DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Structural Analysis of Ultrasoft PDMS-g-PDMS Shell-Only Particles

Abstract

We have used anionic polymerization to synthesize polymers of linear and bottlebrush architecture each with a polydimethylsiloxane backbone. The blending of polymer architectures has the effect of changing material properties, e.g., the viscoelasticity, which are connected to the chain conformation. Hence, we investigate the conformation of bottlebrush polymers in a linear host melt both as a function of the concentration and for various molecular weights of the linear host matrices. Our bottlebrush polymers are seen as shell-only particles with a negligible core size. We find a substantial influence of the molecular weight of the linear matrices on the structure of the bottlebrushes and their interactions. In samples with a low molecular weight matrix that have the same degree of polymerization as the side chains, the bottlebrush behavior is consistent with an effective theta solvent condition for all concentrations. With increasing molecular weight of the host matrix, this condition is only reached at the highest concentration of the bottlebrush polymers. The increase of the molecular weight of the host matrix leads to a shrinkage of the bottlebrushes and subsequently to a formation of clusters at higher volume fractions. None of the scattering patterns show a pronounced correlation peak; yet, decreased forwardmore » scattering associated with a structure factor effect is observed.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Louisiana State Univ., Baton Rouge, LA (United States)
  2. Australian Centre for Neutron Scattering, NSW (Australia)
Publication Date:
Research Org.:
Louisiana State Univ., Baton Rouge, LA (United States); Louisiana State University, Baton Rouge, LA, United States
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
U.S. Department of Energy (DoE) under EPSCoR Grant No. DE-SC0012432 ANSTO for access to the QUOKKA SANS instrument through proposal grant P6515 and FRMII for access to the KWSII SANS instrument.
OSTI Identifier:
1605743
Alternate Identifier(s):
OSTI ID: 1677408; OSTI ID: 1773791; OSTI ID: 2271664
Grant/Contract Number:  
SC0012432; SC0019050
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 53; Journal Issue: 1; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 36 MATERIALS SCIENCE; Star polymers; Scattering Polymer; particles; Chemical structure; Polymers; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Star polymers, Scattering, Polymer particles, Chemical structure, Polymers; SANS, neutron scattering, small-angle neutron scattering, bottlebrush; Bottlebrush; Shell-only particle; Colloid-cluster transition; Osmotic shrinkage

Citation Formats

Bichler, Karin J., Jakobi, Bruno, Huber, Stefan O., Gilbert, Elliot P., and Schneider, Gerald J. Structural Analysis of Ultrasoft PDMS-g-PDMS Shell-Only Particles. United States: N. p., 2019. Web. doi:10.1021/acs.macromol.9b01598.
Bichler, Karin J., Jakobi, Bruno, Huber, Stefan O., Gilbert, Elliot P., & Schneider, Gerald J. Structural Analysis of Ultrasoft PDMS-g-PDMS Shell-Only Particles. United States. https://doi.org/10.1021/acs.macromol.9b01598
Bichler, Karin J., Jakobi, Bruno, Huber, Stefan O., Gilbert, Elliot P., and Schneider, Gerald J. Mon . "Structural Analysis of Ultrasoft PDMS-g-PDMS Shell-Only Particles". United States. https://doi.org/10.1021/acs.macromol.9b01598. https://www.osti.gov/servlets/purl/1605743.
@article{osti_1605743,
title = {Structural Analysis of Ultrasoft PDMS-g-PDMS Shell-Only Particles},
author = {Bichler, Karin J. and Jakobi, Bruno and Huber, Stefan O. and Gilbert, Elliot P. and Schneider, Gerald J.},
abstractNote = {We have used anionic polymerization to synthesize polymers of linear and bottlebrush architecture each with a polydimethylsiloxane backbone. The blending of polymer architectures has the effect of changing material properties, e.g., the viscoelasticity, which are connected to the chain conformation. Hence, we investigate the conformation of bottlebrush polymers in a linear host melt both as a function of the concentration and for various molecular weights of the linear host matrices. Our bottlebrush polymers are seen as shell-only particles with a negligible core size. We find a substantial influence of the molecular weight of the linear matrices on the structure of the bottlebrushes and their interactions. In samples with a low molecular weight matrix that have the same degree of polymerization as the side chains, the bottlebrush behavior is consistent with an effective theta solvent condition for all concentrations. With increasing molecular weight of the host matrix, this condition is only reached at the highest concentration of the bottlebrush polymers. The increase of the molecular weight of the host matrix leads to a shrinkage of the bottlebrushes and subsequently to a formation of clusters at higher volume fractions. None of the scattering patterns show a pronounced correlation peak; yet, decreased forward scattering associated with a structure factor effect is observed.},
doi = {10.1021/acs.macromol.9b01598},
journal = {Macromolecules},
number = 1,
volume = 53,
place = {United States},
year = {Mon Dec 16 00:00:00 EST 2019},
month = {Mon Dec 16 00:00:00 EST 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Cylindrical molecular brushes: Synthesis, characterization, and properties
journal, July 2008


Star shaped polymers : a model for the conformation and its concentration dependence
journal, January 1982


Theory and simulation studies of effective interactions, phase behavior and morphology in polymer nanocomposites
journal, January 2014


Depletion and cluster formation in soft colloid - polymer mixtures
journal, November 2005


Conformation of Cyclics and Linear Chain Polymers in Bulk by SANS
journal, October 2004

  • Arrighi, V.; Gagliardi, S.; Dagger, A. C.
  • Macromolecules, Vol. 37, Issue 21
  • DOI: 10.1021/ma049565w

Synthesis of Isocyanate-Based Brush Block Copolymers and Their Rapid Self-Assembly to Infrared-Reflecting Photonic Crystals
journal, August 2012

  • Miyake, Garret M.; Weitekamp, Raymond A.; Piunova, Victoria A.
  • Journal of the American Chemical Society, Vol. 134, Issue 34
  • DOI: 10.1021/ja306430k

Polymer-Mediated Melting in Ultrasoft Colloidal Gels
journal, October 2002


Solvent-free, supersoft and superelastic bottlebrush melts and networks
journal, November 2015

  • Daniel, William F. M.; Burdyńska, Joanna; Vatankhah-Varnoosfaderani, Mohammad
  • Nature Materials, Vol. 15, Issue 2
  • DOI: 10.1038/nmat4508

‘Quokka’—the small-angle neutron scattering instrument at OPAL
journal, November 2006


End grafted polymernanoparticles in a polymeric matrix: Effect of coverage and curvature
journal, January 2011

  • Kalb, Joshua; Dukes, Douglas; Kumar, Sanat K.
  • Soft Matter, Vol. 7, Issue 4
  • DOI: 10.1039/C0SM00725K

Polymer Chain Conformation and Dynamical Confinement in a Model One-Component Nanocomposite
journal, July 2017


QUOKKA, the pinhole small-angle neutron scattering instrument at the OPAL Research Reactor, Australia: design, performance, operation and scientific highlights
journal, March 2018

  • Wood, Kathleen; Mata, Jitendra P.; Garvey, Christopher J.
  • Journal of Applied Crystallography, Vol. 51, Issue 2
  • DOI: 10.1107/S1600576718002534

Dilute solution structure of bottlebrush polymers
journal, January 2019

  • Dutta, Sarit; Wade, Matthew A.; Walsh, Dylan J.
  • Soft Matter, Vol. 15, Issue 14
  • DOI: 10.1039/C9SM00033J

Structure of PAMAM Dendrimers:  Generations 1 through 11
journal, August 2004

  • Maiti, Prabal K.; Çaǧın, Tahir; Wang, Guofeng
  • Macromolecules, Vol. 37, Issue 16
  • DOI: 10.1021/ma035629b

Effective interactions in soft condensed matter physics
journal, July 2001


Utility of trichloroisocyanuric acid in the efficient chlorination of silicon hydrides
journal, April 2007


Exploiting scaling laws for designing polymeric bottle brushes: a theoretical coarse-graining for homopolymeric branched polymers
journal, January 2019

  • Corsi, Pietro; Roma, Elia; Gasperi, Tecla
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 27
  • DOI: 10.1039/C9CP01316D

The anomalous structure factor of dense star polymer solutions
journal, September 1998


Cationic polymerization of 1,3,5,7 tetramethylcyclotetrasiloxane initiated by trifluoromethanesulphonic acid
journal, January 1993


Dispersing hairy nanoparticles in polymer melts
journal, December 2008


Highly Entangled α-Olefin Molecular Bottlebrushes: Melt Structure, Linear Rheology, and Interchain Friction Mechanism
journal, August 2018


Structural and thermodynamic aspects of the cylinder-to-sphere transition in amphiphilic diblock copolymer micelles
journal, January 2011

  • Lund, Reidar; Pipich, Vitaliy; Willner, Lutz
  • Soft Matter, Vol. 7, Issue 4
  • DOI: 10.1039/c0sm00894j

Polymer dynamics under soft confinement in a self-assembled system
journal, January 2010

  • Willner, Lutz; Lund, Reidar; Monkenbusch, Michael.
  • Soft Matter, Vol. 6, Issue 7
  • DOI: 10.1039/b922649d

Small-Angle Neutron Scattering Analysis of Bottlebrush Polymers Prepared via Grafting-Through Polymerization
journal, August 2013

  • Pesek, Stacy L.; Li, Xianyu; Hammouda, Boualem
  • Macromolecules, Vol. 46, Issue 17
  • DOI: 10.1021/ma401246b

Star Polymers
journal, June 2016


Structure, surface excess and effective interactions in polymer nanocomposite melts and concentrated solutions
journal, October 2004

  • Hooper, J. B.; Schweizer, K. S.; Desai, T. G.
  • The Journal of Chemical Physics, Vol. 121, Issue 14
  • DOI: 10.1063/1.1790831

Linear rheology and structure of molecular bottlebrushes with short side chains
journal, May 2015

  • López-Barrón, Carlos R.; Brant, Patrick; Eberle, Aaron P. R.
  • Journal of Rheology, Vol. 59, Issue 3
  • DOI: 10.1122/1.4918977

Small-angle neutron scattering analysis of bottlebrush backbone and side chain flexibility
journal, October 2016

  • Pesek, Stacy L.; Xiang, Qiqi; Hammouda, Boualem
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 55, Issue 1
  • DOI: 10.1002/polb.24251

Molecular brushes as super-soft elastomers
journal, September 2006


Conformation of branched polymers
journal, January 1981


Dynamic phase diagram of soft nanocolloids
journal, January 2015

  • Gupta, Sudipta; Camargo, Manuel; Stellbrink, Jörg
  • Nanoscale, Vol. 7, Issue 33
  • DOI: 10.1039/C5NR03702F

Effects of Core Microstructure on Structure and Dynamics of Star Polymer Melts: From Polymeric to Colloidal Response
journal, July 2014

  • Snijkers, Frank; Cho, Hong Y.; Nese, Alper
  • Macromolecules, Vol. 47, Issue 15
  • DOI: 10.1021/ma5008336

Colloidal nature of star polymer dilute and semidilute solutions
journal, May 1991

  • Dozier, William D.; Huang, John S.; Fetters, Lewis J.
  • Macromolecules, Vol. 24, Issue 10
  • DOI: 10.1021/ma00010a026

Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition
journal, February 2019


Precisely Tunable Photonic Crystals From Rapidly Self-Assembling Brush Block Copolymer Blends
journal, September 2012

  • Miyake, Garret M.; Piunova, Victoria A.; Weitekamp, Raymond A.
  • Angewandte Chemie International Edition, Vol. 51, Issue 45, p. 11246-11248
  • DOI: 10.1002/anie.201205743

Effect of Chain Stiffness on Nanoparticle Segregation in Polymer/Nanoparticle Blends Near a Substrate
journal, October 2011

  • Padmanabhan, Venkat; Frischknecht, Amalie L.; Mackay, Michael E.
  • Macromolecular Theory and Simulations, Vol. 21, Issue 2
  • DOI: 10.1002/mats.201100048

Linear Rheology of Polyolefin-Based Bottlebrush Polymers
journal, June 2015


Ultrasoft Colloid-Polymer Mixtures: Structure and Phase Diagram
journal, May 2011


Small-Angle Scattering from Polymeric Mass Fractals of Arbitrary Mass-Fractal Dimension
journal, April 1996


Anionic polymerization: High vacuum techniques
journal, January 2000


Linear and Extensional Rheology of Model Branched Polystyrenes: From Loosely Grafted Combs to Bottlebrushes
journal, July 2017


Unusual Features of Depletion Interactions in Soft Polymer-Based Colloids Mixed with Linear Homopolymers
journal, February 2010


A Coarse-Grained Description of Star−Linear Polymer Mixtures
journal, February 2007

  • Mayer, Christian; Likos, Christos N.
  • Macromolecules, Vol. 40, Issue 4
  • DOI: 10.1021/ma062117z

On the shape of bottle-brush macromolecules: Systematic variation of architectural parameters
journal, March 2005

  • Rathgeber, Silke; Pakula, Tadeusz; Wilk, Agnieszka
  • The Journal of Chemical Physics, Vol. 122, Issue 12
  • DOI: 10.1063/1.1860531

Clustering of soft colloids due to polymer additives
journal, October 2005


Controlled Anionic Polymerization of Hexamethylcyclotrisiloxane. Model Linear and Miktoarm Star Co- and Terpolymers of Dimethylsiloxane with Styrene and Isoprene
journal, September 2000

  • Bellas, Vasilios; Iatrou, Hermis; Hadjichristidis, Nikos
  • Macromolecules, Vol. 33, Issue 19
  • DOI: 10.1021/ma000635i

Star Polymers Viewed as Ultrasoft Colloidal Particles
journal, May 1998


Hierarchical excluded volume screening in solutions of bottlebrush polymers
journal, January 2017

  • Paturej, Jarosław; Kreer, Torsten
  • Soft Matter, Vol. 13, Issue 45
  • DOI: 10.1039/C7SM01968H

Reduction and analysis of SANS and USANS data using IGOR Pro
journal, November 2006


Effective interactions between star polymers and colloidal particles
journal, June 2001


Phase separation in star-linear polymer mixtures
journal, May 2009

  • Camargo, Manuel; Likos, Christos N.
  • The Journal of Chemical Physics, Vol. 130, Issue 20
  • DOI: 10.1063/1.3141983

A Small-Angle Neutron Scattering Study of a Soft Model Nanofiller in an Athermal Melt
journal, June 2017


Cluster formation in star-linear polymer mixtures: equilibrium and dynamical properties
journal, January 2012

  • Camargo, Manuel; Egorov, Sergei A.; Likos, Christos N.
  • Soft Matter, Vol. 8, Issue 15
  • DOI: 10.1039/c2sm06849d

Bottle-brush polymers as an intermediate between star and cylindrical polymers
journal, September 2003


Influence of Architecture on Arm Dimensions and Interaction Parameters in Polybutadiene Star Polymers
journal, February 1999


Investigation of the conformation of elastic chains in poly(dimethylsiloxane) networks by small-angle neutron scattering
journal, November 1982

  • Beltzung, M.; Picot, Claude; Rempp, P.
  • Macromolecules, Vol. 15, Issue 6
  • DOI: 10.1021/ma00234a026

Molecular structure of bottlebrush polymers in melts
journal, November 2016

  • Paturej, Jarosław; Sheiko, Sergei S.; Panyukov, Sergey
  • Science Advances, Vol. 2, Issue 11
  • DOI: 10.1126/sciadv.1601478

Computer Simulations of Bottle Brushes: From Melts to Soft Networks
journal, July 2015


Molecular dynamics simulations of single-component bottle-brush polymers with flexible backbones under poor solvent conditions
journal, June 2013


Osmotic shrinkage in star/linear polymer mixtures
journal, June 2010


Interaction of cylindrical polymer brushes in dilute and semi-dilute solution
journal, December 2008

  • Bolisetty, Sreenath; Rosenfeldt, Sabine; Rochette, Christophe N.
  • Colloid and Polymer Science, Vol. 287, Issue 2
  • DOI: 10.1007/s00396-008-1962-3

Colloidal star polymers: Models for studying dynamically arrested states in soft matter
journal, January 2004

  • Vlassopoulos, Dimitris
  • Journal of Polymer Science Part B: Polymer Physics, Vol. 42, Issue 16
  • DOI: 10.1002/polb.20152

Analysis of small-angle scattering data from colloids and polymer solutions: modeling and least-squares fitting
journal, July 1997