Photochromic and Fluorescent Probe Studies in Glassy Polymer Matrices. 3. Effects of Physical Aging and Molar Weight on the Size Distribution of Local Free Volume in Polystyrene

John G. Victor; John M Torkelson

doi:10.1021/ma00190a025

Photochromic and Fluorescent Probe Studies in Glassy Polymer Matrices. 3. Effects of Physical Aging and Molar Weight on the Size Distribution of Local Free Volume in Polystyrene

John G. Victor, John M Torkelson^*

^*Corresponding author for this work

Chemical and Biological Engineering

Research output: Contribution to journal › Article › peer-review

96 Scopus citations

Abstract

Changes in the distribution of local free volume in polystyrene glass during physical aging were measured by using photochromic probe molecules requiring different amounts of volume to photoisomerize. The fraction of local free volume in the size range 130-180 Å³ is constant as the polystyrene molar weight decreases to a critical value between 34 000 and 92 000. At lower molar weights the fraction of local free volume in the size range 130-280 Å³ decreases with decreasing molar weight. Physical aging in polystyrene glass reduces or leaves unchanged the fraction of local free volume larger than each probe needs to isomerize. During physical aging the greatest loss of local free volume occurs in the size range larger than 280 Å³, but the amount of loss varies with annealing temperature. The temperature of maximum rate of loss is 20-25 °C less than Tg for polystyrene of 3970 and 9050 molar weight. In polystyrene of 573000 molar weight annealed 250 h at 30 °C, most of the loss of local free volume larger than 280 Å³ occurs within the first 4 h.

Original language	English (US)
Pages (from-to)	3490-3497
Number of pages	8
Journal	Macromolecules
Volume	21
Issue number	12
DOIs	https://doi.org/10.1021/ma00190a025
State	Published - Dec 1 1988

ASJC Scopus subject areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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10.1021/ma00190a025

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@article{d3dd7b11720b4f358dcbc66b4c2508f4,

title = "Photochromic and Fluorescent Probe Studies in Glassy Polymer Matrices. 3. Effects of Physical Aging and Molar Weight on the Size Distribution of Local Free Volume in Polystyrene",

abstract = "Changes in the distribution of local free volume in polystyrene glass during physical aging were measured by using photochromic probe molecules requiring different amounts of volume to photoisomerize. The fraction of local free volume in the size range 130-180 {\AA}3 is constant as the polystyrene molar weight decreases to a critical value between 34 000 and 92 000. At lower molar weights the fraction of local free volume in the size range 130-280 {\AA}3 decreases with decreasing molar weight. Physical aging in polystyrene glass reduces or leaves unchanged the fraction of local free volume larger than each probe needs to isomerize. During physical aging the greatest loss of local free volume occurs in the size range larger than 280 {\AA}3, but the amount of loss varies with annealing temperature. The temperature of maximum rate of loss is 20-25 °C less than Tg for polystyrene of 3970 and 9050 molar weight. In polystyrene of 573000 molar weight annealed 250 h at 30 °C, most of the loss of local free volume larger than 280 {\AA}3 occurs within the first 4 h.",

author = "Victor, {John G.} and Torkelson, {John M}",

year = "1988",

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AU - Victor, John G.

AU - Torkelson, John M

PY - 1988/12/1

Y1 - 1988/12/1

N2 - Changes in the distribution of local free volume in polystyrene glass during physical aging were measured by using photochromic probe molecules requiring different amounts of volume to photoisomerize. The fraction of local free volume in the size range 130-180 Å3 is constant as the polystyrene molar weight decreases to a critical value between 34 000 and 92 000. At lower molar weights the fraction of local free volume in the size range 130-280 Å3 decreases with decreasing molar weight. Physical aging in polystyrene glass reduces or leaves unchanged the fraction of local free volume larger than each probe needs to isomerize. During physical aging the greatest loss of local free volume occurs in the size range larger than 280 Å3, but the amount of loss varies with annealing temperature. The temperature of maximum rate of loss is 20-25 °C less than Tg for polystyrene of 3970 and 9050 molar weight. In polystyrene of 573000 molar weight annealed 250 h at 30 °C, most of the loss of local free volume larger than 280 Å3 occurs within the first 4 h.

AB - Changes in the distribution of local free volume in polystyrene glass during physical aging were measured by using photochromic probe molecules requiring different amounts of volume to photoisomerize. The fraction of local free volume in the size range 130-180 Å3 is constant as the polystyrene molar weight decreases to a critical value between 34 000 and 92 000. At lower molar weights the fraction of local free volume in the size range 130-280 Å3 decreases with decreasing molar weight. Physical aging in polystyrene glass reduces or leaves unchanged the fraction of local free volume larger than each probe needs to isomerize. During physical aging the greatest loss of local free volume occurs in the size range larger than 280 Å3, but the amount of loss varies with annealing temperature. The temperature of maximum rate of loss is 20-25 °C less than Tg for polystyrene of 3970 and 9050 molar weight. In polystyrene of 573000 molar weight annealed 250 h at 30 °C, most of the loss of local free volume larger than 280 Å3 occurs within the first 4 h.

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Photochromic and Fluorescent Probe Studies in Glassy Polymer Matrices. 3. Effects of Physical Aging and Molar Weight on the Size Distribution of Local Free Volume in Polystyrene

Abstract

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