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Layer-By-Layer Self-Assembly of Polyelectrolytic Block Copolymer Worms on a Planar Substrate
Nicholas J W Penfold1, Andrew J Parnell2, Marta Molina1
1Department of Chemistry, The University of Sheffield, Dainton Building , Brook Hill, Sheffield S3 7HF, U.K.
Langmuir : the ACS Journal of Surfaces and Colloids
|November 18, 2017
Summary
Cationic and anionic block copolymer worms were synthesized using reversible addition-fragmentation chain transfer (RAFT) polymerization. These self-assembled worms exhibit rapid adsorption and layer-by-layer deposition, mimicking polyelectrolyte behavior.
Area of Science:
- Polymer Chemistry
- Materials Science
- Nanotechnology
Background:
- Block copolymers are versatile materials for self-assembly.
- Controlled polymerization techniques like RAFT enable precise polymer synthesis.
- Understanding self-assembly of charged polymers is crucial for advanced material design.
Purpose of the Study:
- To synthesize cationic and anionic block copolymer worms.
- To investigate their self-assembly and surface adsorption properties.
- To explore layer-by-layer deposition for surface modification.
Main Methods:
- Reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion copolymerization.
- Polymerization-induced self-assembly of block copolymers.
- Covalent stabilization of worm cores using silane chemistry.
- Aqueous electrophoresis, scanning electron microscopy (SEM), ellipsometry, and surface zeta potential measurements.
Main Results:
- Successfully synthesized cationic and anionic block copolymer worms with stable zeta potentials (+40 mV and -39 mV).
- Demonstrated rapid adsorption kinetics of cationic worms onto anionic surfaces, achieving significant coverage in seconds.
- Confirmed successful layer-by-layer deposition of oppositely charged worms, leading to monotonic thickness increase and surface charge reversal.
- Observed two distinct linear regimes in layer thickness growth during layer-by-layer assembly.
Conclusions:
- The synthesized block copolymer worms effectively mimic rigid polyelectrolyte chains.
- These worms offer a versatile platform for rapid surface functionalization and controlled layer-by-layer assembly.
- The observed distinct regimes in layer growth suggest complex interfacial interactions during multilayer formation.
