The new crystal structure models of forms I and II of isotactic polybutene-1 have been proposed by analyzing the 2-dimensional X-ray diffraction data measured for the highly oriented samples of almost pure crystal forms. The crystal form I was found to take the hexagonal packing structure of the (3/1) helices with the space group P3̅ , different from the previously reported R3̅ c or R3c models. The right-and left-handed chains are packed alternately with the random directionality along the chain axis. The crystal form II was concluded to take the tetragonal unit cell of the (11/3) helical chains, the space group of which is P4̅ b2. The righthanded (left-handed) chains are positioned at one site with the statistical disorder of upward and downward directionality along the chain axis. The time-dependent electron diffraction measurement showed that the crystal lattices of forms I and II are related to each other with the common 110 plane boundary, as already reported by the other researchers. By referring to the crystal structures confirmed in this study, a new phase transition mechanism has been proposed for understanding this geometrical relation between these two crystal phases. The mechanism is based on a kind of soft mode concept; the mutually opposite translational movements of the right-and left-handed chains occur along the 110 plane of the tetragonal lattice of form II. The phase angle between the neighboring unit cells along the [110] direction is π. This translational lattice vibrational mode increases the amplitude and causes the softening of the original form II unit cell into a transient structure composed of the hexagonally packed pairs of right-and left-handed chains. Then, this transient structure is stabilized to the crystal form I, during which the chain conformation changes cooperatively from (11/3) to (3/1) form by a slight change in the trans and gauche torsional angles of the skeletal chains. This newly proposed transition mechanism can explain also the formation of twin structure of form I crystals.

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The structural evolutions and kinetics of melt-quenched poly(L-lactic acid) (PLLA) during the process of isothermal physical aging below the glass transition temperature (T(g)) were investigated by time-resolved infrared spectroscopy. The results show that local ordered structure is developed with aging time. Such local ordered structure shows the same characteristic band at 918 cm(-1) as that of the mesomorphic structure formed during the unaxially drawn process of PLLA from the glassy state. On the basis of spectroscopic evidence, we therefore proposed that the so-called local ordered structure formed by physical aging can be ascribed to a kind of mesophase of PLLA. Of particular note, a very small amount of mesophase already exists in the initial state of melt-quenched PLLA sample, whereas it is totally undetectable in the melt-quenched poly(D,L-lactide) (PDLLA) sample. By temperature-dependent IR spectroscopy, it is found that the local ordered structure formed during the physical aging process will be "partially molten" rather than "totally molten" in the temperature region corresponding to the physical aging peak of aged PLLA. Such an observation can explain the phenomenon of physical aging enhanced cold crystallization rate.

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The crystallization behavior of isotactic poly(1-butene) (iPBu) from melt on the surface of melt-drawn oriented isotactic polypropylene (iPP) thin films and in the melt-drawn oriented iPBu/ iPP blend thin films was studied. It has been found that iPBu in the melt-drawn iPBu/iPP blend films is form I crystals like in the meltdrawn thin films on its own. The form I iPBu crystals exhibit, however, an oriented edge-on lamellar structure rather than the fibrils or shish crystals observed in melt-drawn pure iPBu films, reflecting the influence of iPP on the melt-draw behavior of iPBu. Melt recrystallization of iPBu in the iPBu/iPP melt-drawn films does not change its orientation status and crystalline modification, reflecting the epitaxial capability of iPBu on oriented iPP. This has been further confirmed by oriented form I crystallization of the spin-coated iPBu thin films from melt on oriented iPP melt-drawn films, which eliminates the confinement effect on the form I iPBu crystallization in the melt-drawn iPBu/iPP film. In situ IR study also confirms that the high melting temperature form I iPBu crystals are directly formed on the iPP substrate. The IR results further demonstrated that the crystallization of form I iPBu at 104 °C on iPP substrate is faster than its form II. Taking all of the experimental results into account, the epitaxial crystallization of iPBu on oriented iPP substrate in its form I is believed to be the synergistic effect of lattice matching between iPP and form I iPBu as well as the crystallization kinetics of iPBu.

A new technique has been developed for in situ study of the form II to I phase conversion of isotactic poly­(1-butene) (iPBu) in real space. It can distinguish the nucleation and crystal growth processes unequivocally, especially in the early nucleation stage, which can hardly be followed by other traditionally used techniques owing to the limited amount of the transformed form I crystals. Moreover, the subsequent growth process of the form I crystals revealed by the time-dependent images taken during the transition process makes it possible to estimate the growth rate of the form I iPBu crystals during phase transition of ca. 1.65 nm/min at room temperature, which is about 500 times slower than the melt crystallization process. It has also revealed the slow-down crystal growth in the late transformation stage. All of these indicate that the technique is powerful in studying many aspects related to the II–I phase transition of iPBu.