Search results for "Theta solvent"

Solidification behavior of the theta system 2-propanol/poly(n-butyl methacrylate) I. Influences of thermoreversible gelation on stationary flow

1994

Zero shear viscosities, η0, were determined by means of a magnetoviscometer for melts of poly(n-butyl methacrylate) (M = 8.7 to 450 kg/mol, T =53.5 to 200°C) and for concentrated solutions of the highest molecular weight sample in isopropanol (T = 34.8 to 131.5 °C). Master curves can be constructed in both cases if the reference temperature is set proportional to the gelation temperature of the particular fluid. Special intersegmental interactions (eventually leading to thermoreversible gelation) can above all be felt in η0 (T) and in M c , the critical molecular weight determined in plots of log η0 vs. log M. As the temperature is lowered, the behavior changes from WLF to Arrhenius, and M …

Computer simulation of bottle-brush polymers with flexible backbone: good solvent versus theta solvent conditions.

2011

By Molecular Dynamics simulation of a coarse-grained bead-spring type model for a cylindrical molecular brush with a backbone chain of $N_b$ effective monomers to which with grafting density $\sigma$ side chains with $N$ effective monomers are tethered, several characteristic length scales are studied for variable solvent quality. Side chain lengths are in the range $5 \le N \le 40$, backbone chain lengths are in the range $50 \le N_b \le 200$, and we perform a comparison to results for the bond fluctuation model on the simple cubic lattice (for which much longer chains are accessible, $N_b \le 1027$, and which corresponds to an athermal, very good, solvent). We obtain linear dimensions of …

Impulsive solvent heating probed by picosecond x-ray diffraction

2006

The time-resolved diffraction signal from a laser-excited solution has three principal components: the solute-only term, the solute-solvent cross term, and the solvent-only term. The last term is very sensitive to the thermodynamic state of the bulk solvent, which may change during a chemical reaction due to energy transfer from light-absorbing solute molecules to the surrounding solvent molecules and the following relaxation to equilibrium with the environment around the scattering volume. The volume expansion coefficient alpha for a liquid is typically approximately 1 x 10(-3) K(-1), which is about 1000 times greater than for a solid. Hence solvent scattering is a very sensitive on-line t…

1988

Light scattering, neutron scattering and viscosity measurements on a nematic and a smectic polymethacrylate demonstrate the presence of molecularly disperse coils in solution. For the nematic polymer, toluene is a theta solvent, the behaviour familiar from conventional polymers (unperturbed coil conformation) being exhibited at the theta point. The isotropic melts likewise contain unperturbed coils; in the case of the nematic polymers, however, the coils in the melt have a radius of gyration which is about 30% smaller than that in solution at the theta point. In the liquid-crystalline phase, the mean radii of gyration in both cases are identical to the corresponding parameters in the isotro…

1993

The viscosities of moderately concentrated solutions of poly(butyl methacrylate)—Mw = 1820 kg/mol–in the thermodynamically good solvent toluene and in the theta solvent 2-propanol were measured up to pressures of 2000 bar as a function of shear rate in the temperature interval from 40 to 70°C. Both systems obey Graessley's equation so that it is possible to obtain the following rheological parameters in addition to the zero-shear viscosity η0 from the dependences . η can be split into an entanglement part ηent plus a frictional contribution ηfric, and the characteristic viscometric relaxation time τ0 becomes accessible. The present results demonstrate that the application of pressure raises…

Kramers potential study of the Rouse-like dynamics of short alkane chains.

1999

In this work we present a Kramers potential study of the orientational dynamics and shear viscosity of short chain alkanes. In this approach the determination of the orientational relaxation time is reduced to the calculation of static moments of single chain conformations. We study a chemically realistic alkane model that asymptotically produces Gaussian chain conformations by means of a Monte Carlo simulation. Our results are applicable to single chain descriptions of polymer melt dynamics and to the intrinsic viscosity of molecules in a Theta solvent. When we map the unknown time unit of our relaxation time result for one particular chain length and temperature to the value obtained for …

1986

Poly(methylmethacrylate) (PMMA), poly(butylmethacrylate) (PBMA), and poly(decylmethacrylate) (PDMA) are completely miscible with toluene at normal pressure from room temperature up to the boiling point of the solvent. In alkanes (C6 to C10) and 1-pentanol the solubility increases with the length of the side chain of the polymer: PMMA always exhibits a solubility gap within the above temperature range, PBMA shows upper critical solution temperatures (except n-hexane, which is a non-solvent), and PDMA mixes completely with all alkanes under consideration. Alcohols (up to C4) are non-solvents for PMMA but theta solvents for PBMA and PDMA (except ethanol which is a non-solvent for the latter). …

On what terms and why the thermodynamic properties of polymer solutions depend on chain length up to the melt

2003

Theoretical considerations based on chain connectivity and conformational variability of polymers have lead to an uncomplicated relation for the dependence of the Flory-Huggins interaction parameter, chi, on the volume fraction of the polymer, phi, and on its number of segments, N. The validity of this expression is being tested extensively by means of vapor pressure measurements and inverse gas chromatography (complemented by osmotic and light scattering data from literature) for solutions of poly(dimethylsiloxane) in the thermodynamically vastly different solvents n-octane (n-C8), toluene (TL), and methylethylketone (MEK) over the entire range of composition for at least six different mol…

Polymer solutions confined in slit-like pores with attractive walls: An off-lattice Monte Carlo study of static properties and chain dynamics

1996

Using a bead spring model of flexible polymer chains, the density profiles and chain configurational properties of polymer solutions confined between parallel plates were studied. A wide range of density ϕ, chain length N, and strength e of a short-range attractive wall potential was investigated. Both a temperature T in the good solvent regime (T > θ, θ being the Theta temperature where a chain in unconfined bulk three-dimensional solution would behave ideally) and a temperature in the bad solvent regime (T θ) show a crossover from two-dimensional excluded volume behavior (Rg ∝ N2ν with ν = 3/4) to ideal random walk behavior (ν = 1/2), the relaxation times show effective exponents Zeff (τ …

Vitrification of polymer solutions as a function of solvent quality, analyzed via vapor pressures.

2006

Vapor pressures (headspace sampling in combination with gas chromatography) and glass transition temperatures [differential scanning calorimetry (DSC)] have been measured for solutions of polystyrene (PS) in either toluene (TL) (10-70 degrees C) or cyclohexane (CH) (32-60 degrees C) from moderately concentrated solutions up to the pure polymer. As long as the mixtures are liquid, the vapor pressure of TL (good solvent) is considerably lower than that of CH (theta solvent) under other identical conditions. These differences vanish upon the vitrification of the solutions. For TL the isothermal liquid-solid transition induced by an increase of polymer concentration takes place within a finite …