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Abstract In this study, poly(ethylene terephthalate)‐block‐polyethylene (PET‐PE) multiblock copolymers (MBCPs) with block molar masses of ~4 or 7 kg mol⁻¹and either alternating or random block sequencing, and a PE‐PET‐PE triblock copolymer (TBCP) of comparable total molar mass, were synthesized. To explore the effect of molecular architecture on compatibilization, both MBCPs and TBCPs were blended into 80/20 wt/wt mixtures of PET/linear low‐density PE (LLDPE). Compatibilization was remarkably efficient for all MBCP types, with the addition of 0.2 wt% yielding blends nearly as tough as PET homopolymer. Addition of MBCP also significantly decreases LLDPE dispersed phase sizes compared to PET/LLDPE neat blends, as much as 80% in as‐mixed blends and by a factor of 10 in post‐mixing thermally annealed samples. Conversely, the TBCP was less efficient at decreasing domain sizes of the blends and improving the mechanical properties, requiring loadings of 1 wt% to produce comparably tough blends. Peel tests of PET/BCP/LLDPE trilayer films showed that both MBCPs and TBCP all improve interfacial strength over a PET‐PE bilayer film by two orders of magnitude; however, when the BCPs were preloaded into LLDPE, only the MBCP containing films showed strong adhesion highlighting their potential utility as adhesive agents in multilayer films. 

Abstract Poly(lactic acid) (PLA) is a commercially available bio‐based polymer that is a potential alternative to many commodity petrochemical‐based polymers. However, PLA's thermomechanical properties limit its use in many applications. Incorporating polymer‐grafted cellulose nanocrystals (CNCs) is one potential route to improving these mechanical properties. One key challenge in using these polymer‐grafted nanoparticles is to understand which variables associated with polymer grafting are most important for improving composite properties. In this work, poly(ethylene glycol)‐grafted CNCs are used to study the effects of polymer grafting density and molecular weight on the properties of PLA composites. All CNC nanofillers are found to reinforce PLA above the glass transition temperature, but non‐grafted CNCs and CNCs grafted with short PEG chains (<2 kg mol⁻¹) are found to cause significant embrittlement, generally resulting in less than 3% elongation‐at‐break. By grafting higher molecular weight PEG (10 kg mol⁻¹) onto the CNCs at a grafting density where the polymer chains are predicted to be in the semi‐dilute polymer brush conformation (~0.1 chains nm⁻²), embrittlement can be avoided. 

Abstract Extensional flow properties of polymer solutions in volatile solvents govern many industrially-relevant coating processes, but existing instrumentation lacks the environment necessary to control evaporation. To mitigate evaporation during dripping-onto-substrate (DoS) extensional rheology measurements, we developed a chamber to enclose the sample in an environment saturated with solvent vapor. We validated the evaporation-controlled DoS device by measuring a model high molecular weight polyethylene oxide (PEO) in various organic solvents both inside and outside of the chamber. Evaporation substantially increased the extensional relaxation time$$\lambda _{E}$$ ${\lambda }_E$for PEO in volatile solvents like dichloromethane and chloroform. PEO/chloroform solutions displayed an over 20-fold increase in$$\lambda _{E}$$ ${\lambda }_E$due to the formation of an evaporation-induced surface film; evaporation studies confirmed surface features and skin formation reminiscent of buckling instabilities commonly observed in drying polymer solutions. Finally, the relaxation times of semi-dilute PEO/chloroform solutions were measured with environmental control, where$$\lambda _{E}$$ ${\lambda }_E$scaled with concentration by the exponent$$m=0.62$$ $m=0.62$. These measurements validate the evaporation-controlled DoS environment, and confirm that chloroform is a good solvent for PEO, with a Flory exponent of$$\nu =0.54$$ $\nu =0.54$. Our results are the first to control evaporation during DoS extensional rheology, and provide guidelines establishing when environmental control is necessary to obtain accurate rheological parameters. 

Tuning the molecular architecture of block copolymer blends is a powerful strategy to optimize their performance in pressure-sensitive adhesive (PSA) formulations.