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Polymer Classification: Crystallinity

Polymer Classification: Crystallinity

Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
Crystalline domains are the regions where polymer chains are aligned in an orderly manner and held together in proximity by intermolecular forces. For example, chains in the crystalline domains of polyethylene and nylon are bound together by van der Waals...

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Updated: Sep 22, 2025

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

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Published on: September 26, 2016

Fractionated Crystallization of Defect-Free Poly(3-hexylthiophene).

P Kohn¹, S Huettner¹, U Steiner¹

¹Cavendish Laboratory, Department of Physics, University of Cambridge, J J Thomson Avenue, Cambridge CB3 0HE, United Kingdom.

ACS Macro Letters

|May 24, 2022

Summary

This summary is machine-generated.

Fractionated crystallization, a chain-sorting mechanism, was observed in poly(3-hexylthiophene). Its extent depends on molecular weight and polydispersity, impacting material properties.

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Area of Science:

Polymer Science and Engineering
Materials Science
Crystallization Phenomena

Background:

Regioregular poly(3-hexylthiophene) is a semiconducting polymer with applications in organic electronics.
Understanding crystallization behavior is crucial for optimizing polymer properties and device performance.
Fractionated crystallization (FC) is a sorting mechanism that can influence polymer morphology and thermal properties.

Purpose of the Study:

To identify and characterize fractionated crystallization (FC) in well-defined regioregular poly(3-hexylthiophene) (P3HT).
To investigate the influence of molecular weight and polydispersity on the extent of FC.
To elucidate the impact of FC on the crystallization and melting behavior of P3HT.

Main Methods:

Utilized X-ray scattering (WAXS) and differential scanning calorimetry (DSC) to analyze bulk P3HT samples.
Performed temperature-dependent investigations of long period (Lp) and (100)-WAXS reflections.
Studied samples with varying molecular weights and polydispersities.

Main Results:

Fractionated crystallization (FC) was identified in low molecular weight, defect-free regioregular P3HT.
While WAXS indicated similar crystallinity, DSC showed varying melting enthalpies due to FC over a broad temperature range.
FC extent decreased with increasing molecular weight and increased with higher polydispersity.

Conclusions:

FC is a significant factor affecting the thermal properties of P3HT, particularly at lower molecular weights and higher polydispersities.
The study disentangles main-chain and side-chain crystallization effects by examining samples without FC.
Findings provide insights into controlling polymer morphology and properties through crystallization mechanisms.