Physico-chemical aspects of polyethylene processing in an open mixer. Part 26: Formal kinetics of aldehyde and carboxylic acid formation at a constant rate

Formation of carboxylic acids at a constant rate can be easily explained. It seems to result from the formation and decomposition of α,γ-keto-hydroperoxides. Formal kinetics based on formation and decomposition of these structural units is in agreement with the experimental findings. The activation energy deduced from the calculations is negligible, in agreement with the experimental data showing the constant rate to be practically temperature independent. Comparison of the acids with the hydroperoxides and ketones formed initially shows that the rate of oxygen addition to alkyl radicals is significantly smaller than in low molecular mass liquids. The same conclusion is reached on comparing directly the acids formed on decomposition of α,γ-keto-hydroperoxides in polyethylene melt and in hexadecane. The rate of oxygen addition in polyethylene melt is closer to 2 × 10⁵ than to 6 × 10⁵ (s⁻¹) that is valid in hexadecane.It is possible to attribute the relatively small amount of aldehydes that might be formed at a constant rate to different reactions of alkoxy radicals that are not in a cage with other radicals. These alkoxy radicals result from the addition of peroxy radicals to unsaturated bonds. This addition is followed mainly by epoxide formation and simultaneous release of an alkoxy radical.     

Radiolytic unsaturation decay in polyethylene. Part III—the effect of certain chain transfer agents

Small amounts of certain halogenated compounds are found to have, at most, only a slight enhancing effect on the radiolytic decay rates of added poly-unsaturated compounds in polyethylene, but significantly increase the elastic modulus at 433 K (melt modulus) obtained thereby. Experiments with model chlorine-containing additives suggest that this increase is due to a more random distribution of polymer and monomer mediated crosslinks in the polymer, that it does not result from a significant increase in crosslinking and that it is mediated by chlorine atoms, in a similar manner to radiolytic hydrogen atoms, through facilitation of long range free radical migration. Although low molecular weight chloro-paraffins inhibit radiolytically induced growth of melt modulus in monomer containing polyethylenes, even very small additions of chlorinated polyethylenes, which form a separate phase, increase the melt modulus. This again indicates that the active species is the chlorine radical.     

High power CW solid-state multilaser system

A laser system containing four CW Nd:YAG double-rod lasers, transforming optics and a fibre with input-output optics has been designed and investigated. It is shown that reduction of the beam parameter product of the non-Gaussian beams in the image space of the lens has made it possible to collect the emission of four lasers to the same fibre. Independent laser operation has provided the output power control in the range of 10–900 W with a stable light spot size on the input end of the fibre.     

Physico-chemical aspects of polyethylene processing in an open mixer. Part 29: Experimental kinetics and mechanisms of γ-lactone formation

The experimental kinetics for γ-lactone formation shows more complexity than that for acids. Nonetheless, it can be concluded to the existence of a constant rate of formation from the beginning of the experiments with polyethylene melts. There is an additional term contributing to γ-lactone formation in the initial stages that is cubic in processing time. In the advanced stages of processing, in the high temperature range (170-200 °C), the concentration of γ-lactones increases linearly with the processing time.There are many mechanisms susceptible to give γ-lactones on polyethylene melt processing. Some of them are based on decomposition of intermediates formed directly on chain propagation. This is so for the α,γ-keto-hydroperoxides in 4-position to hydroxyl groups. Since decomposition of these intermediates is very fast, the reaction might account for a constant rate of γ-lactone formation from the beginning of polyethylene processing. Decomposition of the α,δ-keto-hydroperoxides formed on intramolecular reactions on chain propagation is not so fast as that of the α,γ-keto-hydroperoxides. Nonetheless, it might account for part of the delayed formation of γ-lactones. The same is valid for the mechanisms based on peroxidation of aldehydes and γ-hydroxy trans-vinylene groups that involve intermediates that are formed on polyethylene peroxidation. They might be important for explaining the cubic term as well as γ-lactone formation in the advanced stages of polyethylene processing.     

An optical fibre pH sensor based on dye doped mesostructured silica

This paper describes the synthesis and optical pH sensing properties of a pH indicator dye activated mesostructured silica coated optical fibre. The pH-sensitive dye bromothymol blue was incorporated into the mesostructure sol precursor and thin films/coatings were used for pH-sensing applications without prior removal of the surfactant. The pH sensitivity range and operating wavelength were analysed by absorption measurements on layer dip-coated on glass slides. The pH sensing properties of coated optical fibre were tested by evanescent wave method. Experiments were carried out by using a series of solutions of known pH. No leaching was observed (except at very high pH) and an excellent reversibility was obtained between pH=2 and 5.     

Low noise double pass L-band erbium-doped fiber amplifier

A new double pass long wavelength band erbium-doped fiber amplifier with enhanced noise figure characteristics is demonstrated. The noise figure is improved by about 2.6 dB with the incorporation of broadband conventional-band fiber Bragg grating (FBG) in between the two segments of erbium-doped fiber. By incorporating both the pre-amplifier and the FBG, the noise figure is further improved, which varies from 4.0 to 5.0 dB in the flat gain region from 1570 to 1600 nm. The gain varies from 32.0 to 33.4 dB within this region. The new amplifier with high gain and low noise figure can be useful as an inline amplifier in a wavelength division multiplexing transmission system.     

Controlling the gain shape of Er^3＋—doped fluorozirconate fibre amplifier by a coherent field

We proposed a four-level system to explore the quantum interference effects on optical amplification.We found that the gain of the probe.including positions and values of gain peaks,can be adjusted by changing the coherent field and the incoherent pumping.At the same time,we can also modify the absorption profile of electromagnetically induced transparency by the incoherent pump.The results provide a method to flatten the gain of Erbium-doped fibre amplifiers.     

Size exclusion chromatographic determination of hydroxypropyl methyl cellulose and polyethylene glycol 400 in an ophthalmic solution

Summary Hydroxypropyl methyl cellulose (HPMC) and polyethylene glycol 400 (PEG 400) content in HypoTears™ Daily Dose ophthalmic solution are determined simultaneously by size exclusion chromatography. The retention times of HPMC and PEG 400 are 10.6 and 15.4 minutes, respectively. The method requires minimal sample pretreatment and is accurate and reproducible. The peak area response from a refractive index detector versus HPMC and PEG 400 concentration is linear over the range of 50–150 % of their label claims of 2.5 mg/mL and 10 mg/mL, respectively. The mean absolute recoveries of HPMC and PEG 400 at their label claim using the described method are 98.9±1.3 % and 100.4±1.2 % (mean±SD, n=12), respectively.     

RPS增容LDPE／PS研究

用ＨＡＡＫＥ、ＤＳＣ、ＩＲ等方法研究了侧基含有过氧键的反聚苯乙烯与ＬＤＰＥ之间的反应，并将其应用到ＬＤＰＥ／ＰＳ共混体系。考察了不同添加方式，交联助剂等对共混物力学性能、流变性能及微观结构的影响。     

A telescope illumination system for a wide-field endoscope

Endoscopic illumination systems conduct light down a built-in fibre-optic bundle to illuminate the object. Many modern endoscopes employ wide-field imaging optical systems and therefore require an illuminating beam of large divergence. This is commonly provided by placing a strong diverging lens at the far end of the fibre bundle, but it results in a poor uniformity of illumination in the object space. This paper describes the design of a telescopic illumination system to overcome this problem.