English

Order-Disorder Tricriticality in $\mathrm{A}_n \mathrm{B}_n$ Star Polymer Melts

Statistical Mechanics 2026-05-25 v1 Soft Condensed Matter

Abstract

Tricriticality usually requires tuning an additional thermodynamic parameter. Here we show that, in symmetric AnBn\mathrm{A}_n\mathrm{B}_n star-polymer melts, the arm number nn itself plays this role and drives the order--disorder transition (ODT) from second order to first order. By developing a sixth-order free-energy expansion within the random phase approximation and comparing it with self-consistent field theory (SCFT) calculations, we analytically identify a tricritical arm number, ntc5.4475n_{\mathrm{tc}}\approx 5.4475. For n<ntcn<n_{\mathrm{tc}}, the lamellar ordering transition remains continuous and occurs at the spinodal point, (χN)s10.495(\chi N)_{\mathrm{s}}\approx 10.495. For n>ntcn>n_{\mathrm{tc}}, the transition becomes first order, and (χN)ODT(\chi N)_{\mathrm{ODT}} shifts below (χN)s(\chi N)_{\mathrm{s}} with a quadratic dependence near the tricritical point. SCFT calculations confirm the predicted transition character and phase-boundary shift. The origin of this behavior is traced to inter-arm correlations generated by the common junction. We further show that the noninteger tricritical arm number can be effectively realized in binary mixtures of star polymers. This provides a rare analytically tractable example of architecture-induced tricriticality in a microphase-separating polymer system.

Keywords

Cite

@article{arxiv.2605.23758,
  title  = {Order-Disorder Tricriticality in $\mathrm{A}_n \mathrm{B}_n$ Star Polymer Melts},
  author = {Minhoon Kim and Wonjun Kang and Daeseong Yong and Junhan Cho and Jaeup U. Kim},
  journal= {arXiv preprint arXiv:2605.23758},
  year   = {2026}
}