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Polymer Classification: Crystallinity01:21

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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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Polymers: Molecular Weight Distribution01:10

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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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Polymers: Defining Molecular Weight01:01

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Unlike small molecules with definite molecular weights, polymers are a mixture of individual polymer chains of varying lengths, each with a unique molecular weight.  So, the molecular weight of a polymer is expressed as an average value based on the average size of the polymer chains. The two most common forms of averages used for polymers are the number average molecular weight and weight average molecular weight.
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Molecular Weight of Step-Growth Polymers01:08

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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...
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Polymer Classification: Architecture01:14

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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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Polymers02:34

Polymers

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The word polymer is derived from the Greek words “poly” which means “many” and “mer” which means “parts”. Polymers are long chains of molecules composed of repeating units of smaller molecules, known as monomers. They either occur naturally, such as DNA and proteins, or can be constructed synthetically, like plastics. They have varied structural characteristics, such as linear chains, branched chains, or complex networks, that contribute to the...
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Resolving Dynamic Properties of Polymers through Coarse-Grained Computational Studies.

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Atomistic detail is crucial for accurately modeling polymer dynamics and viscoelastic properties. This study reveals the optimal coarse-graining scale for capturing long-time polymer behavior in polyethylene melts.

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Area of Science:

  • Polymer Science
  • Computational Chemistry
  • Materials Science

Background:

  • Polymer dynamics and viscoelastic properties are governed by coupled length and time scales.
  • Accurately modeling long-time dynamics requires understanding the necessary time and length scales for simulation.
  • Determining the appropriate degree of coarse-graining is essential for bridging atomistic detail with large-scale phenomena.

Purpose of the Study:

  • To investigate the impact of coarse-graining scale on polymer dynamics.
  • To determine the minimum length scale required for accurate modeling of polymer properties.
  • To assess the retention of atomistic details while accessing large length and time scales in polymer simulations.

Main Methods:

  • Utilized linear polyethylene as a model system.
  • Employed Iterative Boltzmann Inversion to derive coarse-grained potentials.
  • Simulated polyethylene melts with varying coarse-graining levels (2-6 methylene groups per bead) from atomistic data.
  • Performed simulations reaching over 500 microseconds to capture long-time dynamics.

Main Results:

  • Demonstrated that atomistic detail is critical for capturing large-scale polymer dynamics.
  • Showcased how the degree of coarse-graining influences measured polymer dynamics.
  • Established a link between coarse-graining scale and the minimum length scale relevant to polymer properties.

Conclusions:

  • Coarse-graining scale significantly affects the accuracy of simulated polymer dynamics.
  • Retaining sufficient atomistic detail is paramount for modeling the viscoelastic properties of entangled polymer melts.
  • The findings provide guidance on selecting appropriate coarse-graining strategies for polymer simulations.