PMID- 36226549
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20221026
IS  - 1744-6848 (Electronic)
IS  - 1744-683X (Linking)
VI  - 18
IP  - 41
DP  - 2022 Oct 26
TI  - Controlling the anisotropic self-assembly of polybutadiene-grafted silica 
      nanoparticles by tuning three-body interaction forces.
PG  - 8034-8045
LID - 10.1039/d2sm00943a [doi]
AB  - Recently, the significant improvements in polymer composites properties have been 
      mainly attributed to the ability of filler nanoparticles (NPs) to self-assemble 
      into highly anisotropic self-assembled structures. In this work, we investigate 
      the self-assembly of core-shell NPs composed of a silica core grafted with 
      polybutadiene (PB) chains, generating the so-called "hairy" NPs (HNPs), immersed 
      in tetrahydrofuran solvent. While uncoated silica beads aggregate forming uniform 
      compact structures, the presence of a PB shell affects the silica NPs 
      organization to the point that by increasing the polymer density at the corona, 
      they tend to self-assemble into linear chain-like structures. To reproduce the 
      experimental observations, we propose a theoretical model for the two-body that 
      considers the van der Waals attractive energy together with the polymer-induced 
      repulsive steric contribution and includes an additional three-body interaction 
      term. This term arises due to the anisotropic distribution of PB, which increases 
      their concentration near the NPs contact region. The resulting steric repulsion 
      experienced by a third NP approaching the dimer prevents its binding close to the 
      dimer bond and favors the growth of chain-like structures. We find good agreement 
      between the simulated and experimental self-assembled superstructures, confirming 
      that this three-body steric repulsion plays a key role in determining the cluster 
      morphology of these core-shell NPs. The model also shows that further increasing 
      the grafting density leads to low-density gel-like open structures.
FAU - Di Credico, Barbara
AU  - Di Credico B
AUID- ORCID: 0000-0003-0431-0148
AD  - Department of Materials Science, INSTM, University of Milano-Bicocca, Via R. 
      Cozzi, 55, 20125 Milano, Italy. barbara.dicredico@unimib.it.
FAU - Odriozola, Gerardo
AU  - Odriozola G
AUID- ORCID: 0000-0002-0093-2129
AD  - Area de Fisica de Procesos Irreversibles, Division de Ciencias Basicas e 
      Ingenieria, Universidad Autonoma Metropolitana-Azcapotzalco, Av. San Pablo 180, 
      02200 Ciudad de Mexico, Mexico.
FAU - Mascotto, Simone
AU  - Mascotto S
AUID- ORCID: 0000-0002-3503-6391
AD  - Institut fur Anorganische und Angewandte Chemie, Universitat Hamburg, 
      Martin-Luther-King-Platz 6, 20146 Hamburg, Germany.
FAU - Meyer, Andreas
AU  - Meyer A
AD  - Institut fur Physikalische Chemie, Universitat Hamburg, Grindelallee 117, 20146 
      Hamburg, Germany.
FAU - Tripaldi, Laura
AU  - Tripaldi L
AD  - Department of Materials Science, INSTM, University of Milano-Bicocca, Via R. 
      Cozzi, 55, 20125 Milano, Italy. barbara.dicredico@unimib.it.
FAU - Moncho-Jorda, Arturo
AU  - Moncho-Jorda A
AUID- ORCID: 0000-0002-2001-2987
AD  - Institute Carlos I for Theoretical and Computational Physics, Facultad de 
      Ciencias, Universidad de Granada, Campus Fuentenueva S/N, 18071, Granada, Spain. 
      moncho@ugr.es.
AD  - Departamento de Fisica Aplicada, Universidad de Granada, Campus Fuentenueva S/N, 
      18071 Granada, Spain.
LA  - eng
PT  - Journal Article
DEP - 20221026
PL  - England
TA  - Soft Matter
JT  - Soft matter
JID - 101295070
SB  - IM
EDAT- 2022/10/14 06:00
MHDA- 2022/10/14 06:01
CRDT- 2022/10/13 04:23
PHST- 2022/10/14 06:00 [pubmed]
PHST- 2022/10/14 06:01 [medline]
PHST- 2022/10/13 04:23 [entrez]
AID - 10.1039/d2sm00943a [doi]
PST - epublish
SO  - Soft Matter. 2022 Oct 26;18(41):8034-8045. doi: 10.1039/d2sm00943a.