Origin of Tensile Stress-Induced Rate Increases in the Photochemical Degradation of Polymers

Chen, Rui; Tyler, David R.

doi:10.1021/ma0496302

Cited by 47 publications

(23 citation statements)

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“…A similar effect has been reported for photodegradation of polymers. [36] Linear heating DMA-MS run at 2°C min -1 . DMA run is performed at frequency 10 Hz.…”

Section: Summary Of the Most Important Resultsmentioning

confidence: 99%

A Method of Monitoring Explosive Under Cyclic Mechanical Stress

Vyazovkin¹

2004

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Public Reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. 45489.1-EG-IIDynamic mechanical analysis is combined with mass spectrometry to study nitrocellulose under oscillating strain. At a constant temperature (150 -160°C) and frequency 400 -600 Hz nitrocellulose fractures demonstrating a modulus drop and release of products with m/z=30 and 44. At linear heating (2°C min-1) and frequency 10 -50 Hz similar products are released in two steps, the second of which demonstrates a modulus drop and a temperature increase indicating ignition. 8 Nitrocellulose, mechanodegradation, fractoemission, dynamic mechanical analysis, mass specrometry

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“…A similar effect has been reported for photodegradation of polymers. [36] Linear heating DMA-MS run at 2°C min -1 . DMA run is performed at frequency 10 Hz.…”

Section: Summary Of the Most Important Resultsmentioning

confidence: 99%

A Method of Monitoring Explosive Under Cyclic Mechanical Stress

Vyazovkin¹

2004

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“…Note that the metal radicals formed by photolysis can be captured with an appropriate radical trap, typically an organic halide or molecular oxygen (21,22). Specific examples of such polymers are the following (23,24):…”

Section: Photodegradable Polymers: Reactivity Overview and Design Primentioning

confidence: 99%

“…Mechanistic hypotheses to explain the effects of stress on photochemical degradation rates fall into three main categories (24). These categories are illustrated by reference to Scheme 9.…”

Section: Effect Of Stressmentioning

confidence: 99%

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Photodegradable plastics: end-of-life design principles

Daglen

Tyler

2010

Green Chemistry Letters and Reviews

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Photochemically degradable polymers and plastics are reviewed with an emphasis on the environmental and molecular factors that control the onset of degradation and the rate of degradation. A number of principles are beginning to emerge for the design of viable photochemically degradable plastics. Among the principles discussed are those relating to the effects of chromophores, initiators, antioxidants, temperature, oxygen diffusion into the plastic, polymer crystallinity, tensile and compressive stress, and the absorbed light intensity on the plastic. To obtain a plastic with a controlled lifetime and a specific rate of degradation, many of these parameters can be controlled or adjusted in the design stage of the plastic.

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“…Figure 8.9 shows the effect of tensile stress on quantum yield of PVC degradation. 16 The hypothesis predicts an eventual downturn in degradation efficiency because of polymer chain ordering; the increased order hinders diffusion apart of the radicals and thus increases their probability of recombination. 16 The DRRE hypothesis proposes that the function of stress is to increase the initial separation of the photochemically generated radical pair, which has the effect of decreasing their recombination efficiency and thus increasing degradation efficiency.…”

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confidence: 99%