Infrared Spectroscopic Study of the Thermo-Oxidative Aging of Polyethylene Containing Pro-Oxidant

2013 ◽  
Vol 685 ◽  
pp. 316-323 ◽  
Author(s):  
Samira Kerouani ◽  
Tahar Sadoun ◽  
Noureddine Azzouz

Synthetic polymers are not normally biodegradable until they are degraded into low molecular mass species that can be assimilated by microorganisms. This means that biodegradation must be preceded by an abiotic degradation that produces monomeric and oligomeric products. It has been shown that carboxylic acids, alcohols, ketones, etc... can be utilized by microorganisms as nutrients to produce cell biomass. Polyethylene is resistant to oxidation and biodegradation because of the presence of antioxidants and stabilizers. However, it can be made oxo-biodegradable by the use of prooxidant additives. The most active prooxidants are those based on transition metal particulary Fe, Co and Mn. This study is an attempt to investigate the effect of prooxidant additives on the thermo-oxidation of polyethylene. Three differentes mulch films of polyethylene, two films with prooxidant additives consisting of salt based on cobalt and iron and the third film whitout prooxidant, were subjected to thermo-oxidative degradation which was conducted in an air oven at 70°C that normally occur during composting conditions, for extended time periods. Based on Fourier transform infrared spectroscopy the chemical and structural changes induced by this exposure were followed by monitoring the changes in carbonyl index and cristallinity. The results reveal an increase in the carbonyl groups with aging time more important for the polyehylene films containing a combination of Fe and Co additives than these obtained by the films with only one transition metal additive (Co) while the LDPE without additives represents no increase in carbonyl groups. The results show also a small variation of cristallinity for the two differents polyethylene films with pro-oxidant. This indicates that the transition metal prooxidant plays an important role in the degradation of PE films and accelerates the degradation of PE.

1969 ◽  
Vol 42 (4) ◽  
pp. 1095-1121 ◽  
Author(s):  
C. S. Kim

Abstract Zhurkov's molecular kinetic concept of failure for hard solid materials was extended for application to rubber systems which undergo oxidative degradation during long-term atmospheric exposure. In an effort to analyze the chemical and mechanical effects separately, the dependency of the life-time of the uniaxially stressed rubber was expressed in terms of (1) chemical effects involving the primary chemical bonds in the effective chains, and (2) mechanical effects involving the network structure of the rubber.


Polymers ◽  
2022 ◽  
Vol 14 (2) ◽  
pp. 226
Author(s):  
Jinsong Yang ◽  
Weitao Lou

The effects of oxidative aging on the static and dynamic properties of nitrile rubber at the molecular scale were investigated by molecular dynamics simulation. The aged nitrile rubber models were constructed by introducing hydroxyl groups and carbonyl groups into rubber molecular chains to mimic oxidative aging. The static and dynamic properties of the unaged and aged nitrile rubber under different conditions were evaluated by mean square displacement, self-diffusion coefficients, hydrogen bond, fractional free volume, radial distribution function, cohesive energy density and solubility parameter. The results show that the elevated temperature intensified significantly the mobility of rubber molecular chains and fractional free volume, while the compressive strain displayed the opposite effect resulting in packing and rearrangement of rubber chains. The introduction of hydroxyl groups and carbonyl groups enhanced the polarity, intermolecular interactions, the volume and rigidity of molecular chains, implying weaker mobility of molecular chains as compared to unaged models. The compressive strain and oxidative aging both decreased the fractional free volume, which inhibited gaseous and liquid diffusion into the rubber materials, and slowed down the oxidative aging rate. This study provides insights to better understand the effect of molecular changes due to oxidative aging on the structural and dynamic properties of rubber materials at the molecular level.


1983 ◽  
Vol 38 (5) ◽  
pp. 587-591 ◽  
Author(s):  
Alexander Filippou ◽  
Ernst Otto Fischer

AbstractReaction of trans-bromotetracarbonyl(phenylcarbyne)-complexes of chromium, molybdenum and tungsten and trans-bromotetracarbonyl(methylcarbyne) complexes of chromium and tungsten with the bidentate ligands 2,2′-bipyridyl and 1,10-phenanthroline results in the replacement of two carbonyl groups leading to very thermostable carbyne complexes with the general formula Br(CO)2LMCR (L: 2,2′-bipy, ophen; M: Cr, Mo, W; R : CH3, C6H5).


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