Engineering topics
Publications and source records attributed to Golub, M. A..
The work described was carried out to study the thermal rearrangements of two unsaturated diene polymers - 1,2-poly(cis-1,4-hexadiene) (CHD) and 1,2-poly(trans-1.4-hexadiene) (THD). It is shown that both CHD and THD have a predominatly 1,8 diene structure and seem to cyclize mainly by the (2 + 2) thermal cycloaddition of double bonds, and to a small extent also by sigmatropic rearrangement with hydrogen shift.
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Comparative laboratory and field tests were conducted on experimental and state-of-the-art aircraft tire tread materials in a program aimed at seeking new elastomeric materials which would provide improved aircraft tire tread wear, traction, and blowout resistance in the interests of operational safety and economy. The experimental stock was formulated of natural rubber and amorphous vinyl polybutadiene to provide high thermal-oxidative resistance, a characteristic pursued on the premise that thermal oxidation is involved both in the normal abrasion or wear of tire treads and probably in the chain of events leading to blowout failures. Results from the tests demonstrate that the experimental stock provided better heat buildup (hysteresis) and fatigue properties, at least equal wet and dry traction, and greater wear resistance than the state-of-the-art stock.
An investigation was conducted concerning the microstructural changes occurring in cis- and trans-1,4-polyisoprenes during uncatalized thermal oxidation in the solid phase. The investigation made use of approaches based on proton and carbon-13 NMR spectroscopy. The oxidation of squalene and dihydromyrcene in the liquid phase was also studied. The studies provide the first NMR spectroscopic evidence for the presence of epoxy and peroxide, hydroperoxide, and alcohol groups within the oxidized polyisoprene chain.
Experiments were conducted to show that polypentenamer and polyoctenamer, in common with 1,4-polybutadiene, undergo anaerobic thermal cis-trans isomerization at temperatures as low as 200 degrees C. Their activation energies for isomerization are comparable to that of polybutadiene. The relative rate constants are found to decrease in the order: polybutadiene, polypentenamer, polyoctenamer. When heated in a vacuum at 200 to 270 degrees C, polypentenamer exhibits a loss of double bonds. This disappearance of unsaturation has no counterpart in polybutadiene or polyoctenamer. In polypentenamer, a mechanism for a thermally-induced ring closure that is different from the one shown for the cyclization-depolymerization of various unsaturated polymers is evident. The cyclization-depolymerization process does cause a loss of double bonds in polybutadiene and polyoctenamer at temperatures greater than or equal to 275 degrees C.
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Polymers for aircraft and spacecraft structures are considered, giving attention to novel foams and porous structures, aircraft nacelle composite structure technology, properties and processing of polyimidazoquinazoline composites, and the processing of organic matrices into structural composites. Other subjects discussed are related to high temperature resins and composites, elastomers for high temperature applications, fire retardant materials, polymers for critical pollution control, and polymers for critical medical use. Individual items are announced in this issue.
The mechanisms of the direct photochemical reactions which occur in unsaturated polymers when irradiated as thin films in vacuo are reviewed. Important reactions in 1,4-polyisoprene and 1,4-polybutadiene are cis-trans isomerization, loss of 1,4-unsaturation, formation of new external double bonds (vinylidene and/or vinyl units) and cyclopropyl formation. In 1,2-polybutadiene and 3,4-polyisoprene, on the other hand, the main reaction is consumption of the external double bonds through cyclization. Recent work on the photoinduced microstructural changes in cis and trans polypentenamers is also discussed.
Radiation induced photochemical reactions in polyisoprene and polybutadiene thin films including microstructural changes
Photolysis of HCl photosensitized evolution from dichlorobutane in solution by aliphatic ketones
Direct sensitized photolysis of various dichlorobutanes yielding HCl
IR absorption spectra of high-cis forms of deuterated polyisoprenes
Photodecomposition of 1,4-dichlorobutane sensitized by n, pi singlet state of acetone as chemical process
Vacuum ultraviolet irradiation of polybutadiene
Technique for correlation of flight and ground tests of effects of ultraviolet radiation on polymer films