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Moderately concentrated solutions and gels of atactic polystyrene in solvent mixtures of carbon disulfide and tricresyl phosphate
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Image of FIG. 1.
FIG. 1.

(a) The viscosity at divided by that at for mixed solvents: 29, 50, 62, and 67 weight fraction for diamond, square, circle, and triangle, respectively. (b) The viscosity at for mixtures of (circle) or toluene (square) with TCP.

Image of FIG. 2.
FIG. 2.

(a) Gel formation temperature estimates: gel formation detected flow cessation by inverted tube (circle) change in (triangle), or (filled and open diamonds, respectively), and data reported [Chen et al. (1995)], filled circles; melt detected by flow onset detected by falling ball, , or inverted tube, . (b) The fraction of in the binary solvent mixtures in (a); the data for the filled circles are in pure .

Image of FIG. 3.
FIG. 3.

Example of damped torsional oscillation in the intensity correlation function observed with a polystyrene gel (, 0.18, and 0.30 weight fraction and , respectively).

Image of FIG. 4.
FIG. 4.

Examples of (upper) and (lower) vs temperature obtained in the damped torsional oscillation of with a polystyrene composition in Fig. 3.

Image of FIG. 5.
FIG. 5.

Behavior on cooling: is the viscosity at temperature divided by that at (pregel). The shading designates values from the viscosity determined in creep (black for creep alone, and gray for creep and dynamic) or from the “horizontal” shift of dynamic data (white): symbols are for 0.082, 0.092, 0.111, 0.114, 0.116, 0.131, 0.138, 0.141, 0.159, 0.161, and 0.171 weight fraction in , respectively; , , for 0.136 and 0.186 toluene/TCP, respectively, and the symbols were used separately or in combination as for solvent mixtures with 0.29, 0.50, 0.62, and 0.67 weight fraction TCP, respectively, with these points lowered by 0.5 log units for clarity.

Image of FIG. 6.
FIG. 6.

Behavior on isothermal ageing leading to a gel: is the viscosity at age divided by for the viscosity obtained by extrapolation of the viscosity vs on the pregel solution, possibly smaller than that reported for the actual pregel at the specified : , diamonds, , squares, and , circles, for weight fractions and (temperatures), and for 0.57, 0.62, 0.61 weight fractions , respectively.

Image of FIG. 7.
FIG. 7.

Behavior of for the heating of postgel samples, referred to the relevant pregel viscosity at for 0.131 (diamonds), 0.159 (squares), and 0.160 (circles) weight fraction ; the unfilled and filled symbols are for heating and cooling, respectively.

Image of FIG. 8.
FIG. 8.

Bilogarithmic plots of , and vs or (filled squares and circles, respectively) and and vs (unfilled squares and circles, respectively) for a sample with , in a mixed solvent with 38% ; .

Image of FIG. 9.
FIG. 9.

Bilogarithmic plots of vs and vs or (unfilled and filled symbols, respectively) for a sample with , 67% ; , and , for circles, triangles, diamonds, points, and squares, respectively). The lines have slopes 1 and 0.5.

Image of FIG. 10.
FIG. 10.

(a) vs and vs (unfilled and filled symbols, respectively) for solution ; (circles), (squares), (diamonds), and (triangles). (b) The ratio vs for the same, using the same shift parameters.

Image of FIG. 11.
FIG. 11.

Behavior on cooling: is the recoverable compliance divided by that at (pregel), as determined from the “vertical” shift of creep/recovery and/or dynamic. Symbol scheme as in Fig. 5.

Image of FIG. 12.
FIG. 12.

Behavior on cooling: , with and given in Figs. 10 and 11, respectively. The solid line is for the line for in Fig. 10 and . Symbol scheme as in Fig. 5.

Image of FIG. 13.
FIG. 13.

The approximation to based on the recoverable strain in the apparent gel state. The creep was accompanied by a small non recoverable portion, corresponding to a viscosity in excess of : data from either creep or recovery (filled circles), recovery only (open circles) or the low frequency value of (triangles).

Image of FIG. 14.
FIG. 14.

(a) Dependence of the relative viscosity on and : filled circles, this study content in mixtures in the order of increasing , 57, 47, 53, 62, 61, 50, 37, 68, 38, 53; unfilled circles, this study for mixtures; diamond [Chen et al. (1995)] for ; unfilled and filled squares, this study and Liu (1990) for TCP, respectively; filled and unfilled triangles, toluene [Poh and Ong (1984); Kulicke and Kniewske (1984)], respectively. (b) The normalized recoil multiplied by the square of the polymer volume fraction as a function of the polymer volume fraction. The symbols are as in part (a).

Image of FIG. 15.
FIG. 15.

The degree of association in the pregel solution from analysis of vs volume fraction; ; the is shown for each data point.

Image of FIG. 16.
FIG. 16.

The development of an incipient gel: the solid lines for pure power-law, dashed for modified power law: the squares and circles are for and , respectively, with white, gray, and black points for as cooled, and annealed for 2 and , respectively. The solid and dashed lines are for pure and modified power-laws.


Generic image for table

Steady-state parameters for .


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Moderately concentrated solutions and gels of atactic polystyrene in solvent mixtures of carbon disulfide and tricresyl phosphate