NMR study of the radiation-induced cross-linking of poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether)

The gamma-radiolysis of poly(tetrafluoroethylene-co-perfuoromethyl vinyl ether) (TFE/PMVE) was investigated using solid state F-19 and C-13 NMR spectroscopy. Chain scission products identified in the polymer were saturated chain ends -CF2CF3 (G = 1.0), methyl ether end groups -CF2OCF3 (G = 0.9), acid end groups -CF2COOH (G = 0.5), and a small amount of terminal unsaturation -CF=CF2 (G = 0.2). A mechanism for the formation of these scission products was proposed and the G value for main chain scission, G(S), was determined to be 1.4. Cross-linking of TFE/PMVE was found to proceed via a Y-linking mechanism. The G value for cross-linking, G(X), was determined to be 0.9. A maximum of 0.2 mol % cross-links were formed under the experimental conditions.

Effect of temperature on the gamma-radiolysis of poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether)

The effect of irradiation temperature on the polymer properties was investigated for the fluoroelastomer poly(tetrafluoroethylene-co-perfluoromethylvinyl ether) (TFE/PMVE). TFE/PMVE samples were gamma-irradiated to 150 kGy at temperatures ranging from 77 K to 373 K. Analysis of the sol/gel behaviour, tensile properties, and glass transition temperatures indicated that crosslinking commenced in the temperature range 195 to 263 K, for a dose of 150 kGy. The latter temperature was 13 K below the glass transition temperature. Crosslinking remained relatively constant to higher temperatures. Chain scission reactions were found to occur well below the glass transition temperature and increased at higher temperatures. The optimum temperature for the radiation crosslinking of TFE/PMVE, for the temperatures investigated, was 263 K. (C) 1998 Elsevier Science Ltd. All rights reserved.

Thermal and mechanical properties of radiation crosslinked poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether)

The gamma-radiolysis of poly(tetrafluoroethylene-co-perfluoromethyl vinyl ether) (TFE/PMVE) was investigated using chemical and mechanical analyses. The polymer was found to form an insoluble network with a dose of gelation of 15.8 kGy. Tensile and glass transition temperature measurements indicated the predominance of crosslinking, with optimal elastomeric properties reached in the dose range of 120 to 200 kGy. Photoacoustic FTIR spectroscopy CPAS) showed the formation of new carboxylic acid end groups on irradiation. These new end groups were shown to decrease the thermal oxidative stability of the crosslinked network as determined by thermal gravimetric analysis. Electron spin resonance (ESR) studies of the polymer at 77 K indicated the presence of radical precursors. A G-value of 1.1 was determined for radical production at 77 K. Comparison of radical concentrations for a copolymer with a different mole ratio of PMVE, indicated that the PMVE units contribute to scission reactions. (C) 1998 Elsevier Science Ltd. All rights reserved.

The use of crosslinking promoters in the gamma-radiolysis of poly(tetrafluoroethylene-co-perfluoromethylvinyl ether). I

Incorporation of 1 wt % of triallyl isocyanurate (TAIC) significantly enhanced the radiation crosslinking of the perfluoroelastomer, poly(tetrafluoroethylene-co-perfluoromethylvinyl ether) (TFE/PMVE). The dose for gelation was lowered by 70% with the presence of TAIC. The additive also improved the tensile properties of TFE/ PMVE both before and after crosslinking by irradiation. Higher radical yields were obtained with the presence of TAIC at 77 K, indicating the crosslinking promoter was acting as a radical trap. ESR studies showed that radiolysis of TAIC and subsequent photobleaching cleaved an allyl branch from the ring structure. Upon thermal annealing, an allyl radical on the TAIC molecule was observed. (C) 1999 John Wiley & Sons, Inc.

Polymerization of diglycidyl ether of bisphenol A/diaminodiphenyl sulfone epoxy resins using radio frequency fields

Curing of diglycidyl ether of bisphenol A/diaminodiphenyl sulfone (DGEBA/DDS) epoxy resin has been effected by heating with radio frequency (RF) radiation at frequencies of 30-99 MHz. The epoxy resins can be cured rapidly at low RF power levels. Comparison of the kinetics of the RF curing with thermal curing while maintaining the same curing temperature revealed no differences. Previous differences in rates of thermal and microwave curing are believed to be due to lack of temperature control during microwave curing. For RF curing,the rate of cure, at constant power level, increases at lower RF frequency, thus emphasizing one of the principal advantages of RF curing over microwave curing. (C) 1999 John Wiley & Sons, Inc.

Late-season non-selective herbicide application reduces Lolium rigidum seed numbers, seed viability, and seedling fitness

Experiments were conducted to investigate the effect of Lolium rigidum (annual ryegrass) seed developmental stage and application rate of glyphosate and SpraySeed (paraquat 135 g/L+ diquat 115 g/L) on the number, germinability, and fitness of seeds produced. Glyphosate (450 g/L) was most effective when applied at a rate of 0.5-1 L/ha during heading and anthesis, reducing the number of filled seeds produced compared with unsprayed plants. Application post-anthesis, when seeds were at the milk to soft dough stage, was less effective. SpraySeed was most effective when applied post-anthesis, during the milk and early dough stages of seed development at a rate of 0.5-1L/ha, resulting in the production of few viable seeds. Although some filled seeds were produced, most of the seeds were dead. Application during anthesis or once the seeds reached soft dough stage was less effective. For both herbicides, those seeds that were capable of germinating were smaller and had slower radicle and coleoptile growth, resulting in slower early seedling growth and reduced biomass production within the first month of growth. Additionally, glyphosate application reduced the proportion of seeds exhibiting dormancy. The anticipated reduction in seed competitive ability and altered emergence timing resulting from late-season herbicide application, even when application timing is not optimal, could be exploited to reduce the likelihood of successful L. rigidum establishment in the following season.

An ESR study of irradiated poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA)

Poly(tetrafluoroethylene-co-perfluoropropyl vinyl ether) (PFA) with 2 mol% perfluoropropyl vinyl ether (PPVE) was exposed to gamma -irradiation in vacuum at both 77 K and room temperature and the ESR spectra recorded. Both the main chain, similar to CF2-(CF)-F-.-CF(2)similar to, and end chain, similar to (CF2CF2)-F-. radicals were identified at both temperatures and their thermal stabilities measured, No radicals unique to the radiolytic cleavage at the PPVE units were observed at room temperature, either due to the low concentration of the comonomer or beta -scission to form a chain end radical and a nonradical species. G-values for radical formation at room temperature and 77 K were found to be 0.93 and 0.16, respectively. (C) 2001 Elsevier Science Ltd. All rights reserved.