AFM Studies of Semicrystalline Polymer/Inorganic Nanocomposites

Open Access
Strawhecker, Kenneth Edward
Graduate Program:
Materials Science and Engineering
Doctor of Philosophy
Document Type:
Date of Defense:
March 15, 2002
Committee Members:
  • Evangelos Manias, Committee Chair
  • Sridhar Komarneni, Committee Member
  • Ralph H Colby, Committee Member
  • Sanat Kumar, Committee Member
  • polymer
  • inorganic
  • nanocomposites
  • AFM
  • layered silicates
  • composites
  • materials
The aims of this work are to elucidate the effects of interaction strength on the crystallization of a polymer near an inorganic surface; connect filler induced polymer crystallinity with resulting property changes, especially for strongly interacting (i.e. hydrogen bonding) systems; and to devise atomic force microscopy (AFM) methods for probing the crystallinity and properties of polymer/layered silicate systems at the nanometer level. Three inorganically filled systems were studied: (1) poly(vinyl alcohol) (PVA), (2) poly(ethylene oxide) (PEO), and (3) polypropylene (PP). Since it has the strongest interactions, the PVA system is investigated first. AFM is used in conjunction with x-ray diffraction and differential scanning calorimetry (DSC) to show that strong polymer/filler interactions can promote a different crystalline structure and a different morphology than those seen in the bulk. The study then proceeds to the weakly interacting PEO/inorganic system where it is found that the inorganic layers disrupt crystalline morphology, but do not change the crystal structure. Furthermore, crystallization always occurs in volumes away from the inorganic filler. The third system (neutral interactions), PP/inorganic is then discussed. The three systems are compared with each other, and it is found that the crystalline morphology and structure is highly dependent upon the strength of interaction between the polymer and filler. Due to its far-reaching morphology changes, the strongly interacting system was chosen for property studies. The composite structure study revealed a coexistence of exfoliated and intercalated MMT layers, especially for low and moderate silicate loadings. The inorganic layers promote a new crystalline phase different than the one of the respective neat PVA, characterized by higher melting temperature and a different crystal structure. This new crystal phase reflects on the composite materials properties, which have mechanical, thermal, and water vapor transmission properties superior to that of the neat polymer and its conventionally filled composites. For example, for a 5wt.% MMT exfoliated composite, the softening temperature increases by 25 degrees celcius, the Young's modulus triples with a decrease of only 20% in toughness, whereas there is also a 60% reduction in the water permeability. Furthermore, due to the nanoscale dispersion of filler, the nanocomposites retain their optical clarity. Finally, to better connect changes in morphology with property enhancements, AFM methods were devised which allow direct imaging of morphology as well as local properties.