A Simple Relationship Relating Linear Viscoelastic Properties and Chemical Structure in a Model Diels–Alder Polymer Network

Abstract The purpose of this work is to develop a new analytical method for simulating the microscopic mechanical property of the cross-linked polymer system using the coarse-grained molecular dynamics simulation. This new analytical method will be utilized for the molecular designing of the tire rubber compound to improve the tire performances such as rolling resistance and wet traction. First, we evaluate the microscopic dynamic viscoelastic properties of the cross-linked polymer using coarse-grained molecular dynamics simulation. This simulation has been conducted by the coarse-grained molecular dynamics program in the OCTA) (http://octa.jp/). To simplify the problem, we employ the bead-spring model, in which a sequence of beads connected by springs denotes a polymer chain. The linear polymer chains that are cross-linked by the cross-linking agents express the three-dimensional cross-linked polymer network. In order to obtain the microscopic dynamic viscoelastic properties, oscillatory deformation is applied to the simulation cell. By applying the time-temperature reduction law to this simulation result, we can evaluate the dynamic viscoelastic properties in the wide deformational frequency range including the rubbery state. Then, the stress is separated into the nonbonding stress and the bonding stress. We confirm that the contribution of the nonbonding stress is larger at lower temperatures. On the other hand, the contribution of the bonding stress is larger at higher temperatures. Finally, analyzing a change of microscopic structure in dynamic oscillatory deformation, we determine that the temperature/frequency dependence of bond stress response to a dynamic oscillatory deformation depends on the temperature dependence of the average bond length in the equilibrium structure and the temperature/frequency dependence of bond orientation. We show that our simulation is a useful tool for studying the microscopic properties of a cross-linked polymer.

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Preparation, Characterization and Processing of PCL/PHO Blends by 3D Bioplotting

International Polymer Processing ◽

10.1515/ipp-2020-350508 ◽

2020 ◽

Vol 35 (5) ◽

pp. 458-470

Author(s):

S. Gopi ◽

B. A. Ramsay ◽

J. A. Ramsay ◽

M. Kontopoulou

Keyword(s):

Viscoelastic Properties ◽

Biomedical Applications ◽

Synergistic Effects ◽

Thermal And Mechanical Properties ◽

Flow Properties ◽

Immiscible Blends ◽

Melt Compounding ◽

Linear Viscoelastic ◽

Matrix Morphology ◽

Good Flow

Abstract Blends of polycaprolactone (PCL) and poly(3-hydroxyoctanoate) P(3HO) were prepared by melt compounding. These immiscible blends exhibited droplet-matrix morphology at compositions up to 30 wt% P(3HO). Even though the addition of amorphous P(3HO) decreased the crystallinity of PCL, the crystallization temperature of the blends increased by 6 to 7 8C. Blends containing up to 30 wt% P(3HO) had higher crystallization rates, and lower crystallization half-times compared to neat PCL. The viscosity of PCL decreased upon addition of P(3HO), making the blends suitable for processing using a 3D bioplotter. Compositions with 10 to 30 wt% P(3HO) were ideal for processing, because of their improved crystallization kinetics, reduced stickiness and good flow properties. Estimation of the interfacial tension by fitting the Palierne model to the linear viscoelastic properties of the blends revealed good compatibility, which gave rise to synergistic effects in the thermal and mechanical properties. The fibres prepared by 3D bioplotting maintained droplet matrix morphology, with finer particle size than the original compounded material. In addition to favourable viscosity and thermal properties, the extruded fibres containing 30 wt% P(3HO) had comparable modulus to the neat PCL, while exhibiting good ductility. These blends may be suitable alternatives to PCL for biomedical applications, because they provide a range of crystallinities, crystallization rates and viscosities.

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