3. Macromolecules in solution

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24 Terms

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Macromolecules

Large molecules built up by small molecules (monomers), that are covalently linked 

Examples: 

Biological polymers: 

  • Polysaccharides such as starch, cellulose etc.

    • Sugar monomers

  • Lignin

    • Phenolic monomers

Proteins: Not strictly polymers

  • Amino acid monomers

Synthetic polymers:

  • Polyethylene (PE)

  • Polyethylene glycol (PEG)

  • Polyvinylalcohol (PVA)

  • Polystyrene (PS)

  • Polyacrylamide etc.

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What is homopolymer, copolymer, block copolymer and branched homopolymer?

Homopolymer- same type of monomer

Copolymer- alternating monomer

Block copolymer- alternating in block→ making them surface-active 

Branched homopolymer- branching can occur for others

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Polymer size - Hydrodynamic radius

Hydrodynamic radius is obtained from the Stokes-Einstein equation. It describes how diffusion of a particle or polymeric structure depends on its radius.


D= diffusion coefficient [m2/s]

k= Boltzmann constant (J/K)=1.38×10−23 J/K

T= temperature (K)

η=dynamic viscosity of continuous phase [Pa•s]

d=hydrodynamic diameter of particle [m]

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Polymer size - Radius of gyration

 Based on the distance of each monomer unit to the polymer’s center of mass. Used for random coil polymer 


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Debey’s definition of radius of gyration

It is most common one. Distance of every mass to the center of mass. The average distance is rg

rg=average distance

Mi=molar mass 

ri=distance to the center of mass

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Polymer conformation in solutions depends on

  • Interactions with solvent molecules

  • pH

  • Salt 

  • Temperature

  • Interactions with other polymer molecules

Really likes solvent: polymer swell

Doesn’t like it as much: polymer minimises

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Conformation in dilute solutions

Rod: stiff

Double helix: two molecules 

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Flory-Huggins theory

Describes solubility of a polymer and thermodynamics of macromolecular solutions.

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Flory-Huggins parameter (χ)

– 0.1< χ<0.5 ”Good” solvent (molecule swell)

– χ ≈ 0.5 ”θ-solvent” (transition between good and poor solvents) (reduce it bellow to precipitate, increase to allow it dissolve)

– χ > 0.5 ”Poor” solvent (molecule shrink)

– χ >> 0.5 Insoluble

• χ can change with temperature, pH, ionic strength etc.


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Phase behaviour of macromolecule solutions (miscibility, segregative phase separation and associated phase separation)

Polymer 1 and polymer 2 are chemically different 

Miscibility: polymers like the solvent, don’t care about each other 

Segregative phase separation: Polymers don’t like each other but like solvent 

  • The rule for mixtures of non-ionic polymers

Associated phase separation: Polymers like each other better than solvents (e.g polymer could have opposite charges)

  • Polyelectrolytes of opposite charge, proteins-polysaccharides

<p>Polymer 1 and polymer 2 are chemically different&nbsp;</p><p><u>Miscibility</u>: polymers like the solvent, don’t care about each other&nbsp;</p><p><u>Segregative phase separation</u>: Polymers don’t like each other but like solvent&nbsp;</p><ul><li><p><mark data-color="yellow">The rule for mixtures of non-ionic polymers</mark></p></li></ul><p><u>Associated phase separation</u>: Polymers like each other better than solvents (e.g polymer could have opposite charges)</p><ul><li><p>Polyelectrolytes of opposite charge, proteins-polysaccharides</p></li></ul><p></p>
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Applications of macromolecules

• Thickening to increasing viscosity to preferred value and flow properties in liquid formulations. Example: Pharmaceutics, Foods and Paints and coatings

• Stabilization of dispersions

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Rheology

Rheology is the study of the flow and deformation of matter, including liquids, solids, and soft materials, under applied forces or stresses.

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Shear stress

Shear stress is the external force applied parallel to the surface, which causes deformation. 

σ=shear stress [Pa]

F=applied external force [N]

A=cross-sectional area [m2]

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Shear rate

Shear rate 𝛾 is the rate at which strain changes over time, which is the rate of deformation. 

γ=shear rate [1/s]

v=velocity [m/s]

y=distance between moving plates [m]

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Describe viscosity is in pure liquid and solution of polymer

In a pure liquid: friction between molecules

In a solution of polymers: resistance to a deforming flow compared to pure solvent → increase in viscosity

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Dynamic viscosity

γ=shear rate [1/s]

σ=shear stress [Pa]

η=dynamic viscosity [Pa・s=N・s/m2]

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Newtonian flow

• Shear stress proportional to shear rate → viscosity independent of shear rate.

• Low molar mass liquids (water, organic solvent etc.).

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What happens viscosity from flow field is distrub?

Viscosity increase in dispersions arises from disturbances in the flow field

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Non-Newtonian flow

• The viscosity is shear rate dependant.

• Pseudo-plastic flow: The viscosity decreases with increasing shear rate (as known as shear-thinning). For example paint 

• Dilatent flow: The viscosity increases with increasing shear rate. For example wet sand (particle volume fraction increase locally)

• Apparent viscosity


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Herschel-Bulkley flow

• Above the yield stress the system starts to flow.

• Below the yield stress the system appears solid (i.e. gel)

Example: Tooth paste, tomate ketchup 

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Overlap concentration (c*)

The point where solution viscosity increases sharply

with polymer concentration

• c* depends on the volume occupied by polymer in the solution.

– Large volume → lower c*

– Small volume → higher c*

• Note that the volume is 3D!

– i.e. rod-like conformation occupies a large volume


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Relation to overlap concentration (c*) for different concentrations

c correlation to c*

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Thixotropy

Thixotropic fluids are a type of non-Newtonian liquids that exhibit shear thinning during increased shear rate and a slow recovery to the original viscosity after the shear rate is removed.

• Time-dependent viscosity decrease during constant shear

• Obtained with associative thickeners – dissociation and orientation give a decrease in viscosity

• The viscosity is recovered when shearing/deformation stops

• Example: Important for controlling paint viscosity and application

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Associative thickeners

Hydrophobic interaction can play a role in polymer network formation

Surfactant micelles can associate with hydrophobic groups