Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers

Mah, Adeline Huizhen; Laws, Travis; Li, Wei; Mei, Hao; Brown, Chance C.; Ievlev, Anton; Kumar, Rajeev; Verduzco, Rafael; Stein, Gila E.

doi:10.1021/acs.macromol.8b02242

Title: Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers

Abstract

We present a combined experimental and computational study of surface segregation in thin films of nearly athermal blends of linear and bottlebrush polymers. The lengths of bottlebrush backbone (N_b), bottlebrush side chain (N_sc), and linear polystyrene host (N_m) are systematically varied to examine the effects of polymer architecture on phase behavior. From the experiments, combinations of architectural parameters are identified that produce enrichment and depletion of bottlebrush at the polymer–air interface. These surface segregation behaviors are consistent with entropy-dominated thermodynamics. In addition, the experiments reveal conditions where bottlebrush and linear polymers are equally preferred at the surface. Simulations based on the self-consistent field theory (SCFT) qualitatively capture the three types of surface segregation behaviors and highlight the delicate interplay of entropic and enthalpic effects. Finally, our investigations demonstrate that controlling both entropic and enthalpic driving forces is critical for the design of surface-active bottlebrush polymer additives.

Authors:

Mah, Adeline Huizhen ^[1]; Laws, Travis ^[2];

^[3]; Mei, Hao ^[4]; Brown, Chance C. ^[3];

^[3];

^[5];

^[6];

^[2]

Univ. of Houston, Houston, TX (United States). Materials Science and Engineering Program and Dept. of Chemical and Biomolecular Engineering
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS), and Computational Chemical and Materials Sciences
Rice Univ., Houston, TX (United States). Dept. of Chemical and Biomolecular Engineering, Dept. of Materials Science and NanoEngineering

Publication Date:: Wed Feb 06 00:00:00 EST 2019

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1494878

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: Macromolecules

Additional Journal Information:: Journal Volume: 52; Journal Issue: 4; Journal ID: ISSN 0024-9297

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Mah, Adeline Huizhen, Laws, Travis, Li, Wei, Mei, Hao, Brown, Chance C., Ievlev, Anton, Kumar, Rajeev, Verduzco, Rafael, and Stein, Gila E. Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers.  United States: N. p., 2019. 
Web.  doi:10.1021/acs.macromol.8b02242.

Copy to clipboard


                    Mah, Adeline Huizhen, Laws, Travis, Li, Wei, Mei, Hao, Brown, Chance C., Ievlev, Anton, Kumar, Rajeev, Verduzco, Rafael, & Stein, Gila E. Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers.  United States.  https://doi.org/10.1021/acs.macromol.8b02242

Copy to clipboard


                    Mah, Adeline Huizhen, Laws, Travis, Li, Wei, Mei, Hao, Brown, Chance C., Ievlev, Anton, Kumar, Rajeev, Verduzco, Rafael, and Stein, Gila E. Wed .  
"Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers".  United States.  https://doi.org/10.1021/acs.macromol.8b02242.  https://www.osti.gov/servlets/purl/1494878.

Copy to clipboard


                    
@article{osti_1494878,

  title        = {Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers},

  author       = {Mah, Adeline Huizhen and Laws, Travis and Li, Wei and Mei, Hao and Brown, Chance C. and Ievlev, Anton and Kumar, Rajeev and Verduzco, Rafael and Stein, Gila E.},

  abstractNote = {We present a combined experimental and computational study of surface segregation in thin films of nearly athermal blends of linear and bottlebrush polymers. The lengths of bottlebrush backbone (Nb), bottlebrush side chain (Nsc), and linear polystyrene host (Nm) are systematically varied to examine the effects of polymer architecture on phase behavior. From the experiments, combinations of architectural parameters are identified that produce enrichment and depletion of bottlebrush at the polymer–air interface. These surface segregation behaviors are consistent with entropy-dominated thermodynamics. In addition, the experiments reveal conditions where bottlebrush and linear polymers are equally preferred at the surface. Simulations based on the self-consistent field theory (SCFT) qualitatively capture the three types of surface segregation behaviors and highlight the delicate interplay of entropic and enthalpic effects. Finally, our investigations demonstrate that controlling both entropic and enthalpic driving forces is critical for the design of surface-active bottlebrush polymer additives.},

  doi          = {10.1021/acs.macromol.8b02242},

  journal      = {Macromolecules},

  number       = 4,

  volume       = 52,

  place        = {United States},

  year         = {Wed Feb 06 00:00:00 EST 2019},

  month        = {Wed Feb 06 00:00:00 EST 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acs.macromol.8b02242

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 30 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Molecular design of functional polymer surfaces
journal, January 2004

Koberstein, Jeffrey T.
Journal of Polymer Science Part B: Polymer Physics, Vol. 42, Issue 16
DOI: 10.1002/polb.20157

Multi-End-Functionalized Polymers: Additives to Modify Polymer Properties at Surfaces and Interfaces
journal, March 2007

Narrainen, Amilcar Pillay; Hutchings, Lian R.; Ansari, Imtiyaz
Macromolecules, Vol. 40, Issue 6
DOI: 10.1021/ma062349y

Synthesis of bottlebrush copolymers based on poly(dimethylsiloxane) for surface active additives
journal, August 2016

Pesek, Stacy L.; Lin, Yen-Hao; Mah, Hui Zhen
Polymer, Vol. 98
DOI: 10.1016/j.polymer.2016.01.057

A lattice model for the surface segregation of polymer chains due to molecular weight effects
journal, July 1990

Hariharan, Arvind; Kumar, Sanat K.; Russell, Thomas P.
Macromolecules, Vol. 23, Issue 15
DOI: 10.1021/ma00217a009

Detection of Surface Enrichment Driven by Molecular Weight Disparity in Virtually Monodisperse Polymers
journal, March 2018

Hill, Jacob A.; Endres, Kevin J.; Mahmoudi, Pendar
ACS Macro Letters, Vol. 7, Issue 4
DOI: 10.1021/acsmacrolett.7b00993

Distribution of chain ends at the surface of a polymer melt: Compensation effects and surface tension
journal, December 1995

Wu, David T.; Fredrickson, Glenn H.; Carton, Jean-Pierre
Journal of Polymer Science Part B: Polymer Physics, Vol. 33, Issue 17
DOI: 10.1002/polb.1995.090331709

Free surfaces of polymer blends. I. Theoretical framework and application to symmetric polymer blends
journal, April 1993

Hariharan, Arvind; Kumar, Sanat K.; Russell, Thomas P.
The Journal of Chemical Physics, Vol. 98, Issue 8
DOI: 10.1063/1.464792

Entropically driven segregation in blends of branched and linear polymers
journal, September 1996

Walton, D. G.; Mayes, A. M.
Physical Review E, Vol. 54, Issue 3
DOI: 10.1103/PhysRevE.54.2811

Entropic Attraction of Polymers toward Surfaces and Its Relationship to Surface Tension
journal, October 2006

Minnikanti, Venkatachala S.; Archer, Lynden A.
Macromolecules, Vol. 39, Issue 22
DOI: 10.1021/ma061377d

Surface Tension of Symmetric Star Polymer Melts
journal, July 2008

Qian, Zhenyu; Minnikanti, Venkatachala S.; Sauer, Bryan B.
Macromolecules, Vol. 41, Issue 13
DOI: 10.1021/ma8002888

Surface tension of polystyrene blends: Theory and experiment
journal, September 2009

Qian, Zhenyu; Minnikanti, Venkatachala S.; Sauer, Bryan B.
Journal of Polymer Science Part B: Polymer Physics, Vol. 47, Issue 17
DOI: 10.1002/polb.21771

Surface migration of branched molecules: Analysis of energetic and entropic factors
journal, October 2005

Minnikanti, Venkatachala S.; Archer, Lynden A.
The Journal of Chemical Physics, Vol. 123, Issue 14
DOI: 10.1063/1.2052627

Surface enrichment of branched polymers in linear hosts: Effect of asymmetry in intersegmental interactions and density gradients
journal, February 2005

Minnikanti, Venkatachala S.; Archer, Lynden A.
The Journal of Chemical Physics, Vol. 122, Issue 8
DOI: 10.1063/1.1850452

Effect of Architecture in the Surface Segregation of Polymer Blends
journal, January 1996

Wu, David T.; Fredrickson, Glenn H.
Macromolecules, Vol. 29, Issue 24
DOI: 10.1021/ma9602278

Effectiveχ and surface segregation in blends of star and linear polystyrene
journal, January 2000

Foster, Mark D.; Greenberg, Carmen C.; Teale, David M.
Macromolecular Symposia, Vol. 149, Issue 1
DOI: 10.1002/1521-3900(200001)149:1<263::AID-MASY263>3.0.CO;2-0

Surface segregation driven by molecular architecture asymmetry in polymer blends
journal, November 2014

Lee, Jae Sik; Lee, Nam-Heui; Peri, Somesh
Physical Review Letters, Vol. 113, Issue 22
DOI: 10.1103/PhysRevLett.113.225702

Surfactant-induced lyotropic behavior of flexible polymer solutions
journal, May 1993

Fredrickson, Glenn H.
Macromolecules, Vol. 26, Issue 11
DOI: 10.1021/ma00063a029

Influence of broken conformational symmetry on the surface enrichment of polymer blends
journal, December 1992

Fredrickson, Glenn H.; Donley, James P.
The Journal of Chemical Physics, Vol. 97, Issue 12
DOI: 10.1063/1.463969

Entropic Corrections to the Flory-Huggins Theory of Polymer Blends: Architectural and Conformational Effects
journal, April 1994

Fredrickson, Glenn H.; Liu, Andrea J.; Bates, Frank S.
Macromolecules, Vol. 27, Issue 9
DOI: 10.1021/ma00087a019

Microphase separation in thin films of lamellar forming polydisperse di-block copolymers
journal, January 2015

Kumar, Rajeev; Lokitz, Bradley S.; Sides, Scott W.
RSC Advances, Vol. 5, Issue 27
DOI: 10.1039/C5RA00974J

Drug-Loaded, Bivalent-Bottle-Brush Polymers by Graft-through ROMP
journal, December 2010

Johnson, Jeremiah A.; Lu, Ying Y.; Burts, Alan O.
Macromolecules, Vol. 43, Issue 24
DOI: 10.1021/ma1021506

pH-Sensitive brush polymer-drug conjugates by ring-opening metathesis copolymerization
journal, January 2011

Zou, Jiong; Jafr, Goran; Themistou, Efrosyni
Chemical Communications, Vol. 47, Issue 15
DOI: 10.1039/c0cc05531j

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

Broad-wavelength-range chemically tunable block-copolymer photonic gels
journal, October 2007

Kang, Youngjong; Walish, Joseph J.; Gorishnyy, Taras
Nature Materials, Vol. 6, Issue 12
DOI: 10.1038/nmat2032

Bioinspired Bottle-Brush Polymer Exhibits Low Friction and Amontons-like Behavior
journal, April 2014

Banquy, Xavier; Burdyńska, Joanna; Lee, Dong Woog
Journal of the American Chemical Society, Vol. 136, Issue 17
DOI: 10.1021/ja501770y

Unraveling the Correlations between Conformation, Lubrication, and Chemical Stability of Bottlebrush Polymers at Interfaces
journal, October 2017

Faivre, Jimmy; Shrestha, Buddha Ratna; Xie, Guojun
Biomacromolecules, Vol. 18, Issue 12
DOI: 10.1021/acs.biomac.7b01063

Surface Properties of Bottlebrush Polymer Thin Films
journal, August 2012

Li, Xianyu; Prukop, Stacy L.; Biswal, Sibani Lisa
Macromolecules, Vol. 45, Issue 17
DOI: 10.1021/ma301046n

Creation of Stable Poly(ethylene oxide) Surfaces on Poly(methyl methacrylate) Using Blends of Branched and Linear Polymers
journal, November 1997

Walton, D. G.; Soo, P. P.; Mayes, A. M.
Macromolecules, Vol. 30, Issue 22
DOI: 10.1021/ma970698+

Thin Film Phase Behavior of Bottlebrush/Linear Polymer Blends
journal, July 2014

Mitra, Indranil; Li, Xianyu; Pesek, Stacy L.
Macromolecules, Vol. 47, Issue 15
DOI: 10.1021/ma501070w

Boundary-induced segregation in nanoscale thin films of athermal polymer blends
journal, January 2016

Teng, Chih-Yu; Sheng, Yu-Jane; Tsao, Heng-Kwong
Soft Matter, Vol. 12, Issue 20
DOI: 10.1039/C6SM00559D

Effect of Butadiene End-Capping of Arms in a Star Polystyrene on Solution Properties, Bulk Dynamics, and Bulk Thermodynamic Interactions in Binary Blends
journal, December 2004

Lee, Jae S.; Quirk, Roderic P.; Foster, Mark D.
Macromolecules, Vol. 37, Issue 26
DOI: 10.1021/ma048758g

Effects of Branch Points and Chain Ends on the Thermodynamic Interaction Parameter in Binary Blends of Regularly Branched and Linear Polymers
journal, July 2006

Lee, Jae S.; Foster, Mark D.; Wu, David T.
Macromolecules, Vol. 39, Issue 15
DOI: 10.1021/ma060023j

Surface Enrichment in an Isotopic Polymer Blend
journal, January 1989

Jones, Richard A. L.; Kramer, Edward J.; Rafailovich, Miriam H.
Physical Review Letters, Vol. 62, Issue 3
DOI: 10.1103/PhysRevLett.62.280

Facile syntheses of cylindrical molecular brushes by a sequential RAFT and ROMP “grafting-through” methodology
journal, October 2009

Li, Zhou; Zhang, Ke; Ma, Jun
Journal of Polymer Science Part A: Polymer Chemistry, Vol. 47, Issue 20
DOI: 10.1002/pola.23626

A Versatile Precursor for the Synthesis of New Ruthenium Olefin Metathesis Catalysts
journal, December 2001

Sanford, Melanie S.; Love, Jennifer A.; Grubbs, Robert H.
Organometallics, Vol. 20, Issue 25
DOI: 10.1021/om010599r

Generating thickness gradients of thin polymer films via flow coating
journal, February 2006

Stafford, Christopher M.; Roskov, Kristen E.; Epps, Thomas H.
Review of Scientific Instruments, Vol. 77, Issue 2
DOI: 10.1063/1.2173072

Improving Brush Polymer Infrared One-Dimensional Photonic Crystals via Linear Polymer Additives
journal, December 2014

Macfarlane, Robert J.; Kim, Bongkeun; Lee, Byeongdu
Journal of the American Chemical Society, Vol. 136, Issue 50
DOI: 10.1021/ja5093562

Bottlebrush Block Polymers: Quantitative Theory and Experiments
journal, October 2015

Dalsin, Samuel J.; Rions-Maehren, Thomas G.; Beam, Marissa D.
ACS Nano, Vol. 9, Issue 12
DOI: 10.1021/acsnano.5b05473

Isotope-Induced Quantum-Phase Transitions in the Liquid State
journal, September 1986

Bates, F. S.; Wignall, G. D.
Physical Review Letters, Vol. 57, Issue 12
DOI: 10.1103/PhysRevLett.57.1429

Thin films of block copolymer
journal, May 1997

Matsen, M. W.
The Journal of Chemical Physics, Vol. 106, Issue 18
DOI: 10.1063/1.473778

Defectivity in Laterally Confined Lamella-Forming Diblock Copolymers: Thermodynamic and Kinetic Aspects
journal, July 2012

Takahashi, Hassei; Laachi, Nabil; Delaney, Kris T.
Macromolecules, Vol. 45, Issue 15
DOI: 10.1021/ma300993x

Dispersing Nanoparticles in a Polymer Film via Solvent Evaporation
journal, May 2016

Cheng, Shengfeng; Grest, Gary S.
ACS Macro Letters, Vol. 5, Issue 6
DOI: 10.1021/acsmacrolett.6b00263

Surface and Interfacial Segregation in Blends of Polystyrene with Functional End Groups and Deuterated Polystyrene
journal, June 2007

Kawaguchi, Daisuke; Tanaka, Keiji; Torikai, Naoya
Langmuir, Vol. 23, Issue 13
DOI: 10.1021/la700418j

Works referencing / citing this record:

The influence of curvature on domain distribution in binary mixture membranes
journal, January 2019

Li, Wei; Carrillo, Jan-Michael Y.; Katsaras, John
Soft Matter, Vol. 15, Issue 33
DOI: 10.1039/c9sm01262a

Similar Records in DOE PAGES and OSTI.GOV collections:

Understanding interfacial segregation in polymer blend films with random and mixed side chain bottlebrush copolymer additives

Journal Article Mei, Hao ; Mahalik, Jyoti P. ; Lee, Dongjoo ; ... - Soft Matter

Bottlebrush polymers are complex macromolecules with tunable physical properties dependent on the chemistry and architecture of both the side chains and the backbone. Prior work has demonstrated that bottlebrush polymer additives can be used to control the interfacial properties of blends with linear polymers but has not specifically addressed the effects of bottlebrush side chain microstructures. Here, using a combination of experiments and self-consistent field theory (SCFT) simulations, we investigated the effects of side chain microstructures by comparing the segregation of bottlebrush additives having random copolymer side chains with bottlebrush additives having a mixture of two different homopolymer side chainmore »« less
https://doi.org/10.1039/d1sm01146d

Full Text Available
Entropy and Enthalpy Mediated Segregation of Bottlebrush Copolymers to Interfaces

Journal Article Mei, Hao ; Laws, Travis S. ; Mahalik, Jyoti P. ; ... - Macromolecules

The composition of polymer blends near interfaces can differ from the average blend composition because the attraction of each polymer toward surfaces is controlled by its chemistry, size, and architecture. In this work, we studied thin film blends of bottlebrush copolymers and linear homopolymers to understand the enthalpic and entropic effects that drive preferential segregation of one constituent to film interfaces. Bottlebrush copolymers containing polystyrene (PS) and poly(methyl methacrylate) (PMMA) side chains were blended with either linear PS or linear PMMA, and time-of-flight secondary ion mass spectroscopy was used to quantify the distribution of bottlebrushes through the film thickness asmore »« less
Cited by 19
https://doi.org/10.1021/acs.macromol.9b01801

Full Text Available
Effects of Grafting Density on Block Polymer Self-Assembly: From Linear to Bottlebrush

Journal Article Lin, Tzu-Pin ; Chang, Alice B. ; Luo, Shao-Xiong ; ... - ACS Nano

Grafting density is an important structural parameter that imparts significant influences over the physical properties of architecturally complex polymers. In this paper, the physical consequences of varying the grafting density (z) were studied in the context of block polymer self-assembly. Well-defined block polymers spanning the linear, comb, and bottlebrush regimes (0 ≤ z ≤ 1) were prepared via grafting-through ring-opening-metathesis polymerization (ROMP). ω-norbornenyl poly(D,L-lactide) (PLA) and polystyrene (PS) macromonomers were copolymerized with discrete co-monomers in different feed ratios, enabling precise control over the grafting density. Small-angle X-ray scattering (SAXS) experiments demonstrate that these graft block polymers can self-assemble into long-range-orderedmore »« less
Cited by 74
https://doi.org/10.1021/acsnano.7b06664

Full Text Available
Bottlebrush Block Polymers: Quantitative Theory and Experiments

Journal Article Dalsin, Samuel J. ; Rions-Maehren, Thomas G. ; Beam, Marissa D. ; ... - ACS Nano

The self-assembly of bottlebrush block polymers into a lamellar phase was investigated using a combination of experiment and self-consistent field theory (SCFT). Nine diblock bottlebrush polymers were synthesized with atactic polypropylene side chains (block A) and polystyrene side chains (block B) attached to poly(norbornene) backbones of various contour lengths, L, and the resulting lamellar structures were analyzed using small-angle X-ray scattering. The scaling of the lamellar period, d0 ~ Lγ, exhibited an increasing exponent from γ ≈ 0.3 at small L to γ ≈ 0.9 at large L. The small exponents occurred for starlike molecules where the size of themore »« less
Cited by 128
https://doi.org/10.1021/acsnano.5b05473
Self-Assembly of Flexible Linear–Semiflexible Bottlebrush–Flexible Linear Triblock Copolymers

Journal Article Nian, Shifeng ; Fan, Zhouhao ; Freychet, Guillaume ; ... - Macromolecules

Block copolymer (BCP) self-assembly is a fundamental process in which incompatible blocks spontaneously form organized microstructures with broad practical applications. Classical understanding is that the domain spacing is limited by the contour length of the polymer backbone. Here, using a combination of molecular design, chemical synthesis, small-/wide-angle X-ray scattering, transmission electron microscopy, and electron tomography, we discover that this molecular picture does not hold for architecturally semiflexible BCPs. For strongly segregated linear–semiflexible bottlebrush–linear triblock copolymers, the size of the bottlebrush domain can be twice the bottlebrush backbone contour length. The mechanism of such anomalous self-assembly is likely that the interfacialmore »« less
https://doi.org/10.1021/acs.macromol.1c01911

Full Text Available

Similar Records

Title: Entropic and Enthalpic Effects in Thin Film Blends of Homopolymers and Bottlebrush Polymers

Abstract

Citation Formats

Molecular design of functional polymer surfaces journal, January 2004

Multi-End-Functionalized Polymers: Additives to Modify Polymer Properties at Surfaces and Interfaces journal, March 2007

Synthesis of bottlebrush copolymers based on poly(dimethylsiloxane) for surface active additives journal, August 2016

A lattice model for the surface segregation of polymer chains due to molecular weight effects journal, July 1990

Detection of Surface Enrichment Driven by Molecular Weight Disparity in Virtually Monodisperse Polymers journal, March 2018

Distribution of chain ends at the surface of a polymer melt: Compensation effects and surface tension journal, December 1995

Free surfaces of polymer blends. I. Theoretical framework and application to symmetric polymer blends journal, April 1993

Entropically driven segregation in blends of branched and linear polymers journal, September 1996

Entropic Attraction of Polymers toward Surfaces and Its Relationship to Surface Tension journal, October 2006

Surface Tension of Symmetric Star Polymer Melts journal, July 2008

Surface tension of polystyrene blends: Theory and experiment journal, September 2009

Surface migration of branched molecules: Analysis of energetic and entropic factors journal, October 2005

Surface enrichment of branched polymers in linear hosts: Effect of asymmetry in intersegmental interactions and density gradients journal, February 2005

Effect of Architecture in the Surface Segregation of Polymer Blends journal, January 1996

Effectiveχ and surface segregation in blends of star and linear polystyrene journal, January 2000

Surface segregation driven by molecular architecture asymmetry in polymer blends journal, November 2014

Surfactant-induced lyotropic behavior of flexible polymer solutions journal, May 1993

Influence of broken conformational symmetry on the surface enrichment of polymer blends journal, December 1992

Entropic Corrections to the Flory-Huggins Theory of Polymer Blends: Architectural and Conformational Effects journal, April 1994

Microphase separation in thin films of lamellar forming polydisperse di-block copolymers journal, January 2015

Drug-Loaded, Bivalent-Bottle-Brush Polymers by Graft-through ROMP journal, December 2010

pH-Sensitive brush polymer-drug conjugates by ring-opening metathesis copolymerization journal, January 2011

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

Broad-wavelength-range chemically tunable block-copolymer photonic gels journal, October 2007

Bioinspired Bottle-Brush Polymer Exhibits Low Friction and Amontons-like Behavior journal, April 2014

Unraveling the Correlations between Conformation, Lubrication, and Chemical Stability of Bottlebrush Polymers at Interfaces journal, October 2017

Surface Properties of Bottlebrush Polymer Thin Films journal, August 2012

Creation of Stable Poly(ethylene oxide) Surfaces on Poly(methyl methacrylate) Using Blends of Branched and Linear Polymers journal, November 1997

Thin Film Phase Behavior of Bottlebrush/Linear Polymer Blends journal, July 2014

Boundary-induced segregation in nanoscale thin films of athermal polymer blends journal, January 2016

Effect of Butadiene End-Capping of Arms in a Star Polystyrene on Solution Properties, Bulk Dynamics, and Bulk Thermodynamic Interactions in Binary Blends journal, December 2004

Effects of Branch Points and Chain Ends on the Thermodynamic Interaction Parameter in Binary Blends of Regularly Branched and Linear Polymers journal, July 2006

Surface Enrichment in an Isotopic Polymer Blend journal, January 1989

Facile syntheses of cylindrical molecular brushes by a sequential RAFT and ROMP “grafting-through” methodology journal, October 2009

A Versatile Precursor for the Synthesis of New Ruthenium Olefin Metathesis Catalysts journal, December 2001

Generating thickness gradients of thin polymer films via flow coating journal, February 2006

Improving Brush Polymer Infrared One-Dimensional Photonic Crystals via Linear Polymer Additives journal, December 2014

Bottlebrush Block Polymers: Quantitative Theory and Experiments journal, October 2015

Isotope-Induced Quantum-Phase Transitions in the Liquid State journal, September 1986

Thin films of block copolymer journal, May 1997

Defectivity in Laterally Confined Lamella-Forming Diblock Copolymers: Thermodynamic and Kinetic Aspects journal, July 2012

Dispersing Nanoparticles in a Polymer Film via Solvent Evaporation journal, May 2016

Surface and Interfacial Segregation in Blends of Polystyrene with Functional End Groups and Deuterated Polystyrene journal, June 2007

The influence of curvature on domain distribution in binary mixture membranes journal, January 2019

Molecular design of functional polymer surfaces
journal, January 2004

Multi-End-Functionalized Polymers: Additives to Modify Polymer Properties at Surfaces and Interfaces
journal, March 2007

Synthesis of bottlebrush copolymers based on poly(dimethylsiloxane) for surface active additives
journal, August 2016

A lattice model for the surface segregation of polymer chains due to molecular weight effects
journal, July 1990

Detection of Surface Enrichment Driven by Molecular Weight Disparity in Virtually Monodisperse Polymers
journal, March 2018

Distribution of chain ends at the surface of a polymer melt: Compensation effects and surface tension
journal, December 1995

Free surfaces of polymer blends. I. Theoretical framework and application to symmetric polymer blends
journal, April 1993

Entropically driven segregation in blends of branched and linear polymers
journal, September 1996

Entropic Attraction of Polymers toward Surfaces and Its Relationship to Surface Tension
journal, October 2006

Surface Tension of Symmetric Star Polymer Melts
journal, July 2008

Surface tension of polystyrene blends: Theory and experiment
journal, September 2009

Surface migration of branched molecules: Analysis of energetic and entropic factors
journal, October 2005

Surface enrichment of branched polymers in linear hosts: Effect of asymmetry in intersegmental interactions and density gradients
journal, February 2005

Effect of Architecture in the Surface Segregation of Polymer Blends
journal, January 1996

Effectiveχ and surface segregation in blends of star and linear polystyrene
journal, January 2000

Surface segregation driven by molecular architecture asymmetry in polymer blends
journal, November 2014

Surfactant-induced lyotropic behavior of flexible polymer solutions
journal, May 1993

Influence of broken conformational symmetry on the surface enrichment of polymer blends
journal, December 1992

Entropic Corrections to the Flory-Huggins Theory of Polymer Blends: Architectural and Conformational Effects
journal, April 1994

Microphase separation in thin films of lamellar forming polydisperse di-block copolymers
journal, January 2015

Drug-Loaded, Bivalent-Bottle-Brush Polymers by Graft-through ROMP
journal, December 2010

pH-Sensitive brush polymer-drug conjugates by ring-opening metathesis copolymerization
journal, January 2011

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

Broad-wavelength-range chemically tunable block-copolymer photonic gels
journal, October 2007

Bioinspired Bottle-Brush Polymer Exhibits Low Friction and Amontons-like Behavior
journal, April 2014

Unraveling the Correlations between Conformation, Lubrication, and Chemical Stability of Bottlebrush Polymers at Interfaces
journal, October 2017

Surface Properties of Bottlebrush Polymer Thin Films
journal, August 2012

Creation of Stable Poly(ethylene oxide) Surfaces on Poly(methyl methacrylate) Using Blends of Branched and Linear Polymers
journal, November 1997

Thin Film Phase Behavior of Bottlebrush/Linear Polymer Blends
journal, July 2014

Boundary-induced segregation in nanoscale thin films of athermal polymer blends
journal, January 2016

Effect of Butadiene End-Capping of Arms in a Star Polystyrene on Solution Properties, Bulk Dynamics, and Bulk Thermodynamic Interactions in Binary Blends
journal, December 2004

Effects of Branch Points and Chain Ends on the Thermodynamic Interaction Parameter in Binary Blends of Regularly Branched and Linear Polymers
journal, July 2006

Surface Enrichment in an Isotopic Polymer Blend
journal, January 1989

Facile syntheses of cylindrical molecular brushes by a sequential RAFT and ROMP “grafting-through” methodology
journal, October 2009

A Versatile Precursor for the Synthesis of New Ruthenium Olefin Metathesis Catalysts
journal, December 2001

Generating thickness gradients of thin polymer films via flow coating
journal, February 2006

Improving Brush Polymer Infrared One-Dimensional Photonic Crystals via Linear Polymer Additives
journal, December 2014

Bottlebrush Block Polymers: Quantitative Theory and Experiments
journal, October 2015

Isotope-Induced Quantum-Phase Transitions in the Liquid State
journal, September 1986

Thin films of block copolymer
journal, May 1997

Defectivity in Laterally Confined Lamella-Forming Diblock Copolymers: Thermodynamic and Kinetic Aspects
journal, July 2012

Dispersing Nanoparticles in a Polymer Film via Solvent Evaporation
journal, May 2016

Surface and Interfacial Segregation in Blends of Polystyrene with Functional End Groups and Deuterated Polystyrene
journal, June 2007

The influence of curvature on domain distribution in binary mixture membranes
journal, January 2019