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Unger, Roland:
Kristallisations- und Phasenverhalten in Blockcopolymeren des Ethylenoxids mit tert.-Butylmethacrylat und Methylmethacrylat
(Crystallization and phase behaviour in block copolymers of ethylene oxide with tert.-butyl methacrylate and methyl methacrylate)
Merseburg: Technical University, Faculty of Natural Sciences, 1989.
Bibliographic notes: VIII, 144 pages, 6 sheets; figures, tables; 30 cm
(Defence on 15.07.1990)


By means of differential scanning calorimetry, X-ray scattering, and microscopic techniques, the thermal and phase behaviour of crystalline (PEO = poly(ethylene oxide)) amorphous block copolymers have been investigated in dependence of the compatibility (PEO/PTBMA = poly(tert.-butyl methacrylate) incompatible polymer pair; PEO/PMMA = poly(methyl methacrylate) compatible polymer pair), of the block structure and composition. In any case a strong structure dependence of the crystallization and melting behaviour can be observed. The crystallization mechanisms are different: As a rule, in the case of the PEO/PMMA system the crystallization takes place in the compatible blend (UCST behaviour) whereas in the PEO/PTBMA system this is performed in the PEO domains. Crystal lamella and domain sizes are given for both the non-equilibrium and, partly, for the equilibrium (conformity with theory). The behaviour of homo-PEO block-copolymer systems is discussed.


  • Table of contents
  • Abbreviations used
  • Symbols and formula signs
  • Preface
  1. Introduction

Part I

  1. Crystallization kinetics and melting in polymers
    1. Thermodynamic description of the crystallization
    2. Nucleation in the melt
      1. Temperature dependence of the free enthalpy and the critical nucleus size
      2. Nucleation rate: Supercooling and molecular mobility
    3. Crystal growth
      1. Phenomenological description of the crystal growth
      2. Analytical description of the crystal growth
    4. Nucleation and crystal growth rate for the crystallization from the solution and compatible polymer blend
    5. Melting behaviour
  2. Properties of polymer-polymer blends
    1. Compatibility and incompatibility in polymer blends
    2. Properties of incompatible blends
    3. Properties of compatible blends
    4. Compatibility in polymer systems with PEO
      1. Estimation of the compatibility by the Nishi-Wang theory
      2. Compatibility of PEO with different polymers
      3. Compatibility of PEO with PMMA
  3. Micro-phase morphology in block copolymers
    1. Amorphous-amorphous block copolymers
    2. Micro-phase morphology in block copolymers with one crystalline component
    3. Blends of homo polymers and block copolymers
  4. Behaviour in block copolymers of PEO with different amorphous blocks
    1. Incompatible polymer blocks
    2. Compatible polymer blocks

Part II

  1. Experimental
    1. Synthesis and characterization of the substances used
    2. Measurement techniques used and analysis
      1. Differential scanning calorimetry (DSC)
      2. X-ray scattering techniques
      3. Additional techniques
  2. Physical properties of the homo polymers and homo-polymer blends used
    1. Poly(ethylene oxide) (PEO)
    2. Poly(tert.-butyl methacrylate) (PTBMA) and poly(methyl methacrylate) (PMMA)
    3. Thermal stability
    4. Phase behaviour in PEO/PTBMA and PEO/PMMA blends
    5. Low-temperature behaviour in PEO/PMMA blends and block copolymers
  3. Crystallization and phase behaviour in the PEO/PTBMA and PEO/PMMA systems. Results and discussion
    1. Outline
    2. PEO-PTBMA diblock copolymers
      1. Crystallization and phase behaviour in the non-equilibrium
      2. Isothermal investigations and conclusions on the phase behaviour in the thermodynamic equilibrium
      3. WAXS investigations for crystal-lattice analysis
      4. Long-term behaviour
    3. P(MMA-b-EO-b-MMA) and P(TBMA-b-EO-b-TBMA) triblock copolymers with increasing PMMA and PTBMA block lengths
    4. Block copolymer with alternating block structure
    5. Star-shaped block copolymers
    6. Influence of the initiator on the thermal and phase behaviour
    7. Crystallization and phase behaviour in homo-PEO block copolymer blends
    8. Differences for the structure formation for the crystallization from the melt and from the diluted solution
  4. Conclusion
  • References
  • Addendum 1: Sample data for the PEO/PTBMA system
  • Addendum 2: Blends
  • Addendum 3: Thermal characterization of the samples noted in add. 1
  • Addendum 4: Thermal characterization of the blends noted in add. 2
  • Addendum 5: PEO/PMMA system: sample data and thermal characterization
  • Addendum 6: Blends of the PEO/PMMA system
  • Addendum 7: WAXS: PEO reflexes at CuKα (λ = 0.15418 nm)
  • Addendum 8: Physical properties of PEO
  • Addendum 9: Physical properties of PMMA and PTBMA
  • Addendum 10: Legend of the samples in Figures 40 and 41
  • Addendum 11: Additional results
  • Addendum 12: Additional figures

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