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Related Concept Videos

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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Anionic Chain-Growth Polymerization: Mechanism01:04

Anionic Chain-Growth Polymerization: Mechanism

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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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Polymer Classification: Stereospecificity01:26

Polymer Classification: Stereospecificity

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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...
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Shearing Strain01:20

Shearing Strain

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The shearing strain represents a cubic element's angular change when subjected to shearing stress. This type of stress can transform a cube into an oblique parallelepiped without influencing normal strains. The cubic element experiences a significant transformation when exposed solely to shearing stress. Its shape alters from a perfect cube into a rhomboid, clearly demonstrating the effect of shearing strain. The degree of this strain is considered positive if it reduces the angle between...
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Cationic Chain-Growth Polymerization: Mechanism00:57

Cationic Chain-Growth Polymerization: Mechanism

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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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Shearing Stress01:19

Shearing Stress

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Shearing stress, denoted by the Greek letter tau (τ), is stress caused by forces acting transversely on an object. These forces create internal ones within the entity in the plane where the external forces are applied. The resultant of these internal forces is the shear in the section.
The average shearing stress can be calculated by dividing the shear by the area of the cross-section.
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Measuring Material Microstructure Under Flow Using 1-2 Plane Flow-Small Angle Neutron Scattering
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Shear Banding in Telechelic Associative Polymers by Molecular Dynamics.

J Castillo-Tejas1, S Carro1, O Manero2

  • 1Facultad de Ciencias Básicas, Ingeniería y Tecnología, Universidad Autónoma de Tlaxcala, Apizaco, Tlaxcala 90300, México.

ACS Macro Letters
|June 2, 2022
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Summary

Nonequilibrium molecular dynamics simulations reveal that increasing hydrophobic interactions in telechelic associative polymers induces non-monotonic stress-shear rate behavior, leading to steady banding flow. This phenomenon arises from micellar aggregate instability and migration.

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Area of Science:

  • Polymer Physics
  • Rheology
  • Computational Materials Science

Background:

  • Telechelic associative polymers exhibit complex flow behavior due to reversible cross-linking.
  • Understanding shear flow is crucial for predicting material properties and processing.
  • Previous studies have explored shear-induced phenomena, but direct simulation of banding flow in these systems is limited.

Purpose of the Study:

  • To investigate the shear flow of telechelic associative polymers using nonequilibrium molecular dynamics (NEMD).
  • To elucidate the mechanism behind the emergence of steady banding flow.
  • To establish a predictive simulation framework for associative polymer rheology.

Main Methods:

  • Nonequilibrium molecular dynamics (NEMD) simulations were employed.
  • A novel approach was developed to calculate particle stream velocities from peculiar velocities and imposed profiles.
  • The effect of varying interaction forces between hydrophobic sites was systematically studied.

Main Results:

  • A non-monotonic relationship between stress and shear rate was observed upon increasing hydrophobic interactions.
  • Steady banding flow was predicted and characterized.
  • The banding flow was linked to local instabilities from micellar aggregate breakage and migration to low-velocity gradient regions.

Conclusions:

  • NEMD simulations successfully predict the banding flow of telechelic associative polymers.
  • Hydrophobic interactions play a critical role in inducing non-Newtonian rheological behavior.
  • The findings provide fundamental insights into shear-induced phase separation and flow instabilities in associative polymers.