Hierarchical morphologies, functional properties, and electrospun fibers of supramolecular complexes of diblock copolymer/amphiphile systems

Dissertation

Research output: ThesisDissertationCollection of Articles

Abstract

This thesis consists of 5 publications, where morphologies, functional properties, and electrospun fibers of supramolecular diblock copolymer/amphiphile systems are studied. Supramolecular systems consists of polystyrene-block- poly(4-vinylpyridine), its methane sulphonic acid and toluene sulphonic acid salts, and different oligomeric amphiphilic molecules physically bonded to the latter block. In Article I, morphologies of polystyrene-block-poly(4-vinylpyridine) and its methane sulphonic acid salts, and hydrogen bonded pentadecylphenol were investigated at different temperatures. Based on reversibility of the hydrogen bonding and polymer/pentadecylphenol phase behaviour, novel structures and reversible order-order and order-disorder transitions were observed as a function of temperature. In Article II, a block copolyelectrolyte complex based on toluene sulphonic acid salt of polystyrene-block-poly(4- vinylpyridine) hydrogen bonded to pentadecylphenol was investigated. After shear alignment, lamellar-within-cylindrical self-assembly with parallel structures was observed. Anisotropic conductivity of the sample was investigated and observed to be astonishingly small due to residual defects and domain boundaries still found in the sample. In Article III, porous materials were prepared using polystyrene-block-poly(4-vinylpyridine) with coordinated zinc dodecylbenzene sulphonate. Porous lamellar structures with dense set of brushes at the pore interfaces were obtained as the coordination bonding between the amphiphiles and poly(4-vinylpyridine) block was cleaved. Collapse of the structure was prevented probably due to the defects and grain boundaries of the non-aligned glassy matrix. In Article IV, porous mesoscale fibers were prepared by electrospinning polystyrene-block-poly(4-vinylpyridine) with hydrogen bonded pentadecylphenol. This leads to structure formation at three different length scales. The porosity was achieved by cleaving the amphiphiles from the structure by extraction. In Article V, studies of electrospun fibers were continued, and it was shown that the block copolymer level structures can be tuned to some extent even if the structures after the electrospinning are not in the thermal equilibrium. Englanninkieliset avainsanat self-assembly hierarchy physical bonding porosity electrospinning
Original languageEnglish
QualificationDoctor Degree
Awarding Institution
  • Helsinki University of Technology
Award date19 Jan 2007
Place of PublicationEspoo
Publisher
Print ISBNs978-951-22-8583-9
Electronic ISBNs978-951-22-8584-6
Publication statusPublished - 2007
MoE publication typeG5 Doctoral dissertation (article)

Fingerprint

Amphiphiles
Sulfonic Acids
Block copolymers
Electrospinning
Fibers
Hydrogen
Salts
Methane
Toluene
Self assembly
Porosity
Defects
Lamellar structures
Order disorder transitions
Brushes
Phase behavior
Porous materials
Zinc
Hydrogen bonds
Polymers

Keywords

  • self-assembly
  • hierarchy
  • physical bonding
  • porosity
  • electrospinning

Cite this

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title = "Hierarchical morphologies, functional properties, and electrospun fibers of supramolecular complexes of diblock copolymer/amphiphile systems: Dissertation",
abstract = "This thesis consists of 5 publications, where morphologies, functional properties, and electrospun fibers of supramolecular diblock copolymer/amphiphile systems are studied. Supramolecular systems consists of polystyrene-block- poly(4-vinylpyridine), its methane sulphonic acid and toluene sulphonic acid salts, and different oligomeric amphiphilic molecules physically bonded to the latter block. In Article I, morphologies of polystyrene-block-poly(4-vinylpyridine) and its methane sulphonic acid salts, and hydrogen bonded pentadecylphenol were investigated at different temperatures. Based on reversibility of the hydrogen bonding and polymer/pentadecylphenol phase behaviour, novel structures and reversible order-order and order-disorder transitions were observed as a function of temperature. In Article II, a block copolyelectrolyte complex based on toluene sulphonic acid salt of polystyrene-block-poly(4- vinylpyridine) hydrogen bonded to pentadecylphenol was investigated. After shear alignment, lamellar-within-cylindrical self-assembly with parallel structures was observed. Anisotropic conductivity of the sample was investigated and observed to be astonishingly small due to residual defects and domain boundaries still found in the sample. In Article III, porous materials were prepared using polystyrene-block-poly(4-vinylpyridine) with coordinated zinc dodecylbenzene sulphonate. Porous lamellar structures with dense set of brushes at the pore interfaces were obtained as the coordination bonding between the amphiphiles and poly(4-vinylpyridine) block was cleaved. Collapse of the structure was prevented probably due to the defects and grain boundaries of the non-aligned glassy matrix. In Article IV, porous mesoscale fibers were prepared by electrospinning polystyrene-block-poly(4-vinylpyridine) with hydrogen bonded pentadecylphenol. This leads to structure formation at three different length scales. The porosity was achieved by cleaving the amphiphiles from the structure by extraction. In Article V, studies of electrospun fibers were continued, and it was shown that the block copolymer level structures can be tuned to some extent even if the structures after the electrospinning are not in the thermal equilibrium. Englanninkieliset avainsanat self-assembly hierarchy physical bonding porosity electrospinning",
keywords = "self-assembly, hierarchy, physical bonding, porosity, electrospinning",
author = "Teemu Ruotsalainen",
note = "TK603 Helsinki University of Technology. Department of Engineering Physics and Mathematics Optics and Molecular Materials 45 p. + app. 51 p.",
year = "2007",
language = "English",
isbn = "978-951-22-8583-9",
series = "TKK Dissertations",
publisher = "Helsinki University of Technology",
address = "Finland",
school = "Helsinki University of Technology",

}

Hierarchical morphologies, functional properties, and electrospun fibers of supramolecular complexes of diblock copolymer/amphiphile systems : Dissertation. / Ruotsalainen, Teemu.

Espoo : Helsinki University of Technology, 2007. 96 p.

Research output: ThesisDissertationCollection of Articles

TY - THES

T1 - Hierarchical morphologies, functional properties, and electrospun fibers of supramolecular complexes of diblock copolymer/amphiphile systems

T2 - Dissertation

AU - Ruotsalainen, Teemu

N1 - TK603 Helsinki University of Technology. Department of Engineering Physics and Mathematics Optics and Molecular Materials 45 p. + app. 51 p.

PY - 2007

Y1 - 2007

N2 - This thesis consists of 5 publications, where morphologies, functional properties, and electrospun fibers of supramolecular diblock copolymer/amphiphile systems are studied. Supramolecular systems consists of polystyrene-block- poly(4-vinylpyridine), its methane sulphonic acid and toluene sulphonic acid salts, and different oligomeric amphiphilic molecules physically bonded to the latter block. In Article I, morphologies of polystyrene-block-poly(4-vinylpyridine) and its methane sulphonic acid salts, and hydrogen bonded pentadecylphenol were investigated at different temperatures. Based on reversibility of the hydrogen bonding and polymer/pentadecylphenol phase behaviour, novel structures and reversible order-order and order-disorder transitions were observed as a function of temperature. In Article II, a block copolyelectrolyte complex based on toluene sulphonic acid salt of polystyrene-block-poly(4- vinylpyridine) hydrogen bonded to pentadecylphenol was investigated. After shear alignment, lamellar-within-cylindrical self-assembly with parallel structures was observed. Anisotropic conductivity of the sample was investigated and observed to be astonishingly small due to residual defects and domain boundaries still found in the sample. In Article III, porous materials were prepared using polystyrene-block-poly(4-vinylpyridine) with coordinated zinc dodecylbenzene sulphonate. Porous lamellar structures with dense set of brushes at the pore interfaces were obtained as the coordination bonding between the amphiphiles and poly(4-vinylpyridine) block was cleaved. Collapse of the structure was prevented probably due to the defects and grain boundaries of the non-aligned glassy matrix. In Article IV, porous mesoscale fibers were prepared by electrospinning polystyrene-block-poly(4-vinylpyridine) with hydrogen bonded pentadecylphenol. This leads to structure formation at three different length scales. The porosity was achieved by cleaving the amphiphiles from the structure by extraction. In Article V, studies of electrospun fibers were continued, and it was shown that the block copolymer level structures can be tuned to some extent even if the structures after the electrospinning are not in the thermal equilibrium. Englanninkieliset avainsanat self-assembly hierarchy physical bonding porosity electrospinning

AB - This thesis consists of 5 publications, where morphologies, functional properties, and electrospun fibers of supramolecular diblock copolymer/amphiphile systems are studied. Supramolecular systems consists of polystyrene-block- poly(4-vinylpyridine), its methane sulphonic acid and toluene sulphonic acid salts, and different oligomeric amphiphilic molecules physically bonded to the latter block. In Article I, morphologies of polystyrene-block-poly(4-vinylpyridine) and its methane sulphonic acid salts, and hydrogen bonded pentadecylphenol were investigated at different temperatures. Based on reversibility of the hydrogen bonding and polymer/pentadecylphenol phase behaviour, novel structures and reversible order-order and order-disorder transitions were observed as a function of temperature. In Article II, a block copolyelectrolyte complex based on toluene sulphonic acid salt of polystyrene-block-poly(4- vinylpyridine) hydrogen bonded to pentadecylphenol was investigated. After shear alignment, lamellar-within-cylindrical self-assembly with parallel structures was observed. Anisotropic conductivity of the sample was investigated and observed to be astonishingly small due to residual defects and domain boundaries still found in the sample. In Article III, porous materials were prepared using polystyrene-block-poly(4-vinylpyridine) with coordinated zinc dodecylbenzene sulphonate. Porous lamellar structures with dense set of brushes at the pore interfaces were obtained as the coordination bonding between the amphiphiles and poly(4-vinylpyridine) block was cleaved. Collapse of the structure was prevented probably due to the defects and grain boundaries of the non-aligned glassy matrix. In Article IV, porous mesoscale fibers were prepared by electrospinning polystyrene-block-poly(4-vinylpyridine) with hydrogen bonded pentadecylphenol. This leads to structure formation at three different length scales. The porosity was achieved by cleaving the amphiphiles from the structure by extraction. In Article V, studies of electrospun fibers were continued, and it was shown that the block copolymer level structures can be tuned to some extent even if the structures after the electrospinning are not in the thermal equilibrium. Englanninkieliset avainsanat self-assembly hierarchy physical bonding porosity electrospinning

KW - self-assembly

KW - hierarchy

KW - physical bonding

KW - porosity

KW - electrospinning

M3 - Dissertation

SN - 978-951-22-8583-9

T3 - TKK Dissertations

PB - Helsinki University of Technology

CY - Espoo

ER -