Melting Point and Composition Distribution of Polyolefins by Fractionation

The fractionation technique described in this paper was used to characterize the melting-point, monomer, and blocking distributions for polymers and copolymers. It is different from the molecular-weight fractionation technique in that the fractions are obtained by using a single solvent to extract the solid polymer below its melting point at stepwise-increasing temperatures. The reproducibility of this technique is excellent, and the technique is sufficient to distinguish pellet-to-pellet variation in a commercially available polypropylene. It was used to show the influence of preparation variables on the melting-point distributions of polyethylene and polypropylene and on the monomer and blocking distribution of copolymers, and to distinguish copolymers from blends.     

连续波锁模Pr3+:YLF激光器

本文报导了采用氩离子激光器来泵浦Pr³⁺:YLF晶体,应用声光调制器实现了主动锁模;同时应用振动─高反射平面镜也实现了被动锁模,两种锁模均得到了ps光脉冲.据作者了解这是这种晶体材料的第一次锁模运转.     

THE AVAILABILITY OF SOLAR RADIATION BELOW 290 nm AND ITS IMPORTANCE IN PHOTOMODIFICATION OF POLYMERS

Abstract— On a percentage basis, ozone is a very minor component of the atmosphere; at STP it would make a layer only about 2 mm thick. On almost every other basis (biological, meteorological, paleontological, photochemical, etc.) it is a major component, due mainly to the tremendous reduction in solar ultraviolet flux which it causes in the 220–290 nm region. Since no data are available for Λ < 285 nm, a rational basis for estimating the flux reaching the earth's surface in this region is discussed. Variations in ozone concentration are of great importance, and it is possible to have more radiation with Λ < 270 nm fall on a surface in one extreme day than in several years of typical days. Often, persons involved in studies of polymer degradation by sunlight mention that a negligible fraction (1 ppm) of the radiant flux reaching the earth's surface is associated with wavelengths below 290 nm and infer that studies at shorter wavelengths will not be of much practical value. Such inferences are questionable for at least two reasons. (1) The quantum flux density below 290 nm is about 10¹⁶ photons cm^-2 month^-1, so that considerable long-term damage is possible since most of the flux will be absorbed in a layer only a few microns thick. (2) Even if solar radiation below 290 nm were completely absent, the existence of correlations between absorption peaks in the near ultraviolet and visible, and in the infrared with ionization potentials typically 6–12 eV or 200-100 nm) is evidence that we may expect studies in the ultraviolet and extreme ultraviolet (EUV) to provide important clues to the problem of improving the resistance of polymers to sunlight.     

CHANGES IN TOTAL DIFFUSE SPECTRAL REFLECTANCE OF AMINO ACIDS AND PROTEINS AFTER ULTRAVIOLET IRRADIATION

Abstract— Total diffuse reflectance spectra of air-dried surfaces of free and neutralized amino acid preparations before and after irradiation in vitro are reported. It was found that some free or neutralized amino acid surfaces underwent modification which resulted in changes in the diffuse reflectance spectra after U.V. exposure. It is suggested that these reflectance changes result from transformations in the side chains of the amino acids and that the transformations may differ from those occurring when amino acids in solution are irradiated. Histidine, cystine, hydroxyproline and some protein surfaces showed changes in reflectance of 330–400 nm light similar to those reported in skin after U.V. irradiation in viuo.     

Solubility and partial molar volume of carbon dioxide and ethane in crosslinked poly(ethylene oxide) copolymer

Experimental solubility and sorptive dilation data are reported for carbon dioxide and ethane in a crosslinked poly(ethylene oxide) (XLPEO) rubbery copolymer. Five different temperatures (253 ≤ T(K) ≤ 308) were considered, with a maximum gas pressure of 2.09 MPa (20.6 atm). The polymer was prepared by photopolymerization of a solution containing 70 wt % poly(ethylene glycol) methyl ether acrylate (PEGMEA) and 30 wt % poly(ethylene glycol) diacrylate (PEGDA). Sorption isotherms were described by the Flory‐Huggins model. For each gas, the Flory‐Huggins interaction parameter was a decreasing function of temperature and did not show a composition dependence. Dilation and sorption data were combined to calculate the partial molar volume (PMV) of the gases in the polymer, which was an increasing function of temperature. Based on a comparison with literature data for a XLPEO homopolymer prepared from pure PEGDA over the same range of operating conditions, an effect of the network composition on both gas solubility and PMV was found. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 456–468, 2010     

EFFECT OF ULTRAVIOLET RADIATION ON THE ENERGY METABOLISM OF THE CORNEAL EPITHELIUM OF THE RABBIT

The present research was directed at quantifying possible alterations in corneal epithelial metabolic activity secondary to in vivo exposure to ultraviolet radiation (UVR). Microfluorometric energy metabolite assays on microgram (microgram) sized, freeze-dried tissue samples were used as an in vitro means of assessing overall metabolic activity in the epithelium of control rabbit corneas and in the epithelium of UVR-exposed rabbit corneas 2 min after discontinuation of exposure. The specific assays were for glucose, glycogen, adenosine triphosphate (ATP), and phosphocreatine (PCr). The radiant exposures were kept constant at 0.05 J cm-2 for all UVR wavelengths utilized (290, 300, 310 and 360 nm). Experimental UVR exposure conditions served to increase epithelial glucose and glycogen concentrations. Although the epithelial ATP concentrations were unchanged, the epithelial PCr concentrations (a high energy phosphate bond reservoir) decreased as a result of UVR exposure. Overall, the data demonstrate a decrease in corneal epithelial metabolic activity, which may be wavelength-dependent, as a result of UVR exposure. It is suggested that immediate metabolic stress can be responsible for the pattern of epithelial cell loss seen in photokeratitis.     

Laser Mass Spectrometry of Organophosphorus Pesticides and Related Compounds

Abstract

Laser mass spectra obtained for 20 organophosphorus (OP) compounds were systematically evaluated for groups containing analogous structural features. Variations in fragmentation can be understood based on simple organic reactions. While detailed mechanistic interpretations of the laser mass spectra (LMS) were not possible, the qualitative features in the LMS obtained from five compounds, not in the original set, could be predicted based on the characteristics of the other OP compounds studied. The success of the prediction lends credence to the qualitative models developed for rationalizing the LMS. A specific feature in the LMS of aromatic thionophosphates is a thiono-thiolo rearrangement. Detailed investigation into the phenomena involved comparison of LMS obtained from aromatic thionophosphates with spectra from electron impact, chemical ionization, field desorption, and secondary ion mass spectrometry. These results led to the conclusion that the rearrangement in laser mass spectrometry must occur during volatilization while the molecule/ion is in the “cloud” present immediately above the laser impact area.