS
I. INTRODUCTION
Fig. I.1 Schematic diagram of some simple two polymer combinations (Source Ref.5)
I.2. COMMERCIAL IMPORTANCE OF POLYMER BLENDS
I. 3. BLENDING TECHNIQUES
I.3.1 Melt blending
I.3.2 Latex blending
I.3.3 Solution blending
I.3.4 Mechanochemical blending
I.3.5 Freeze drying
I.3.6. Partial block and graft polymerisation
I.4. COMMERCIAL POLYMER BLENDS
I.4.1 Two phase polymer blends
Table I.1Commercial blend of immiscible components
I.4.1.1 Interpenetrating polymer net work (IPN)
Table: I. 2 Examples of IPNs
I.4.1.2 Rubber - rubber polyblends
Table: I.3 Example for rubber - rubber blend
I.4.1.3 Rubber - plastic polyblends
Table: I.4 Examples of rubbecplastic polyblends
I.4.1.4 Plastic -plastic poly blends
Table: I.5 Examples for plastic-plastic blends
I.4.1.5 Block copolymers
I.4.2 One phase polymer blends
Fig I.2. Variation of property with compositionfor a binary polymer blend (Source Ref.5)
Table I.6 Commercial blends of miscible components
I.5 CHARACTERISATION OF POLYMER BLENDS
I.5.1 Optical clarity
I.5.2 Glass transition temperature (Tg)
Fig. I. 3. Variation of Tg with composition (Source Ref.41)
I.5.3 Spectroscopy
I.5.4 Scattering techniques
I.5.5 Inverse gas chromatography
I.5.6 Fluorescence spectroscopy
I.5.7 Microscopy
I.5.8 Melting point depression
I.5.9 Viscosity studies
I.5.10 Mechanical properties
I.5.11 Rheological properties
I.5.12 Empirical approach at predicting compatibility: solubility parameter approach
I.5.13 Interaction parameter and critical interactionparameter
I.5.14 Enthalpy of mixing of polymer-polymer blends
I.6. THERMODYNAMICS AND PHASE SEPARATION OF POLYMER BLENDS
Fig.I.4 Free energy versus blend composition for (a) miscible, and (b) partly miscible polymer blends (Source Ref.78)
Fig. I.5. Schematic phase diagrams for polymer polymer blends: - (Source Ref.88)
I.6.1 Kinetics of phase separation
I.6.2 Polymer mixture theories
Fig. I.6. Modes of phase separation in miscible blends (Source Ref. 88)
I.6.3 Lattice fluid theory
I.6.4 Phase behaviour of ternary polymer blends
I.6.5 Experimental determination of phase separationin polymer blends
I.7. PVC BASED BINARY BLENDS
I.7.1 PVC/NBR blends
I.7.2 PVC/EVA blends
I.7.3 PVC/PCL blends
I.7.4 PVC/PMMA blends
I.7.5 PVC/PU blends
I.7.6 PVC/CPE blends
I.7.7. PVC/ α - methyl styrene based polymer blends
I.8. COMPATIBILISATION OF IMMISCIBLE POLYMER BLENDS
I.8.1 Addition of block copolymers for compatibilisation
I.8.2 Addition of graft copolymers for compatibilisation
I.8.3 Reactive compatibilisation
I.8.4 Homopolymers as compatibilisers
Fig.I.7 Basic phase structure types that may occur for a blend of three high-molecular weight polymers.
I.9. AIM AND SCOPE OF THE INVESTIGATION
I.10. REFERENCES
II. EXPERIMENTAL TECHNIQUES
II.1. MATERIALS USED
Table II.1.Details of the materials used
II.2. PREPARATION OF THE BLENDS
Table II.2 Formulations for binary and ternary blends
Fig. II. 1. Composition of binary and ternary blends of PVC, EVA and SAN.
II.3. CHARACTERISATION
II.3.1. SOLUTION VISCOSITY
II.3.2. DENSITY
II.3.3. SOLUBILITY PARAMETER
II.3.4. INTERACTION PARAMETER AND ENTHALPY OF MIXING
II.3.5. INFRARED SPECTROSCOPY
II.3.6. THERMOGRAVIMETRY
II.3.7. LIMITING OXYGEN INDEX
Table II.3.a Solubility parameter of polymers
Table II.3.b Solubility parameter of EVA
II.3.8. SMOKE CHARACTERISTICS
II.3.9. STATIC THERMAL STABILITY
II.3.10. DIFFERENTIAL SCANNING CALORIMETRY
II.3.11. LOWER CRITICAL SOLUTION TEMPERATURE
II.3.12. SCANNING ELECTRON MICROSCOPYUTION
II.3.13. MECHANICAL PROPERTIES
II.3.14. HARDNESS
II.3.15. SOLUTION RHEOLOGY
REFERENCES
III. RESULTS AND DISCUSSION
Section 1 BINARY BLENDS OF PVC AND EVA
III.1. BINARY BLENDS OF PVC AND EVA
III.1.1 COMPATIBILITY IN SOLUTION
Fig.lll.1.1η sp/C Vs C for PVC and EVA
Table III 1.1Observed and calculated intrinsic viscosities of PVC, EVAand PVC/EVA blends
Fig.lll.l.2.Δb Vs C for PVC/EVA blends, 70/30, 50/50 and 30/70
Fig.lll.l.3.Observed and calculated specific viscosities of PVC/EVA 70/30mixture Vs concentration
Fig.lll.l.4.Observed and calculated specific viscosities of PVC/EVA 50/50 mixture Vs concentration
Fig.lll.l.5.Observed and calculatedspecific viscosities of PVC/EVA 30/70mixture Vs concentration
Fig.lll.l.5.Observed and calculated specific viscosities of PVC/EVA 30/70 mixture Vs concentration
III.1.1.1 Interaction parameter, heat of mixing and density
Table III.1.2Interaction parameters for polymer - polymer system
Table III.1.3 Interaction parameter for polymer blend - solvent system
Fig.lll.l.6.Heat of mixing Vs weight percentage of PVC in PVC/EVA blends
Table III.1.4 Observed and calculated densities of PVC/EVA blends
III.1.2. INFRARED SPECTROSCOPY STUDIES
III.1.3. THERMAL AND FLAME RETARDANT PROPERTIES
III.1.3.1 Thermogravimetry
Fig. Ill. 1.7. Infrared spectrum of pure EVA
Fig. Ill. 1.8. Infrared spectrum of PVC /EVA SO/SO mixture
Fig.llI.l.g. T G and DTG curves of PVC
Fig.III. 1.10. TG and DTG curves of EVA
Fig. III.l. 11. TG and DTG curves of PVC/ EVA 70 / 3 0 blend
Fig.III.1.12. TG and DTG curves of PVC /EVA 50/50 blend.
Fig.III.1.13. TG and DTG curves of PVC/EVA 30/70 blend.
Table III.1.5 Comparison of the thermal properties of PVC, EVA and PVC/EVA blends
III.1.3.2. Differential scanning calorimetry studies of PVC/EVA binary blends.
Fig.lll.1.14.Effect of blend composition on To and T50 values of PVC/EVA blends
Fig.llI.1.15. Effect of blend composition on the amount of residue of PVC/EVA blends
Fig.III.1.16. DSC therrnogrom of PVC and EVA.
Fig.III.1.17.DSC thermogram of PVC/EVA 70/30 and 50/50 blends
III.1.4. MORPHOLOGY
III.1.4.1 Scanning electron microscopy
Fig.lll.1.18.Glass transition temperature (Tg) Vs composition of PVC/EVA blends
III.1.5. PHASE SEPARATION
Fig.III.1.20.LCST of PVC/EVA blends
III.1.6. MECHANICAL PROPERTIES
Fig. III.1.19.a SEM Photomicrograph of PVC/EVA 70130 (EVA phase etched) No signs of phase separation
Fig.III.1.19.b SEM Photomicrograph of PVCIEVA 50150 (PVC phase is etched) Phase separated interconnected morphology.
Fig. III.1.19.c SEM Photomicrograph of PVC/EVA 30/70 (PVC phase etched) No signs of phase separation
Fig.III.1.21. Optical photograph of PVC/EVA 50/50 blend at LCST
Fig.III.1.22. Stress strain behaviour of PVC, EVA and PVC/EVA blends
Fig.lll.1.23.Maximum tensile strength composition of PVC/EVA blends
Fig.III.1.24.Elongation at break Vs composition of PVC/EVA blends
Table III.1.6 Tensile impact strength and hardness of PVC/EVA blends
Fig.lll.1.25.Youngs modulus Vs composition of PVC/EVA blends
Fig.III.1. 26. Tearing force Vs displacement of PVC/EVA blends
Fig.lll.1.27.Tear strength Vs the amount of PVC In PVC/EVA blend
III.1.7. SOLUTION RHEOLOGY
Fig.lll.1.28.Vlscosity Vs shear rate of PVC and EVA
Fig.lll.l.29.Viscosity Vs shear rate of PVC/EVA blends
Fig.III.1.30.Variation of viscosity with composition of PVC/EVA binary blend at a shear rate of 20S -1
Section 2 BINARY BLENDS OF PVC AND SAN
III.2.1 BINARY BLENDS OF PVC AND SAN
III.2.1. COMPATIBILITY IN SOLUTION
Table III.2.1 Observed and calculated intrinsic viscosities of PVC, SAN and PVC/SAN blends
Fig.III.2.1.η sp/C Vs C for PVC and SAN
III.2.1.1. Density, heat of mixing and interaction parameter
Fig.III.2.2.Δb Vs C for PVC/SAN blends, 70/30, 50/50 and 30/70
Fig.III.2.3.Observed and calculated specific viscosltles of PVC/SAN 70/30 mixture Vs concentration
Fig.III.2.4.Observed and calculated specific viscosities of PVC/SAN 50/50 mixture Vs concentration
Fig.lll.2.5.Observed and calculated speciflc vlscositles of PVC/SAN 30/70 mixture Vs concentration
Table III.2.2 Observed and calculated densities of PVC, SANand PVC/SAN blends
Table III.2.3 Interaction parameters for polymer - polymer systems
Fig.III.2.6.Heat of mixing Vs weight percentage of SAN In PVC/SAN blends
Table III.2.4 Interaction parameter for polymer blend solvent system (PVC/SAN)
III.2.2. INFRARED SPECTROSCOPY STUDIES
Fig. III- 2.7. Infrared spectrum of pure SA N
Fig. III. 2. 8 . Infrared spectrum of PVC/ISAN 70/30 blend
III.2 3. THERMAL AND FLAME RETARDANT PROPERTIES
III 2.3.1 Thermogravimetry
Fig.III. 2 . 9 TG and DTG curves of SAN
Fig.III.2.10. TG and DTG curves of PVC/ SAN 70 / 30 blend
Fig.III.2.11.TG and DTG curves of PVC/SAN 50/50 blend
Fig.III.2 -12. TG and DTG curves of PVC/SAN 30/70 blend
Fig.lll.2.13.Effect of blend composition on T0 and T50 values of PVC/SAN blends
Fig.lll.2.14.Effect of blend composition on the amount of residue of PVC/SAN blends
Table III.2.5 Comparison of the thermal properties of PVC, SAN and PVC/SAN blends
III.2.3.2 Differential scanning calorimetry
III.2.4. MORPHOLOGY
Fig.III.2.15. DSC thermogram of PVC, SAN and PVC/SAN blends.
Fig.lll.2.16.Glass transitiontemperature [Tg) Vs composition ofPVC/SAN blends
Fig. III.2.17.a. SEM Photomicrograph of PVC/SAN 70/30 blend (SAN phase etched) Phase separated interconnected morphology.
Fig.III.2.17.b SEM Photomicrograph of PVC/SAN 50/50 (SAN phase is etched) Phase separated interconnected morphology.
III.2.5. PHASE SEPARATION
III.2.6. MECHANICAL PROPERTIES
Fig.2.18.LCST of PVC/SAN blends
Fig.III. 2.20. Stress-strain curve for PVC / SAN blends.
Fig. III.2.19.a. Optical photograph of PVC/SAN 70/30 bIend at LCST.
Fig.III.2.19.b Optical photograph of PVC/SAN 50/50 blend at LCST.
Fig.III.2.21.Maximum tensile strength Vs composition of PVC/SAN blends
Fig.III.2.22.Youngs modulus Vs cornposition of PVC/SAN blends
Fig.ll1.2.23.Elongation at break Vs composition of PVG/SAN blends
Fig.III. 2.24. Tearing force Vs displacement of PVC/SAN blends
Fig.III.2.25.Tear strenfth Vs composition of PVC/SAN blends
Table III.2.6 Tensile impact strength of PVC/SAN blends
III.2.7. SOLUTION RHEOLOGY
Fig.lll.2.26.Viscosity Vs shear rate of PVC and SAN
Fig.III.2.27.Viscosity Vs shear rate of PVC/SAN blends
Fig.lll.2.28.Variation of viscosity with composition of PVC/SAN binary blend at ashear rate of 20s-I
Section 3 BINARY BLENDS OF EVA AND SAN
III.3. BINARY BLENDS OF EVA AND SAN
III.3.1.COMPATIBILITY IN SOLUTION
TableIII.3.1Observed and calculated intrinsic viscosities of EVA/SAN system
Fig.lll.3.1. Δb Vs C for EVA/SAN blends, 70/30, 60/50 and 30/70
III.3.1.1 Density, heat of mixing and interaction parameter
Table III.3.2 Observed and calculated densities of various polymer mixtures
Fig.lll.3.2.0bserved and calculated specific viscosities of EVA/SAN 70/30 mixture Vs concentration
Fig.III.3.3.Observed and calculated specific viscosities of EVA/SAN 60/60 mixture Vs concentration
Fig. lll.3.4.Observed and calculated specific viscositles of EVA/SAN 30/70 mixture Vs concentration
Table III.3.3 Interaction parameter for polymer blend - solvent system (EVA/SAN)
Table III.3.4 Interaction parameter for polymer - polymer systems
Fig.lII.3.5.Heat of mixing Vs weight percentage of SAN in EVA/SAN blend
III.3.2. INFRARED SPECTROSCOPY STUDIES
III.3.3. THERMAL AND FLAME RETARDANT PROPERTIES.
III.3.3.1 Thermogravimetry
Fig. III..3.6 Infrared spectrum of EVA /SAN 50/50 blend
Fig.III.3.7. TG .md DTG Curves of EVA/SAN 70/30 blend.
Fig.III.3.8. TG and DTG curves of EVA /SAN 50/50 blend.
Fig.III.3.9 TG and DTG curves of EVA /SAN 30/70 blend.
Table III.3.5 Comparison of thermal and flammability characteristics of EVA/SAN blend
III. 3.3.2 DSC studies
III.3.4. MORPHOLOGY
Fig.lll.3.10.Effect of blend compositionon To and T50 values of EVA/SAN blends
Fig.III.3.11.DSC Therrnograrn of EVA / S A N blends.
Fig.lll.3.12.Glass transitiontemperature (Tg) Vs composition of EVA/SAN blends
Fig. III.3.13.a. SEM photograph of EVA/SAN 70/30 blend.Particles of SAN resting on the extracted surface
Fig.III.3.13.b SEM photograph of EVA/SAN 50150 blend, co-continuous phases.
Fig. III.3.13.c. SEM photograph of EVA/SAN 30/70 blend.
III.3.5. MECHANICAL PROPERTIES
Fig.III.3.14. Sfress strain curve of EVA / SAN blends
Fig.lll.3.15.Maximum tensile strength Vs composition of EVA/SAN blends
Fig.llI.3.16.Elongation at break Vs composition of EVA/SAN blends
Fig.lll.3.17.Youngs modulus Vs composition of EVA/SAN blends
Fig.III.3.18. Tearing force vs displacement of EVA / SAN blends
Table III.3.6 Tensile impact strength and hardness of EVA/SAN blends
III.3.6. SOLUTION RHEOLOGY
Fig.lll.3.19.Tear strength Vs composition of EVA/SAN blends
Fig.lll.3.20.Viscosity Vs shear rate of EVA/SAN blends
Fig.III.3.21.Variation of viscosity with composition of EVA/SAN binary blend at a shear rate of 20 S - I
Section 4 TERNARY BLENDS OF PVC, EVA AND SAN
III.4. TERNARY BLENDS OF PVC, EVA AND SAN
III.4.1. MORPHOLOGY
Fig. III.4.1 SEM Photomicrograph of PVC/EVA/SAN 35/35/30 ternary blend. No signs of phase separation
Fig.III.4.2 SEM Photomicrograph of PVCIEVAISAN 15/35/50ternary blend. No signs of phase separation.
Fig.III.4.3 SEM Photomicrograph of PVC/EVA/SAN 52.5/52.5/25 ternary blend. Co-continuous phases with marginal phase separation
Fig.III.4.4 SEM Photomicrograph of PVC/EVA/SAN 35/15/50 ternary blend. Co-continuous phases with marginal phase separation.
Fig.III.4.5 SEM Photomicrograph of PVCfEVA/SAN 9/21/70 ternary blend. Phase separated particles resting on the extracted surface.
Fig.III.4.6 SEM Photomicrograph of PVC/EVA/SAN 15/15/70 ternary blend. Interconnected network structure
III.4.2. PHASE SEPARATION
III.4.3 THERMAL AND FLAME RETARDANT PROPERTIES
III.4.3.1 DSC studies
Fig. Ill . 4 . 7 . LC ST of ternary blends.
Fig.III.4.8.L D S C thermogram of PVC/EVA?SAN ternary blends
Fig.III. 4.8.2.DSC thermogrum d PVC / EVA / SAN ternary blends.
Table III.4.2 Glass transition temperature of PVC/EVA/SAN ternary blends
III.4.3.2 Thermogravimetry
Fig.III.4.9. Comparison of glass transition temperatureof miscible ternary blends experimentally determined and calculated according to equation 111.18
Fig.III. 4-10-TG and DTG curves of misciblePVC/EVA /SAN 35/35/30 blend.
Fig.III.4.11 . TG and DTG curves of miscible PVC /EVA/SAN 15/35/50 blend.
Fig.III. 4.12 T.G and DTG Curves of miscible PVC/ EVA/ SAN 35/15 /50 blend.
Fig.III.4.13.TG and DTG curves of immiscible PVC/ EVA/ lSAN 15/15/70 blend
Table III.4.1 Comparison of properties between PVC, EVA, SAN and PVC/EVA/SAN ternary blends
III.4.4. INFRARED SPECTROSCOPY STUDIES
Fig.III.4.14 Ternary phase diagram showing the effect of blend composition onT0 and T50 of PVC/EVA, PVC/ SAN, EVA/SAN and PVC /EVA /SAN blends.
Fig.III.4.15. Infrared spectrum of PVC/EVA/SAN 25/25/50
Fig.III.4.16.Infrared spectrum of ternary blends of PVC/EVA/SAN 9/21/70
III.4.5. MECHANICAL PROPERTIES
Fig. III. 4-17, Stress-strain behaviour of PVC /EVA /SAN ternary blends.
Fig.III. 4-18. Stress-strain behaviour of PVC/EVA/SAN ternary blends.
Table III.4.3 Tensile strength of PVC/EVA/SAN ternary blends
Table III.4.4Youngs modulus of PVC/EVA/SAN ternary blends
Table III.4.5 Elongation at break of ternary blends of PVC/EVA/SAN
Fig.III.4.19 Tearing forces Vs displacement of PVC/ EVA/ SAN blends.
Table III.4.6 Tear strength of PVC/EVA/SAN ternary blends
Table III.4.7Tensile impact strength and hardness of PVC/EVA/SAN ternary blend
III.4.6. SOLUTION RHEOLOGY
Fig.III.4.20.Viscosity Vs shear rate of PVC/EVA/SAN blends
III.4.7. REFERENCES
IV. CONCLUSION AND SCOPE FOR FUTURE STUDIES
IV.1. CONCLUSION
IV.2. SCOPE FOR FUTURE STUDIES
LIST OF PUBLICATION FROM THE PRESENT WORK
International Journals
Papers presented in conferences
CURRICULAM VITAE