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The radical chain-growth polymerization mechanism consists of three steps: initiation, propagation, and termination of polymerization. The polymerization initiates when a free radical generated from the radical initiator adds to the unsaturated bond in the monomer. The unpaired electron of the free radical and one π electron in the unsaturated bond creates a σ bond between the free radical and the monomer. As a result, the other π electron in the unsaturated bond converts this species into...
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Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is...
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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired...
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Radicals adjacent to electron-donating groups are called nucleophilic radicals. These radicals readily react with electrophilic alkenes. The SOMO–LUMO interactions are the driving force for the reaction, where the high-energy SOMO of the electron-rich, nucleophilic radicals interacts with the low-energy LUMO of the electron-deficient, electrophilic alkenes. Such SOMO–LUMO interactions are the basis of reactive radical traps, affecting the selectivity in radical reactions. For...
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Radicals adjacent to electron‐withdrawing groups are called electrophilic radicals. These radicals readily react with nucleophilic alkenes. For example, the malonate radical, in which the radical center is flanked by two electron‐withdrawing groups, reacts readily with butyl vinyl ether, which consists of an electron‐donating oxygen substituent. The reaction between electrophilic malonate radical and nucleophilic vinyl ether is favored because the radical has a...
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Temperature Activated Diffusion of Radicals through Ion Implanted Polymers.

Edgar A Wakelin1, Michael J Davies2, Marcela M M Bilek1

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Summary

Plasma immersion ion implantation (PIII) immobilizes biomolecules on polymers by diffusing radicals. A new model accurately predicts radical diffusion, optimizing biomolecule immobilization for various temperatures.

Keywords:
Fickian diffusionPEEKion implantationpolyetheretherketoneradical diffusion

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Area of Science:

  • Materials Science
  • Surface Chemistry
  • Polymer Science

Background:

  • Plasma immersion ion implantation (PIII) is a key technique for surface modification.
  • PIII generates radicals in polymers for biomolecule immobilization.
  • Controlling radical diffusion is crucial for optimizing PIII.

Purpose of the Study:

  • To develop a predictive model for radical diffusion in PIII.
  • To understand and control radical transport for efficient biomolecule immobilization.
  • To optimize PIII parameters for surface functionalization.

Main Methods:

  • Developed a diffusion model based on Fick's second law.
  • Incorporated temperature-dependent diffusion using the Arrhenius relation.
  • Validated the model against experimental data.

Main Results:

  • Determined Arrhenius parameters: D0 = 3.11 × 10⁻¹⁷ m²/s and EA = 0.31 eV.
  • The model accurately predicts radical diffusion to the polymer surface.
  • Established predictions for surface activity lifetime and optimal radical fluence.

Conclusions:

  • The developed model accurately describes radical diffusion during PIII.
  • This model enables optimization of biomolecule immobilization parameters.
  • Facilitates selection of appropriate storage and incubation temperatures for PIII applications.