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Related Concept Videos

Polymer Classification: Crystallinity01:21

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...
Step-Growth Polymerization: Overview01:03

Step-Growth Polymerization: Overview

Step-growth or condensation polymerization is a stepwise reaction of bi or multifunctional monomers to form long-chain polymers. As all the monomers are reactive, most of the monomers are consumed at the early stages of the reaction to form small chains of reactive oligomers, which then combine to form long polymer chains in the late stages. Hence, the reaction has to proceed for a long time to achieve high molecular weight polymers.
Many natural and synthetic polymers are produced by...
Crystal Growth: Principles of Crystallization01:25

Crystal Growth: Principles of Crystallization

Crystallization is a phase transformation process in which crystals are precipitated from a supersaturated solution or formed from other sources. During crystallization, atoms or molecules arrange themselves into a well-defined, rigid crystal lattice to minimize energy.
Initiating crystallization involves manipulating the concentration of the solute and the temperature of the solution. Since crystal growth occurs when the ratio of concentration and solubility of the solute in the solvent – the...
Anionic Chain-Growth Polymerization: Overview01:20

Anionic Chain-Growth Polymerization: Overview

The polymerization process that involves carbanion as an intermediate is called anionic polymerization. It is also a type of addition or chain-growth polymerization. Anionic polymerization gets initiated by a strong nucleophile such as an organolithium or a Grignard reagent. The most commonly used initiator for anionic polymerization is butyl lithium. Monomers involved in anionic polymerization must possess a vinyl group bonded to one or two electron-withdrawing groups. For instance,...
Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
As the step-growth polymerization involves step-wise condensation of monomers, the molecular weight also builds up eventually. Consequently, high molecular weight polymers are obtained at the late stages of the polymerization, where 99% of monomers have been consumed.
The extent of the...
Ziegler–Natta Chain-Growth Polymerization: Overview01:17

Ziegler–Natta Chain-Growth Polymerization: Overview

Ziegler–Natta polymerization is another form of addition or chain‐growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler–Natta catalyst, high molecular...

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Continuum theory of polymer crystallization.

Arindam Kundagrami1, M Muthukumar

  • 1Department of Polymer Science and Engineering, University of Massachusetts at Amherst, Amherst, Massachusetts 01003, USA.

The Journal of Chemical Physics
|April 21, 2007
PubMed
Summary

This study unifies polymer crystallization into a single kinetic model, explaining both nucleation and diffusion control. It highlights the role of entropic factors in polymer crystal growth across various conditions.

Area of Science:

  • Materials Science
  • Physical Chemistry
  • Polymer Science

Background:

  • Polymer crystallization is broadly classified into two kinetic regimes: nucleation-controlled (high molar mass) and diffusion-controlled (low molar mass).
  • Existing models often treat these regimes separately, lacking a unified theoretical framework.

Purpose of the Study:

  • To develop a unified kinetic model for polymer crystal growth applicable to both melts and solutions.
  • To incorporate entropic barrier theory and account for polymer chain accumulation at the growth front.
  • To investigate the influence of molecular weight and concentration on crystallization dynamics.

Main Methods:

  • Development of a kinetic model for polymer crystallization of finite molecular weight.
  • Numerical calculation of single crystal growth in dilute solutions.

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  • Inclusion of entropic barrier theory and conventional polymer dynamics.

    • Main Results:

    • The model successfully unifies nucleation-controlled and diffusion-controlled crystallization regimes.
    • It explains the observed growth rate dependencies on supercooling (G ~ exp(1/TΔT) and G ~ ΔT).
    • The theory demonstrates that entropic considerations are crucial for understanding polymer crystallization trends.

    Conclusions:

    • A single theoretical framework can describe diverse polymer crystallization phenomena.
    • Entropic factors, alongside energetic arguments, provide a comprehensive understanding of polymer crystal growth.
    • The model offers unifying insights into crystallization processes for both small molecules and flexible polymer chains.