Liquid–liquid equilibria in polymer solutions at negative pressure

Imre, Attila R.; Hook, W. Alexander Van

doi:10.1039/a827117z

Cited by 41 publications

(22 citation statements)

References 22 publications

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“…These include: the effect of the negative pressure during solidification [34][35][36]; the compressibility of mineral oils under tension [13]; the shift of the melting temperature [20] and that of the locus of maximum density for water [19]; the structure of the phospholipide suspension [37]; and the liquid/liquid phase transition in polymer solutions at negative pressure [38][39][40].…”

Section: Experimental Observations Of Negative Pressure In Liquidsmentioning

confidence: 99%

Thermodynamics of Negative Pressures in Liquids

Imre¹,

Martinás²,

Rebelo³

1998

Journal of Non-Equilibrium Thermodynamics

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Nature uses negative pressures in the most resourceful and efficient ways. Yet, negative pressure states are still sometimes considered inaccessible by part of the scientific community. In this paper we show that any condensed phase can exist in absolute negative pressure regimes, while the same is not true for gas phases. We also demonstrate that such states are not merely possible but have, in spite of their metastability, been observed experimentally on numerous occasions. Moreover, physical properties of several substances and mixtures have already been determined in the stretched liquid phase at absolute negative pressures. Nevertheless, conceiving of and succeeding in an experiment that produces high tension in a liquid are rather difficult. Thus, equations of state and computer simulations are powerful tools for studying metastable liquids. By using a simple equation of state we show: how negative pressure regimes can be attained; the maximum intrinsic tension a liquid can sustain; and below which temperature a liquid can be found in this state. Experimental and theoretical work on liquids at negative pressures is reviewed. Furthermore, the similarities and differences between negative temperature and negative pressure states are demonstrated. Due to water's non-trivial behavior as well as its technological and scientific importance, it has been the most studied substance in metastable phenomena. We will thus devote particular attention to some of the rich features of its metastable phase diagram. Water belongs to a class of substances that presents density anomalies. We also show how the negative pressure region of the phase diagram proves to be paramount in understanding the unusual behavior of this class of substances.

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Section: Experimental Observations Of Negative Pressure In Liquidsmentioning

confidence: 99%

Thermodynamics of Negative Pressures in Liquids

Imre¹,

Martinás²,

Rebelo³

1998

Journal of Non-Equilibrium Thermodynamics

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“…1(d) 16 and PS/cyclohexane (but at low M w only). 17 Since solutions at negative pressure are mechanically metastable, and seldom studied, 10,18 experimental investigation of systems with T DCP L at P Ͼ 0 is of special interest. Examples include PS/cyclohexane (at high M w ), 16 PS/diethyloxalate, 19 and PS/ methylcyclohexane (MCH), 20 -22 and PS/deuteromethylcyclohexane (MCHd).…”

Section: Introductionmentioning

confidence: 99%

A polymer-solvent system with two homogeneous double critical points: Polystyrene (PS)/(n-heptane + methylcyclohexane)

Imre

Melnichenko

Hook

1999

J. Polym. Sci. B Polym. Phys.

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“…Detailed descriptions of negative pressures have already appeared (1)(2)(3)(4)(5)(6). In one of them (5), experimental as well as theoretical achievements with respect to reaching negative pressures in the liquid phase are reviewed.…”

Section: Introductionmentioning

confidence: 99%

Achieving Absolute Negative Pressures in Liquids: Precipitation Phenomena in Solution

2002

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A relatively simple and inexpensive experiment to achieve absolute negative pressures in liquids is reported. The liquid is a 1.80% (w/w) solution of polystyrene (M w = 25,000) in acetone. A detailed description of the experiment is followed by photographs, one of which shows a phase transition occurring at negative pressure. By repeating the experiment at different initial volume ratios of liquid to gas, several phase transition points (cloud points) at distinct negative pressures are determined. For each run, the achieved negative pressure is estimated using the isochoric thermal pressure coefficient γ V . To test the reliability of the experimental data, they are compared with data obtained in the positive-pressure region using a different, more precise technique. The two sets of points match reasonably well.

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Liquid–liquid equilibria in polymer solutions at negative pressure

Cited by 41 publications

References 22 publications

Thermodynamics of Negative Pressures in Liquids

Thermodynamics of Negative Pressures in Liquids

A polymer-solvent system with two homogeneous double critical points: Polystyrene (PS)/(n-heptane + methylcyclohexane)

Achieving Absolute Negative Pressures in Liquids: Precipitation Phenomena in Solution

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