The changes in the structure and morphology of a random copolymer containing 92 mol % glycolide units and 8 mol % lactide units as a function of in vitro hydrolysis have been studied. A number of techniques, such as wide‐angle x‐ray diffraction, small‐angle x‐ray scattering, density measurements, infrared spectroscopy, and viscometry were employed in this study. The results showed that the hydrolytic attack was initiated in the amorphous areas of the polymer. After 28 days in the in vitro medium most of the amorphous areas had been chemically converted to lower‐molecular‐weight species such as oligomers of poly(glycolide‐co‐lactide). These low‐molecular‐weight species become water solble and are removed rapidly after day 28. Thus the fiber takes on a Swiss cheese character as the amorphous matter is hydrolyzed and eventually dissolved. As hydrolysis proceeds further, the crystalline areas of the polymer are attacked and eventually removed from the fiber by solubilization. The resulting voids in the fiber are eventually filled by a “collapse” of the structure. The role of the amorphous areas of the polymer in controlling the tensile strength of the suture is discussed.

synopsisTwo types of emulsion-grade polytetrafluoroethylene particles have been studied. We refer to these as ribbons and rods. The ribbons consist of very thin ribbons or lamellae folded upon themselves a number of times. In typical emulsion-grade material prepared at Allied Chemical, the unraveled ribbon measures about 3.25 p in length, 0.25 I( in width, and 60 d in thickness. The folded ribbons, which form the particles, are about 0.5 p long and 0.25 p wide. Electron diffraction shows that the ribbons are single crystals with the chain axis parallel to the long axis of the ribbons thus forming extended chain crystals. This extended-chain packing is consistent with the observed cleavage or fibrillation of the ribbons and with the molecular weight. The rods are formed in lowyield polymerizations. Electron diffraction also shows that the rods are single crystals with the chain axis parallel to the long axis of the rods. Striations parallel to the long axis are believed to result from stacking of parallel segments. Considerable bending of the long axis of rods is observed.

SynopsisA homologous series of aliphatic polyoxamides, nylon 122, 102, 82, and 62, were p r e pared by the bulk polycondensation of dialkyl oxalates with diamines. Infrared spectroscopy, x-ray diff raotion, differential thermal analysis, thermogravimetric analysis, and gas chromatography were used to study the structure and thermal stability of these polxoxamides. From the fiber pattern of nylon 122, a structural repeat distance of 19.5 A was measured. This was in close agreement with the expected value for an extended planar, zigzag chain conformation. With the exception of the expected decrease in the structural repeat distance along the chain axis resulting from the different number of methylene groups, nylons 122,102, and 82 were isostructural. Nylon 62 appeared to pack in a similar manner to the other materials studied. However, there were differences in the diffraction pattern of this polymer; these may be indicative of a different chain conformation or of strain in the crystalline regions of the polymer. The infrared spectra indicate the presence of strong hydrogen bonding in all the polymers. Thermal analysis and pyrolysis data revealed catastrophic polymer degradation between 400 and 500°C in nitrogen, with appreciable homolytic cleavage of the oxamide group.

The crystal structure of the α polymorph of nylon 4 has been determined from the x‐ray diffraction patterns of uniaxially oriented monofilaments. In general the crystal structure of α nylon 4 is similar to that of α nylon 6. The unit cell is monoclinic with the following dimensions: a = 9.29 ± 0.05 A., b = 12.24 ± 0.05 A., c = 7.97 ± 0.05 A., and β = 114.5 ± 1.0°. There are eight monomeric units in the unit cell. The theoretical density is 1.37 g./cc. and the observed density 1.25 g./cc. The space group is P21. The nylon 4 chains are of the extended planar zigzag type, with the plane of the zigzag approximately parallel to the a axis of the unit cell. Along the a axis, every other chain is inverted—an antiparallel arrangement of chains—thus permitting complete hydrogen bonding and the formation of sheets of nylon 4 chains. Along the c axis of the unit cell, the second sheet is displaced by3/10 of the b axis, thus leading to a staggered arrangement of sheets. The sheets are held in place by van der Waals forces.

No abstract