The physical structure of polymer films is important for understanding the observed macroscopic properties. In crystalline−crystalline block copolymers, the hierarchical nature of assembly is even more influential. Controlling this assembly process is crucial for tailoring film properties. In materials where crystallization of each block occurs nearly simultaneously, the ability to manipulate crystallization order is desirable. Poly-(ethylene oxide)-b-poly(ε-caprolactone) (PEO-b-PCL) films were monitored via ATR-FTIR to determine the crystallization order during drying from varying solvents. PCL crystallized first from most solvents except toluene and ethyl acetate, where PEO nucleation occurred first. Moreover, after melting the sample to remove solvent−polymer interaction effects, PCL was first to crystallize from the melt, as has been previously reported. Differences in the films' morphologies based on crystallization order were observed using polarized optical microscopy. These results demonstrate that the order of crystallization and the assembly within the film were controllable when casting symmetric diblock PEO-b-PCL films from different solvents.

Effective control of pain management has the potential to significantly decrease the need for prescription opioids following a surgical procedure. While extended release products for pain management are available commercially, the implementation of a device that safely and reliably provides extended analgesia and is sufficiently flexible to facilitate a diverse array of release profiles would serve to advance patient comfort, quality of care and compliance following surgical procedures. Herein, we review current polymeric systems that could be utilized in new, controlled post-operative pain management devices and highlight where opportunities for improvement exist.

Key hurdles for replacing damaged cartilage with an equivalent synthetic construct are the development of a hydrogel with a strength that exceeds that of cartilage and fixation of this hydrogel onto the surface of an articulating joint. This article describes the first hydrogel with a tensile and compressive strength (51 and 98 MPa) that exceeds those of cartilage (40 and 59 MPa), and the first attachment of a hydrogel to a metal backing with a shear strength (2.0 MPa) that exceeds that of cartilage on bone (1.2 MPa). The hydrogel strength is achieved through reinforcement of crystallized polyvinyl alcohol with bacterial cellulose. The high attachment strength is achieved by securing freeze-dried bacterial cellulose to a metal backing with an adhesive and a shape memory alloy clamp prior to infiltration and crystallization of the polyvinyl alcohol. The bacterial cellulose-reinforced polyvinyl alcohol is three times more wear resistant than cartilage over one million cycles and exhibits the same coefficient of friction. These advances in hydrogel strength and attachment enable the creation of a hydrogel-based implant for durable resurfacing of damaged articulating joints.

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