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. Thus, we explore 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; however, decreased forwardmore »
- Authors:
-
[1];
[1];
[1];
[1]
- Louisiana State Univ., Baton Rouge, LA (United States)
- Australian Centre for Neutron Scattering, NSW (Australia)
- Publication Date:
- Research Org.:
- Louisiana State Univ., 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
- 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
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. Thus, we explore 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; however, 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 = {2019},
month = {12}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 1 work
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Cylindrical molecular brushes: Synthesis, characterization, and properties
journal, July 2008
- Sheiko, Sergei S.; Sumerlin, Brent S.; Matyjaszewski, Krzysztof
- Progress in Polymer Science, Vol. 33, Issue 7
Star shaped polymers : a model for the conformation and its concentration dependence
journal, January 1982
- Daoud, M.; Cotton, J. P.
- Journal de Physique, Vol. 43, Issue 3
Theory and simulation studies of effective interactions, phase behavior and morphology in polymer nanocomposites
journal, January 2014
- Ganesan, Venkat; Jayaraman, Arthi
- Soft Matter, Vol. 10, Issue 1
Depletion and cluster formation in soft colloid - polymer mixtures
journal, November 2005
- Stiakakis, E.; Petekidis, G.; Vlassopoulos, D.
- Europhysics Letters (EPL), Vol. 72, Issue 4
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
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
Polymer-Mediated Melting in Ultrasoft Colloidal Gels
journal, October 2002
- Stiakakis, E.; Vlassopoulos, D.; Likos, C. N.
- Physical Review Letters, Vol. 89, Issue 20
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
‘Quokka’—the small-angle neutron scattering instrument at OPAL
journal, November 2006
- Gilbert, Elliot P.; Schulz, Jamie C.; Noakes, Terry J.
- Physica B: Condensed Matter, Vol. 385-386
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
Polymer Chain Conformation and Dynamical Confinement in a Model One-Component Nanocomposite
journal, July 2017
- Mark, C.; Holderer, O.; Allgaier, J.
- Physical Review Letters, Vol. 119, Issue 4
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
Structural Observation and Kinetic Pathway in the Formation of Polymeric Micelles
journal, May 2009
- Lund, Reidar; Willner, Lutz; Monkenbusch, Michael
- Physical Review Letters, Vol. 102, Issue 18
Dilute solution structure of bottlebrush polymers
journal, January 2019
- Dutta, Sarit; Wade, Matthew A.; Walsh, Dylan J.
- Soft Matter, Vol. 15, Issue 14
Structure of PAMAM Dendrimers: Generations 1 through 11
journal, August 2004
- Maiti, Prabal K.; Çaǧın, Tahir; Wang, Guofeng
- Macromolecules, Vol. 37, Issue 16
Effective interactions in soft condensed matter physics
journal, July 2001
- Likos, Christos N.
- Physics Reports, Vol. 348, Issue 4-5
Utility of trichloroisocyanuric acid in the efficient chlorination of silicon hydrides
journal, April 2007
- Varaprath, Sudarsanan; Stutts, Debra H.
- Journal of Organometallic Chemistry, Vol. 692, Issue 10
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
The anomalous structure factor of dense star polymer solutions
journal, September 1998
- Watzlawek, M.; Löwen, H.; Likos, C. N.
- Journal of Physics: Condensed Matter, Vol. 10, Issue 37
Cationic polymerization of 1,3,5,7 tetramethylcyclotetrasiloxane initiated by trifluoromethanesulphonic acid
journal, January 1993
- Gupta, Sarveshwar Prasad; Moreau, Michel; Masure, Michèle
- European Polymer Journal, Vol. 29, Issue 1
Dispersing hairy nanoparticles in polymer melts
journal, December 2008
- Wang, Xiaorong; Foltz, Victor J.; Rackaitis, Mindaugas
- Polymer, Vol. 49, Issue 26
Highly Entangled α-Olefin Molecular Bottlebrushes: Melt Structure, Linear Rheology, and Interchain Friction Mechanism
journal, August 2018
- López-Barrón, Carlos R.; Tsou, Andy H.; Hagadorn, John R.
- Macromolecules, Vol. 51, Issue 17
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
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
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
Star Polymers
journal, June 2016
- Ren, Jing M.; McKenzie, Thomas G.; Fu, Qiang
- Chemical Reviews, Vol. 116, Issue 12
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
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
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
Molecular brushes as super-soft elastomers
journal, September 2006
- Pakula, Tadeusz; Zhang, Ying; Matyjaszewski, Krzysztof
- Polymer, Vol. 47, Issue 20
Conformation of branched polymers
journal, January 1981
- Daoud, M.; Joanny, J. F.
- Journal de Physique, Vol. 42, Issue 10
Dynamic phase diagram of soft nanocolloids
journal, January 2015
- Gupta, Sudipta; Camargo, Manuel; Stellbrink, Jörg
- Nanoscale, Vol. 7, Issue 33
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
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
Miktoarm Stars via Grafting-Through Copolymerization: Self-Assembly and the Star-to-Bottlebrush Transition
journal, February 2019
- Levi, Adam E.; Lequieu, Joshua; Horne, Jacob D.
- Macromolecules, Vol. 52, Issue 4
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
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
Linear Rheology of Polyolefin-Based Bottlebrush Polymers
journal, June 2015
- Dalsin, Samuel J.; Hillmyer, Marc A.; Bates, Frank S.
- Macromolecules, Vol. 48, Issue 13
Ultrasoft Colloid-Polymer Mixtures: Structure and Phase Diagram
journal, May 2011
- Lonetti, B.; Camargo, M.; Stellbrink, J.
- Physical Review Letters, Vol. 106, Issue 22
Small-Angle Scattering from Polymeric Mass Fractals of Arbitrary Mass-Fractal Dimension
journal, April 1996
- Beaucage, G.
- Journal of Applied Crystallography, Vol. 29, Issue 2
Anionic polymerization: High vacuum techniques
journal, January 2000
- Hadjichristidis, Nikos; Iatrou, Hermis; Pispas, Stergios
- Journal of Polymer Science Part A: Polymer Chemistry, Vol. 38, Issue 18
Linear and Extensional Rheology of Model Branched Polystyrenes: From Loosely Grafted Combs to Bottlebrushes
journal, July 2017
- Abbasi, Mahdi; Faust, Lorenz; Riazi, Kamran
- Macromolecules, Vol. 50, Issue 15
A Coarse-Grained Description of Star−Linear Polymer Mixtures
journal, February 2007
- Mayer, Christian; Likos, Christos N.
- Macromolecules, Vol. 40, Issue 4
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
Clustering of soft colloids due to polymer additives
journal, October 2005
- Likos, C. N.; Mayer, C.; Stiakakis, E.
- Journal of Physics: Condensed Matter, Vol. 17, Issue 45
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
Star Polymers Viewed as Ultrasoft Colloidal Particles
journal, May 1998
- Likos, C. N.; Löwen, H.; Watzlawek, M.
- Physical Review Letters, Vol. 80, Issue 20
Hierarchical excluded volume screening in solutions of bottlebrush polymers
journal, January 2017
- Paturej, Jarosław; Kreer, Torsten
- Soft Matter, Vol. 13, Issue 45
Reduction and analysis of SANS and USANS data using IGOR Pro
journal, November 2006
- Kline, Steven R.
- Journal of Applied Crystallography, Vol. 39, Issue 6, p. 895-900
Effective interactions between star polymers and colloidal particles
journal, June 2001
- Jusufi, A.; Dzubiella, J.; Likos, C. N.
- Journal of Physics: Condensed Matter, Vol. 13, Issue 28
Phase separation in star-linear polymer mixtures
journal, May 2009
- Camargo, Manuel; Likos, Christos N.
- The Journal of Chemical Physics, Vol. 130, Issue 20
A Small-Angle Neutron Scattering Study of a Soft Model Nanofiller in an Athermal Melt
journal, June 2017
- Rizk, M.; Krutyeva, M.; Lühmann, N.
- Macromolecules, Vol. 50, Issue 12
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
Bottle-brush polymers as an intermediate between star and cylindrical polymers
journal, September 2003
- Denesyuk, N. A.
- Physical Review E, Vol. 68, Issue 3
Influence of Architecture on Arm Dimensions and Interaction Parameters in Polybutadiene Star Polymers
journal, February 1999
- Richards, R. W.
- Macromolecules, Vol. 32, Issue 3
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
Soft matter with soft particles
journal, January 2006
- Likos, Christos N.
- Soft Matter, Vol. 2, Issue 6
Molecular structure of bottlebrush polymers in melts
journal, November 2016
- Paturej, Jarosław; Sheiko, Sergei S.; Panyukov, Sergey
- Science Advances, Vol. 2, Issue 11
Computer Simulations of Bottle Brushes: From Melts to Soft Networks
journal, July 2015
- Cao, Zhen; Carrillo, Jan-Michael Y.; Sheiko, Sergei S.
- Macromolecules, Vol. 48, Issue 14
Molecular dynamics simulations of single-component bottle-brush polymers with flexible backbones under poor solvent conditions
journal, June 2013
- Fytas, Nikolaos G.; Theodorakis, Panagiotis E.
- Journal of Physics: Condensed Matter, Vol. 25, Issue 28
Osmotic shrinkage in star/linear polymer mixtures
journal, June 2010
- Wilk, A.; Huißmann, S.; Stiakakis, E.
- The European Physical Journal E, Vol. 32, Issue 2
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
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
Analysis of small-angle scattering data from colloids and polymer solutions: modeling and least-squares fitting
journal, July 1997
- Pedersen, Jan Skov
- Advances in Colloid and Interface Science, Vol. 70