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Polymer Classification: Crystallinity01:21

Polymer Classification: Crystallinity

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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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Step-Growth Polymerization: Overview01:03

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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...
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Characteristics and Nomenclature of Copolymers01:24

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Copolymers are the products obtained from the polymerization of multiple monomer species. So, in a polymer chain itself, there can be multiple repeating units that come from different monomers. The process of synthesizing a polymer from different monomer species is called copolymerization. When two monomers are involved, the polymer is known as a bipolymer. Polymers with three and four monomers are termed terpolymers and quaterpolymers, respectively. Figure 1 depicts the copolymerization of...
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Anionic Chain-Growth Polymerization: Mechanism01:04

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The mechanism for anionic chain-growth polymerization involves initiation, propagation, and termination steps. In the initiation step, a nucleophilic anion, such as butyl lithium, initiates the polymerization process by attacking the π bond of the vinylic monomer. As a result, a carbanion, stabilized by the electron‐withdrawing group, is generated. The resulting carbanion acts as a Michael donor in the propagation step and attacks the second vinylic monomer, which acts as a Michael...
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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...
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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,...
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Superstructural phase transitions in polymer-grafted nanooctahedra.

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Polymer-grafted nanocrystals enable tunable superlattice structures. Adjusting polymer length and grafting density controls phase transitions in 2D and 3D arrangements, paving the way for advanced materials.

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Area of Science:

  • Materials Science
  • Nanotechnology
  • Polymer Science

Background:

  • Superlattices of nanocrystals show unique properties based on structure.
  • Native ligands on nanocrystals limit their design flexibility.
  • Polymeric ligands offer tunable nanocrystal softness via molecular weight and grafting density.

Purpose of the Study:

  • Investigate phase transitions in polymer-grafted nanooctahedra.
  • Explore the impact of polymer length, nanocrystal size, truncation, and ligand density on superlattice structures.

Main Methods:

  • Experimental investigation of phase transitions in 2D and 3D superlattices.
  • Utilized polymer brush theory and thermodynamic perturbation theory.
  • Supported findings with Monte Carlo simulations.

Main Results:

  • Longer polymers or smaller nanooctahedra induced transitions to hexagonal rotator lattices in 2D.
  • In 3D, increased polymer length drove transitions from Minkowski to BCC and hexagonal close-packed phases.
  • Higher grafting densities facilitated transitions to simple hexagonal phases.

Conclusions:

  • Polymer-grafted anisotropic nanocrystals are versatile building blocks.
  • Hierarchical superstructures and metamaterials with customizable properties can be designed.
  • The study elucidates entropic and enthalpic forces governing these structural transitions.