Polymorphism is a well-established phenomenon in crystalline materials and is important for pharmaceutical and polymeric materials. In our study concerning the processability of polymers, we came across an unusual observation related to polymorphism induced by pressure. The experimental observation is that polyethylene crystals transform from the stable orthorhombic crystal into a transient hexagonal phase. The occurrence of a transient hexagonal phase is shown to be dependent on the polymer crystal size; smaller crystals transform into the transient hexagonal phase at temperatures and pressures much below the thermodynamic critical point Qo, which is located at P = 3.6 kbar and T = 230 degreesC. The crystal size dependence in the phase transition was investigated by in situ X-ray studies in the unirradiated and irradiated solution-crystallized films. Since the chain mobility is rather high in the hexagonal phase, sintering has been attempted via this transient phase using ultrahigh molecular weight polyethylene (UHMW-PE) as a model system. UHMW-PE is an intractable polymer due to its high molar mass but possesses excellent abrasion resistance properties. For this reason it is used as an inlay in demanding applications such as artificial hip and knee joints. The service life of UHMW-PE in these artificial joints, however, is limited due to the poor processing characteristics notably during sintering, and often a second operation is needed to replace the UHMW-PE interface. Sintering via the transient hexagonal phase could provide a solution for this important problem which concerns an increasing number of people.

The phase transformations under elevated pressure have been followed in situ by X-ray and Raman spectroscopy for ultrahigh-molecular-weight polyethylene (UHMW-PE) reactor powder. Using the in situ X-ray as a reference for the Raman work, it has been shown that Raman spectroscopy is a convenient method to follow phase transformations in polyethylene under pressure. The distinction has been made between different solid phases in polyethylene (monoclinic, orthorhombic, and hexagonal phases) and the melt by studying the conformational changes occurring within the skeletal mode (1000-1200 cm -1 ) upon the phase transformations. The crystal field splitting (1415/1440 cm -1 ) in the -CH2bending mode of the Raman spectrum of polyethylene, related to the orthorhombic unit cell, was confirmed to be sensitive to transformations between different crystal structures. By following the changes occurring in the methylene bending mode together with the changes within the C-C skeletal mode, it has been shown that the crystalline phases and the melt can be mutually distinguished.

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