Structural Rheology in the Development and Study of Complex Polymer Materials
Abstract
:1. Introduction
2. Rheological Approaches to the Study of Polymer Materials
2.1. Viscosity
2.2. Linear Viscoelasticity
2.3. Nonlinear Viscoelasticity
3. Complex Chain Structure and Its Manifestation in the Polymer Structuring
3.1. Microphase Separation of Block Copolymer Melts
3.2. Microphase Separation of a Multiblock Copolymer Melt
3.3. Macromolecular Association in a Multiblock Copolymer Solution
4. Specific Interactions in Polymer Solutions and Their Structuring
4.1. Supramolecular Structuring of a Random Copolymer’s Dilute Solution
4.2. Microscopic Phase Separation of a Random Copolymer’s Concentrated Solution
4.3. Microscopic Phase Separation of a Homopolymer Solution
4.4. Macromolecular Association and Mesophase Structuring of a Polyelectrolyte Solution
4.5. Structuring of Polymer Solution Due to Conformational Transition
4.6. Microscopic Phase Separation during Cooling of a Polymer Solution
4.7. Microscopic Phase Separation during Heating and Intense Shear of a Polymer Solution
4.8. Phase Separation Initiated by Intense Shear
4.9. Element Sizes in Structuralized Polymer Solutions
5. Specific Interactions in Polymer Dispersions
5.1. Structure Formation in a Dilute Mix of Particle Dispersion and Polymer Solution
5.2. Structure Suppression in a Concentrated Mix of Particle Dispersion and Polymer Solution
5.3. Effect of Dispersed Particles on the Structure and Rheology of Polymer Gels
5.4. Effect of Dispersed Particles on Structure and Rheology of Polymer Melt
5.5. Effects of Medium’s Molecular Weight and Particles’ Size on the Rheology of Dispersions
5.6. Structuring of Dispersions of Polymer Particles
6. Complex Chain Architecture and Its Manifestation in Rheological Properties
6.1. Reflection of Long-Chain Polymer Branching in Elasticity Arising at Flow
6.2. Reflection of Long-Chain Polymer Branching in Linear Viscoelasticity
6.3. Cross-Linked Macromolecular Particles and the Rheology of Their Dispersions
6.4. Highly Branched Macromolecular Particles and Their Blends with Linear Chains
7. Structured Polymer Materials
7.1. Composite Pressure-Sensitive Adhesives
7.2. Asphaltenes as Tackifiers for Hot-Melt Adhesives
7.3. Cellulose Membranes for Nanofiltration
7.4. Ion- and Proton-Exchange Polyoxadiazole Membranes
7.5. Nanocellulose Oleogels as Lubricating Greases
7.6. Greases Based on Cellulose Acetate Butyrate
8. Conclusions
- Growth of chain branching raises the viscosity and, even more so, the elasticity of the polymer melt and ultimately leads to limited miscibility with linear chains of similar monomer structure because of the increases in glass transition temperature, entanglement density, and enthalpy contribution into miscibility.
- Highly branched macromolecular particles, unlike ordinary colloid particles, may be miscible with low- and high-molecular-weight media but, unlike chain macromolecules, do not exhibit a rubbery-like state, and their viscoelasticity is due to glass transition rather than a physical network of entanglements.
- Linear chains are much more willing to dissolve small isomonomer molecules of highly branched architecture within themselves than dissolve in them. As a result, linear chains form a dispersion medium even with an excess of highly branched macromolecules, leading to abnormally low viscosity of the arising emulsion at specific temperatures.
- Large highly branched macromolecules more easily dissolve isomonomer linear chains than dissolve within them. At a moderate excess of the linear chains, this specific feature can lead to the formation of extremely high-viscosity concentrated emulsions of the linear polymer in a glass-forming highly branched dispersion medium.
- A mixing of miscible polymers, one of which has high flow activation energy and glass transition temperature while the other has low, is a way to reduce the viscosity of their melts for the purpose of intensifying their processing.
- Specific interchain and supramolecular interactions in polymer solutions and melts lead to structure formation, i.e., to yield stress and solid-like behavior—the gel formation. However, the dominance of macromolecular entanglements in determining rheological properties may mask these interactions that become evident only at long observation times.
- Large-amplitude oscillatory shear may lead to phase separation of polymer solutions, which is unattainable via continuous shear due to the Weissenberg effect.
- Dispersed particles act as adsorption sites for macromolecules, sharply increasing their apparent molecular weight and competing with macromolecular entanglements for the right to determine the rheological properties: a particle coagulation network or a macromolecular entanglement network. Decreases in the particles’ volume fraction and specific surface area and an increase in the polymer’s molecular weight induce a transition from the first extreme to the other.
- The transition from micro- to nanostructures for organizing macromolecules and improving applied properties is unreasonable, as their structuring operates on a microscopic scale in contrast to the unstructured nanoscale state of their dilute solutions. However, the passage from micro- to nanoparticles as modifiers of polymer media has the sense to reduce the particle doses necessary for chain adsorption and the formation of an interphase polymer layer with enhanced properties.
- The properties of applied polymer materials (adhesives, greases, membranes, etc.) depend on the structure of their precursors—polymer melts, solutions, and gels, which can undergo structural–rheological analysis for subsequent targeted modification of the composition and characteristics of the final materials.
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Ilyin, S.O. Structural Rheology in the Development and Study of Complex Polymer Materials. Polymers 2024, 16, 2458. https://doi.org/10.3390/polym16172458
Ilyin SO. Structural Rheology in the Development and Study of Complex Polymer Materials. Polymers. 2024; 16(17):2458. https://doi.org/10.3390/polym16172458
Chicago/Turabian StyleIlyin, Sergey O. 2024. "Structural Rheology in the Development and Study of Complex Polymer Materials" Polymers 16, no. 17: 2458. https://doi.org/10.3390/polym16172458