Search results for "Phase Transition"

Self-organization of substituted azacrowns based on their discoid and amphiphilic nature

1989

Abstract Cyclame and hexacyclene derivatives, bearing four and six long-chain substituents respectively, were synthesized. They are discussed as monolayer-forming amphiphiles as well as liquid-crystalline-phase-forming thermotropic mesogens. The compounds investigated form ordered monolayers at the gas/water interface. In the monolayer the hydrophilic cyclic head group lies flat on the water surface, whereas the hydrophobic substituents are oriented perpendicularly with respect to the interface. Most derivatives fitted with aromatic substituents exhibit a solid condensed state exclusively. In contrast with this, solid condensed as well as expanded phases can be found when spreading the alip…

Detection of phase transitions in thin films with a quartz crystal microbalance

1996

Abstract The quartz crystal microbalance (QCM) is used to determine the phase transition point of thin films by measuring the change in frequency as a function of temperature. To elucidate this relationship, two types of polymers were studied where the bulk phase transitions were known. We investigated a casted thin film of an amphiphilic polyoxazoline and a Langmuir-Blodgett film comprised of fifteen double layers of an amphotropic polyacrylate. The phase transition points of the thin films could be detected by the QCM which were in the same range as for the bulk materials.

1982

The synthesis and phase behaviour of a series of polymers having liquid crystalline sidechains and a poly(acrylic acid) backbone are described. These polymers show a dependence of the phase transition temperatures on molecular weight. In copolymers of two liquid crystalline acrylic esters, induced smectic phases occur. A comparison of the phase transitions of the different polyacrylates, with those of liquid crystalline polymethacrylates and polysiloxanes, published elsewhere, establishes that the spacer group achieves partial “decoupling” of liquid crystalline and polymer properties.

Differences between smectic homo‐ and co‐polysiloxanes as a consequence of microphase separation

2005

This paper compares smectic phases formed from LC‐homo‐ and LC‐co‐polysiloxanes. In the homopolysiloxane, each repeating unit of the polymer chain is substituted with a mesogen, whereas in the copolysiloxanes mesogenic repeating units are separated by dimethylsiloxane units. Despite a rather similiar phase sequence of the homo‐ and co‐polysiloxanes—higher ordered smectic, smectic C* (SmC*), smectic A (SmA) and isotropic—the nature of their phases differs strongly. For the copolymers the phase transition SmC* to SmA is second order and of the ‘de Vries’ type with a very small thickness change of the smectic layers. Inside the SmA phase, however, the smectic thickness decreases strongly on ap…

Structure and elastic properties of smectic liquid crystalline elastomer films

2001

Mechanical measurements, x-ray investigations, and optical microscopy are employed to characterize the interplay of chemical composition, network topology, and elastic response of smectic liquid crystalline elastomers (LCEs) in various mesophases. Macroscopically ordered elastomer films of submicrometer thicknesses were prepared by cross linking freely suspended smectic polymer films. The cross-linked material preserves the mesomorphism and phase transitions of the precursor polymer. The elastic response of the smectic LCE is entropic, and the corresponding elastic moduli are of the order of MPa. In the tilted ferroelectric smectic-C* phase, the network structure plays an important role. Du…

Rheological Consequences of Hydrogen Bonding: Linear Viscoelastic Response of Linear Polyglycerol and Its Permethylated Analogues as a General Model …

2014

Viscoelastic properties of linear, hydroxyl-functional polymers are only little understood with respect to the effect of functional group interactions. Melt rheology and thermal phase transitions of linear polyethers (polyglycerol, linPG-OH) and their methylated analogues (linPG-OMe) in a broad molecular weight range (Mn = 1–100 kg/mol) with low polydispersities (PDI) have been investigated as a general model for hydroxyl-functional polymers with respect to their functionality and hydrogen bond interactions. We provide detailed insight into the rheodynamics of nonentangled and well-entangled polyethers bearing one functional group per monomer unit. Booij–Palmen plots (BBP) revealed failure …

Phase behavior and elastic properties of a slightly crosslinked liquid crystalline main-chain polymer

1990

A liquid crystalline main-chain polymer was slightly crosslinked by a reaction withα, ω-difunctionalized oligo-siloxanes. Crosslinking does not disturb the liquid crystalline phases, which are identified by x-ray measurements as smecticB and smecticA phases. Measurements of the elastic properties of the crosslinked sample show rubber-like elasticity, even in the liquid crystalline phases. A difference of 7 K was found between cooling and heating for the smecticA/isotropic transition from DSC and mechanical measurements.

Structure and phase transitions of a liquid crystalline polymer

1981

The structures, textures as well as thermodynamic properties of a side chain polymer exhibiting a liquid crystalline phase in addition to a partially crystalline state and the isotropic fluid state were investigated. Furthermore the kinetics of phase transitions between these states were analyzed. It was found that the properties of this polymer are intermediate between that of low molecular weight liquid crystals and common polymers. In particular it was observed that the relation between the liquid crystalline texture and the structure is different from that of low molecular weight liquid crystals and that the properties of the crystalline and liquid crystalline state depend strongly on t…

How Structure-Related Collapse Mechanisms Determine Nanoscale Inhomogeneities in Thermoresponsive Polymers

2012

Continuous wave electron paramagnetic resonance (CW EPR) spectroscopy on the amphiphilic spin probe TEMPO in solutions of selectively chosen functional, thermoresponsive poly(propylene oxide) (PPO)- and poly(ethylene oxide) (PEO)-based copolymers of both linear and branched structure is used to elucidate their host–guest interactions and inverse phase transitions. Three different fundamental types of host–guest interactions between probes and polymers could be correlated to the phase transition mechanisms (supported by MD simulations), evidencing that these proceed via nanoscale inhomogeneities of the polymers. Because of their ability to host small amphiphilic guest molecules, thermorespon…

Spinodal decomposition of chemically fueled polymer solutions

2021

Out-of-equilibrium phase transitions driven by dissipation of chemical energy are a common mechanism for morphological organization and temporal programming in biology. Inspired by this, dissipative self-assembly utilizes chemical reaction networks (CRNs) that consume high-energy molecules (chemical fuels) to generate transient structures and functionality. While a wide range of chemical fuels and building blocks are now available for chemically fueled systems, so far little attention has been paid to the phase-separation process itself. Herein, we investigate the chemically fueled spinodal decomposition of poly(norbornene dicarboxylic acid) (PNDAc) solution, which is driven by a cyclic che…