In Situ Atomic Force Microscopy Tracking of Nanoparticle Migration in Semicrystalline Polymers.

We present in situ tracking of silica nanoparticle (NP) migration from a poly(ethylene oxide) (PEO) melt into interlamellar region using in situ atomic force microscopy (AFM). Our results confirm the previous hypothesis that NPs migrate into the interlamellar regions at crystallization growth rates smaller than a critical value under isothermal conditions. Under these slow crystallization conditions, bare silica NPs are rejected as defects by the growing crystal of PEO, and the in situ imaging on the large (50 nm) NPs helps track the migration into the amorphous zones. We extend this AFM technique to estimate lamellar growth rates that correlate with spherulite growth rates determined by polarized light optical microscopy (PLOM) but at smaller undercoolings than are typical for PLOM.

Terephthalic Acid Copolyesters Containing Tetramethylcyclobutanediol for High-Performance Plastics.

There is a need for high-performance applications for terephthalic acid (TPA) polyesters with high heat resistance, impact toughness, and optical clarity. Bisphenol A (BPA) based polycarbonates and polyarylates have such properties, but BPA is an endocrine disruptor. Therefore, new TPA polyesters that are less hazardous to health and the environment are becoming popular. Tetramethylcyclobutanediol (TMCD) is a difunctional monomer that can be polymerized with TPA and other diols to yield copolyesters with superior properties to conventional TPA polyesters. It has a cyclobutyl ring that makes it more rigid than cyclohexanedimethanol (CHDM) and EG. Thus, TMCD containing TPA copolyesters can have high heat resistance and impact strength. TPA can be made from abundantly available upcycled polyethylene terephthalate (PET). Therefore, this review discusses the synthesis of monomers and copolyesters, the impact of diol composition on material properties, molecular weight, effects of photodegradation, health safety, and substitution of cyclobutane diols for future polyesters.

Impact of chain microstructure on solution and thin film self-assembly of PCHD-based semi-flexible/flexible diblock copolymers.

Self-assembly of semi-flexible/flexible block copolymers in a selective solvent is examined using a set of diblock copolymers where the chain microstructure of the semi-flexible block is manipulated in order to tune chain stiffness. Conceptually, the reduced conformational space of the semi-flexible block is anticipated to alter the way the chains pack, potentially changing the structure of self-assembled aggregates in comparison to flexible diblock copolymer analogs. Semi-flexible/flexible diblock copolymers comprised of poly(styrene)-block-poly(1,3-cyclohexadiene) (PS-b-PCHD) having systematic changes in chain microstructure, as captured by the ratio of 1,4/1,2-linkages between cyclohexenyl repeat units, and molecular weight of the PCHD blocks were synthesized using anionic polymerization. These diblocks were dissolved in tetrahydrofuran (THF), which is a preferential solvent for PS, and the structures formed were examined using laser light scattering and complementary imaging techniques. Results show that PS-b-PCHD copolymers with a chain microstructure of 90% 1,4/10% 1,2 linkages between cyclohexenyl repeat units (referred to simply as 90/10) are able to micellize, forming spherical structures, while diblocks of 70/30 and 50/50 1,4-to-1,2 ratios remain as single chains and ill-defined aggregates, respectively, when dissolved in THF. With inferences drawn from simple structural models, we speculate that this self-assembly behavior arises due to the change in the chain configuration with increasing content of 1,2-links in the backbone. This renders the chain with higher 1,2 content incapable of swelling in response to solvent and unable to pack into well-defined self-assembled structures.