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Kinetics of the thermal degradation of linear polyethylene
Author(s) -
Arnett Raymond L.,
Stacy Carl J.
Publication year - 1966
Publication title -
polymer engineering and science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.503
H-Index - 111
eISSN - 1548-2634
pISSN - 0032-3888
DOI - 10.1002/pen.760060404
Subject(s) - thermodynamics , kinetics , bond , degradation (telecommunications) , reaction rate constant , thermal , molecule , materials science , constant (computer programming) , statistical physics , steady state (chemistry) , chemical physics , mechanics , econometrics , mathematics , computational chemistry , chemistry , physics , organic chemistry , classical mechanics , economics , computer science , telecommunications , finance , programming language
For a system of equivalent bonds undergoing random bond scission it is reasonable to assume that the rate of bond breaking (hence the rate of creation of new molecules) reported in the literature and data presented here demonstrate that the number of molecules created is not proportional to the time of thermal treatment hence they seem to belie this reasonable hypothesis. Other authors have adduced the presence of some non‐equivalent bonds in order to account for the observed cruvature and still retain the hypothesis. Implicit in these arguments is the assumption of a steady‐state concentration of reactive fragments. Our analysis explores the consequences of abandoning the steady‐state assumption and shows that a quantitative explanation of the observed degradation behavior may be had by this means wihile still retaining the hypothesis of a constant probability of a bond being broken per unit time.

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