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

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Main Authors: Kim, Minhoon, Kang, Wonjun, Yong, Daeseong, Cho, Junhan, Kim, Jaeup U.
Format: Preprint
Published: 2026
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_version_ 1866914592599310336
author Kim, Minhoon
Kang, Wonjun
Yong, Daeseong
Cho, Junhan
Kim, Jaeup U.
author_facet Kim, Minhoon
Kang, Wonjun
Yong, Daeseong
Cho, Junhan
Kim, Jaeup U.
contents Tricriticality usually requires tuning an additional thermodynamic parameter. Here we show that, in symmetric $\mathrm{A}_n\mathrm{B}_n$ star-polymer melts, the arm number $n$ 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, $n_{\mathrm{tc}}\approx 5.4475$. For $n<n_{\mathrm{tc}}$, the lamellar ordering transition remains continuous and occurs at the spinodal point, $(χN)_{\mathrm{s}}\approx 10.495$. For $n>n_{\mathrm{tc}}$, the transition becomes first order, and $(χN)_{\mathrm{ODT}}$ shifts below $(χN)_{\mathrm{s}}$ 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.
format Preprint
id arxiv_https___arxiv_org_abs_2605_23758
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Order-Disorder Tricriticality in $\mathrm{A}_n \mathrm{B}_n$ Star Polymer Melts
Kim, Minhoon
Kang, Wonjun
Yong, Daeseong
Cho, Junhan
Kim, Jaeup U.
Statistical Mechanics
Soft Condensed Matter
Tricriticality usually requires tuning an additional thermodynamic parameter. Here we show that, in symmetric $\mathrm{A}_n\mathrm{B}_n$ star-polymer melts, the arm number $n$ 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, $n_{\mathrm{tc}}\approx 5.4475$. For $n<n_{\mathrm{tc}}$, the lamellar ordering transition remains continuous and occurs at the spinodal point, $(χN)_{\mathrm{s}}\approx 10.495$. For $n>n_{\mathrm{tc}}$, the transition becomes first order, and $(χN)_{\mathrm{ODT}}$ shifts below $(χN)_{\mathrm{s}}$ 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.
title Order-Disorder Tricriticality in $\mathrm{A}_n \mathrm{B}_n$ Star Polymer Melts
topic Statistical Mechanics
Soft Condensed Matter
url https://arxiv.org/abs/2605.23758