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Related Concept Videos

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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...
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Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...
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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.
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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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Threading-Unthreading Transition of Linear-Ring Polymer Blends in Extensional Flow.

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Adding ring polymers to linear polymers increases viscosity and causes a stress overshoot. This phenomenon is due to a transient threading-unthreading transition of rings within the polymer network, uniquely altering chain elongation mechanisms.

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Area of Science:

  • Polymer physics
  • Rheology
  • Materials science

Background:

  • Ring polymers mixed with linear polymers increase viscosity due to threading.
  • Pure linear and ring polymers do not exhibit stress overshoot in rheology.

Purpose of the Study:

  • Investigate the cause of stress overshoot in linear-ring polymer blends.
  • Understand the role of ring polymers in altering transient polymer elongation.

Main Methods:

  • Uniaxial extensional rheology measurements
  • Ex-situ small-angle neutron scattering
  • Nonequilibrium molecular dynamics simulations

Main Results:

  • Linear-ring blends show a stress overshoot in extensional rheology.
  • This overshoot is driven by a transient threading-unthreading of rings.
  • Rings deform affinely and enhance linear chain elongation before unthreading.

Conclusions:

  • Ring polymers uniquely modify the transient elongation mechanisms of linear polymers.
  • The threading-unthreading transition is key to the observed rheological behavior.