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Title: Comment on Comment on “Anomalous structural recovery in the near glass transition range in a polymer glass: Data revisited in light of temperature variability in vacuum oven‐based experiments”*

Journal Article · · Polymer Engineering and Science
DOI:https://doi.org/10.1002/pen.26055· OSTI ID:1874831

Abstract Cangialosi, Alegría, and Colmenero have made a comment on a paper of ours [Polym. Eng. Sci. 2022:1–13], in which we discussed the concern that the enthalpy recovery data reported by Cangialosi and co‐workers [Phys. Rev. Lett. 2013;111(9):095701] for polystyrene aged up to 15 K below glass transition temperature was anomalous and contradicted existing experimental results from the literature over a similar range of aging conditions. Their response shifts the focus away from the raised questions about their experimental results and attempts to invalidate the data that we cited in support of our argument. Here we respond to the comment and add additional analysis that suggests the structural recovery response of glassy materials exhibits smooth behavior over the full range of measurements, up to 7 or 8 logarithmic decades. We do this by referring to the work on the intrinsic isotherm down‐jump and memory responses of poly(vinyl acetate) between 40°C and 15°C over six logarithmic decades by Kovacs [Fortsch. Hochpolym. Fo. 1963;3(1/2):394–508], the small‐strain tensile creep of poly(vinyl chloride) quenched from 90°C to 40°C (approximately 40°C below T g ) over seven logarithmic decades from Struik [Polym Eng. Sci., 1977;17:165–173], and the volume recovery behavior for aging times up to 3 months in a temperature range between 95°C and −50°C by Greiner and Schwarzl [Rheol. Acta. 1984;23(4):378–395]. We also add discussion that an isothermal aging procedure using a vacuum oven is highly vulnerable to temperature errors due to the problem of good temperature control when the heat transfer mechanism is primarily radiative.

Sponsoring Organization:
USDOE
Grant/Contract Number:
DE‐SC0018657
OSTI ID:
1874831
Alternate ID(s):
OSTI ID: 1874832
Journal Information:
Polymer Engineering and Science, Journal Name: Polymer Engineering and Science Vol. 62 Journal Issue: 8; ISSN 0032-3888
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
United States
Language:
English

References (10)

Long-Term Physical Aging Tracked by Advanced Thermal Analysis of Poly(N-Isopropylacrylamide): A Smart Polymer for Drug Delivery System journal August 2020
The kinetics of the glass transition and physical aging in germanium selenide glasses journal May 2013
Comment on “Anomalous structural recovery in the near glass transition range in a polymer glass: Data revisited in light of temperature variability in vacuum oven‐based experiments” journal July 2022
Direct Evidence of Two Equilibration Mechanisms in Glassy Polymers journal August 2013
Deformation and flow of matter: Interrogating the physics of materials using rheological methods journal January 2012
Physical aging in plastics and other glassy materials journal March 1977
Thermal contraction and volume relaxation of amorphous polymers journal July 1984
Anomalous structural recovery in the near glass transition range in a polymer glass: Data revisited in light of temperature variability in vacuum oven‐based experiments* journal February 2022
Comparing calorimetric and dielectric polarization modes in viscous 2-ethyl-1-hexanol journal March 2007
Comparison of the Molecular Dynamics of a Liquid Crystalline Side Group Polymer Revealed from Temperature Modulated DSC and Dielectric Experiments in the Glass Transition Region journal May 2001

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