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Related Concept Videos

Characteristics and Nomenclature of Copolymers01:24

Characteristics and Nomenclature of Copolymers

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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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Polymers: Molecular Weight Distribution01:10

Polymers: Molecular Weight Distribution

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For any given polymer, the weight average molecular weight (Mw) is higher than, if not equal to, the number average molecular weight (Mn). The only situation in which the weight average molecular weight and the number average molecular weight are equal is when a polymer consists only of chains with equal molecular weight. However, this never happens in a synthetic polymer, since it is difficult to control the polymerization process up to a molecular level with accuracy to a hundred percent.
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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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Radical Chain-Growth Polymerization: Chain Branching01:17

Radical Chain-Growth Polymerization: Chain Branching

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The skeletal structure of polymers synthesized via radical polymerization is always branched. For example, the polymerization of ethylene by radical polymerization results in a low-density grade of polyethylene with a heavily branched skeletal structure. Here, the radical site abstracts hydrogen from the growing chain, and the radical site shifts from the end (a primary carbon center) to anywhere within the growing chain (a secondary carbon center). Consequently, the part of the chain from the...
2.0K
Molecular Weight of Step-Growth Polymers01:08

Molecular Weight of Step-Growth Polymers

2.3K
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...
2.3K
Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

2.4K
The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the...
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Synthesis of Monodisperse Cylindrical Nanoparticles via Crystallization-driven Self-assembly of Biodegradable Block Copolymers
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Not Even Metastable: Cubic Double-Diamond in Diblock Copolymer Melts.

Michael S Dimitriyev1,2, Benjamin R Greenvall2, Rejoy Mathew2

  • 1Department of Materials Science & Engineering, Texas A&M University, College Station, Texas 77843, United States.

ACS Macro Letters
|August 27, 2025
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Block copolymer melts transform between double-gyroid and double-diamond network phases. The double-diamond phase is unstable, readily deforming into the lower-energy double-gyroid phase.

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

  • Materials Science
  • Polymer Physics
  • Thermodynamics

Background:

  • Block copolymer melts exhibit complex morphologies, including cubic network phases.
  • The double-gyroid and double-diamond structures are key examples of these morphologies.
  • Understanding the phase transformations is crucial for materials design.

Purpose of the Study:

  • Investigate the thermodynamics of continuous transformations between double-gyroid and double-diamond network phases in block copolymer melts.
  • Determine the stability and interconversion pathways of these cubic network morphologies.
  • Identify factors influencing the stability of the double-diamond phase.

Main Methods:

  • Employed a strong-segregation approach to compute free energy landscapes.
  • Utilized structural parameters to map transformations between cubic phases.
  • Performed self-consistent field studies to confirm phase stability at finite segregation.

Main Results:

  • The cubic double-diamond phase is an unstable saddle point, continuously deformable into the more stable double-gyroid phase.
  • Instability of the double-diamond phase arises from entropic free energy costs of chain packing in tetrahedral nodes.
  • Homopolymer blending and elastic asymmetry can stabilize the double-diamond phase into a metastable state.

Conclusions:

  • The double-diamond network morphology is thermodynamically unstable in symmetric diblock melts.
  • Entropic effects related to chain packing are critical for the stability of network phases.
  • Strategies like homopolymer blending can be used to access metastable double-diamond structures.