Viscoelastic properties of polymer melts are particularly challenging to compute due to the intrinsic stress fluctuations in molecular dynamics (MD). We compared equilibrium and non-equilibrium MD approaches for extracting the storage ($G\prime$ ) and loss moduli ($G″$ ) over a wide frequency range from a bead-spring chain model in both unentangled and entangled regimes. We found that, with properly chosen data processing and noise reduction procedures, different methods render quantitatively equivalent results. In equilibrium MD (EMD), applying the Green−Kubo relation with a multi-tau correlator method for noise filtering generates smooth stress relaxation modulus profiles from which accurate $G\prime$ and $G″$ can be obtained. For unentangled chains, combining the Rouse model with a short-time correction provides a convenient option that circumvents the stress fluctuation challenge altogether. For non-equilibrium MD (NEMD), we found that combining a stress pre-averaging treatment with discrete Fourier transform analysis reliably computes $G\prime$ and $G″$ with a much shorter simulation length than previously reported. Comparing the efficiency and statistical accuracy of these methods, we concluded that EMD is both reliable and efficient, and is suitable when the whole spectrum of linear viscoelastic properties is desired, whereas NEMD offers flexibility only when some frequency ranges are of interest.

Polydispersity is inevitable in industrially produced polymers. Established theories of polymer dynamics and rheology, however, were mostly built on monodisperse linear polymers. Dynamics of polydisperse polymers is yet to be fully explored—specifically how chains of different lengths affect the dynamics of one another in a mixture. This study explored the dynamics of bidisperse polymer melts using molecular dynamics and a bead–spring chain model. Binary mixtures between a moderately entangled long-chain species and an unentangled or marginally entangled short-chain species were investigated. We found that adding short chains can significantly accelerate the dynamics of the long chains by substantially lessening their extent of entanglement. Meanwhile, although introducing long chains also hinders the motion of the short chains, it does not qualitatively alter the nature of their dynamics—unentangled short chains still follow classical Rouse dynamics even in a matrix containing entangled chains. Detailed Rouse mode analysis was used to reveal the effects of entanglement at chain segments of different scales. Stress relaxation following a step shear strain was also studied, and semi-empirical mixing rules that predict the linear viscoelasticity of polydisperse polymers based on that of monodisperse systems were evaluated with simulation results.

Surface defects are frequently observed in calendered polyvinyl chloride (PVC) films. Their evaluation in production environments is typically qualitative and operator dependent. Using the common gas entrapment defects as the test case, the present study develops a four-step image-processing workflow that converts scanned film images into pixel intensity matrices and groups defect pixels using density-based clustering (DBSCAN). The procedure provides quantitative measures of defect count, size, and spatial distribution without manual labeling. The effects of roll gap, calendering speed, upstream mixing time, and plasticizer type were examined under controlled conditions. Larger roll gaps and higher speeds reduced degassing efficiency and increased both defect number and defect area. Short mixing times led to incomplete gelation and higher defect frequency. Among the tested plasticizers, TOTM produced the lowest defect counts, followed by DEHP and ESBO. Design-of-experiments analysis ranked parameter sensitivity and identified operating ranges that limit defect formation. The method provides a practical basis for routine surface inspection and supports process adjustment using measurable defect metrics rather than visual judgment alone.