Putative role of attractive and repulsive forces in the glass transition

Putative role of attractive and repulsive forces in the glass transition At a given temperature a balance between repulsive and attractive molecular forces determines liquid density. As temperature is lowered, attractive forces increase, but eventually saturate and asymptote to a near fixed value. At saturation, the attractive/repulsive force balance stabilizes the liquid density, which thereafter becomes effectively temperature independent. Configurational entropy also saturates, but at a much lower temperature. Once entropy begins to saturate, it converges to zero at absolute zero. There is no second order phase transition nor is there a divergent temperature above absolute zero predicted for glass relaxation phenomena. Using a phenomenological argument, it is shown that the relaxation time for volume relaxation varies inversely with configurational entropy. Stoichiometric electron density is proposed as a metric for repulsive force strength, which was determined at Tg and averaged 0.61±0.03 mol/cc for 15 polymers that contain oxygen and 0.53±0.02 mol/cc for 7 hydrocarbon polymers. Qualitatively, similar polymer liquids that pack to higher electron densities at a given temperature are expected to experience a glass transition earlier as temperature is lowered. For certain polymer types, the glass transition appears to be an isoelectronic state. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Polymer Elsevier

Putative role of attractive and repulsive forces in the glass transition

Loading next page...
 
/lp/elsevier/putative-role-of-attractive-and-repulsive-forces-in-the-glass-byqdqpMXFR
Publisher
Elsevier
Copyright
Copyright © 2017 Elsevier Ltd
ISSN
0032-3861
D.O.I.
10.1016/j.polymer.2017.11.037
Publisher site
See Article on Publisher Site

Abstract

At a given temperature a balance between repulsive and attractive molecular forces determines liquid density. As temperature is lowered, attractive forces increase, but eventually saturate and asymptote to a near fixed value. At saturation, the attractive/repulsive force balance stabilizes the liquid density, which thereafter becomes effectively temperature independent. Configurational entropy also saturates, but at a much lower temperature. Once entropy begins to saturate, it converges to zero at absolute zero. There is no second order phase transition nor is there a divergent temperature above absolute zero predicted for glass relaxation phenomena. Using a phenomenological argument, it is shown that the relaxation time for volume relaxation varies inversely with configurational entropy. Stoichiometric electron density is proposed as a metric for repulsive force strength, which was determined at Tg and averaged 0.61±0.03 mol/cc for 15 polymers that contain oxygen and 0.53±0.02 mol/cc for 7 hydrocarbon polymers. Qualitatively, similar polymer liquids that pack to higher electron densities at a given temperature are expected to experience a glass transition earlier as temperature is lowered. For certain polymer types, the glass transition appears to be an isoelectronic state.

Journal

PolymerElsevier

Published: Jan 17, 2018

References

You’re reading a free preview. Subscribe to read the entire article.


DeepDyve is your
personal research library

It’s your single place to instantly
discover and read the research
that matters to you.

Enjoy affordable access to
over 18 million articles from more than
15,000 peer-reviewed journals.

All for just $49/month

Explore the DeepDyve Library

Search

Query the DeepDyve database, plus search all of PubMed and Google Scholar seamlessly

Organize

Save any article or search result from DeepDyve, PubMed, and Google Scholar... all in one place.

Access

Get unlimited, online access to over 18 million full-text articles from more than 15,000 scientific journals.

Your journals are on DeepDyve

Read from thousands of the leading scholarly journals from SpringerNature, Elsevier, Wiley-Blackwell, Oxford University Press and more.

All the latest content is available, no embargo periods.

See the journals in your area

DeepDyve

Freelancer

DeepDyve

Pro

Price

FREE

$49/month
$360/year

Save searches from
Google Scholar,
PubMed

Create lists to
organize your research

Export lists, citations

Read DeepDyve articles

Abstract access only

Unlimited access to over
18 million full-text articles

Print

20 pages / month

PDF Discount

20% off