Heterogeneous Nucleation of High-Density Polyethylene Crystals on Graphene within Microdomains

In polymer processes, nucleating agents are often used to control the kinetics of crystallization, but their application remains largely a matter of trial and error. Thermodynamically, the efficiency of a nucleating agent can be quantified by the difference in substrate/crystal, crystal/melt, and substrate/melt interfacial energies, Δσ. In this work, the efficiency of graphene nanoplatelets (GNP) as nucleating agents for high-density polyethylene (HDPE) is investigated. HDPE nucleates and crystallizes rapidly, so Δσ can be especially difficult to measure experimentally. To overcome this difficulty, blends of HDPE+GNP are confined to microdomains so that crystallization becomes nucleation limited. Two methods of microdomain formation are employed. In the first, HDPE+GNP is melt-blended with an immiscible matrix of polystyrene (PS), and crystallization is characterized using differential scanning calorimetry (DSC); in the second, dispersions of HDPE+GNP in toluene are sprayed onto PS substrates, and crystallization is characterized with polarized optical microscopy (POM). Heterogeneous nucleation rates at several crystallization temperatures and for several GNP loadings were measured by these two methods and found to give excellent agreement across GNP loadings. The value of Δσ for HDPE+GNP is calculated to be 0.83 ± 0.18 erg/cm2. This value is only 2.8 times larger than that reported for HDPE nucleated heterogeneously on a HDPE fiber, a nearly ideal nucleating agent for HDPE, and much smaller than many of the best nucleating agents reported for other polymers. We conclude that GNP is an efficient nucleating agent for HDPE.