聚甲基丙烯酸甲酯热氧化降解的化学动力学研究

使用质谱、热分析手段研究了PMMA热解反应 .结果表明 ,在氮气中 ,PMMA -CH =CH2 有两个失重阶段 ,分别对应于主链末端双键引发的断链和主链无规则断链反应 ,转折点的失重率约为 2 6 % .其中 ,第一阶段的失重速率受扩散过程控制 ,平均表观活化能E为 15 8.5kJ/mol,lnA为 2 7.6 9;第二失重阶段为 1.5级化学反应 ,平均表观活化能E为 2 14 .79kJ/mol,lnA为 4 0 .4 6 .在空气中 ,PMMA也有两个失重阶段 ,反应机理为 1级化学反应 ,转折点处的失重率约为 70 % .其中在第一失重阶段平均表观活化能E为 130 .32kJ/mol,lnA为 2 4 .81,在此阶段中 ,过氧化基团的分解反应对PMMA的失重速率有重要影响 ;在空气中第二失重阶段平均表观活化能E为 78.2 5kJ/mol,lnA为 13.97.     

X-ray photoelectron spectroscopy characterization of composite TiO2–poly(vinylidenefluoride) films synthesised for applications in pesticide photocatalytic degradation

X-ray photoelectron spectroscopy (XPS) was adopted for the analytical characterization of composite titanium dioxide–poly(vinylidenefluoride) (TiO₂–PVDF) films developed for applications in the photocatalytic degradation of pollutants.

The composites were deposited on glass substrates by casting or spin coating from TiO₂–PVDF suspensions in dimethylformamide (DMF). XPS data on the TiO₂–PVDF surface composition were used to optimize preparation conditions (composition of the TiO₂/PVDF suspension, deposition technique) in terms of titanium dioxide surface amount and film stability.

The use of spin-coating deposition and the increase of TiO₂ amount in the DMF suspensions were found to improve the titanium surface content, although high TiO₂/PVDF ratios led to film instability. PVDF–TiO₂ films were also used in preliminary photocatalytic degradation tests on isoproturon, a phenylurea herbicide, under solar UV irradiation; the results were compared to direct photolysis to evaluate the catalytic efficiency of immobilized TiO₂ and the role played by the PVDF film during the degradation process.     

Quantum topological excitations: from the sawtooth lattice to the Heisenberg chain

From the recently determined structure of the delafossite YCuO_2.5, we argue that the Cu-O network has nearly independent Δ chains but with different interactions between the s = 1/2 spins. Motivated by this observation, we study the Δ chain for different ratios of the base-base and base-vertex interactions, J _bb/J _bv. By exact diagonalization and extrapolation, we show that the elementary excitation spectrum is the same for total spins S _tot = 0 and 1, but not for S _tot = 2, and has a gap only in the interval 0.4874(1) ⩽ J _bb/J _bv ⩽ 1.53(1). The gap, known to be dispersionless for J _bb = J _bv, is found to acquire increasing k-dependence as J _bb/J _bv moves away from unity. Received 29 October 2002 / Received in final form 14 January 2003 Published online 6 March 2003 RID="a" ID="a"e-mail: sblundell@cea.fr RID="b" ID="b"e-mail: nunezreg@lps.u-psud.fr     

Heat of adsorption and density distribution in slit pores with defective walls: GCMC simulation studies and comparison with experimental data

The adsorption behavior (capacity, density distribution and packing density) and the isosteric heat versus loading in a slit pore whose walls contain defective graphene layers are investigated in this paper. The defective wall is characterized by the extent and size of the defect. Simulation results obtained with the Grand Canonical Monte Carlo method reveal complex patterns of isosteric heat, and this complex behavior is a result of the interplay between three factors: (i) the surface heterogeneity (solid-fluid interaction, sites with varying degree of affinity), (ii) fluid-fluid interaction and (iii) the overlapping of potentials exerted by the two defective walls. We illustrate this with argon adsorption in pores of various sizes, and results obtained from the simulation agree qualitatively with the experimental data at 77 K on Saran microporous S600H and micro-mesoporous S84 charcoals of Beebe et al. [R.A. Beebe, B. Millard, J. Cynarski, J. Am. Chem. Soc. 75 (1953) 839]. The S600H was found to contain pores predominantly in the neighborhood of 7 Å with 30% of defect and a defective size of 2.84 Å. This is consistent with the argument made by Beebe et al. that this sample is a microporous solid and most pores can accommodate only one layer. The other sample, S84, has larger pores than S600H, and it is found that it has a wider pore size distribution and the pore width is centered at about 12 Å.     

Micro‐Raman and stratigraphic studies of the paintings on the ‘Cembalo’ model musical instrument (A.D. 1650) and laser‐induced degradation of the detected pigments

Micro‐fragments of the painted part of the ‘Cembalo’ model by Michele Todini (1625–1689) are investigated. The technique used for painting the terracotta base was studied via the stratigraphic analyses. No background layer of inorganic materials, e.g. gypsum, was found. To prevent absorption effects due to the terracotta porosity, a very thin layer of proteinaceous material was probably used. The micro‐Raman analyses have revealed the use of pigments currently used in the post‐Renaissance period (lead white, indigo, yellow of iron hydroxide, gypsum, hematite and carbon black) mixed with a pigment, the Prussian blue, discovered in A.D . 1704. This raises the authenticity problem of the work of art, a problem analysed and discussed in presenting the history of the work of art, and after the pigment study. The presence of degraded lead white is recognized via the laser‐induced degradation of the irradiated material. The possibility of a restoring action of the painted parts, as opposite to the non‐originality of the work, is considered and discussed. Since most part of the investigated pigments shows laser‐induced effects, a careful study of this phenomenon is performed by using the modern counterparts of the ancient pigments. For different laser powers, the temperatures of the investigated zones have been obtained via the detailed balance principle and connected to the laser‐induced degradation effects. Copyright © 2007 John Wiley & Sons, Ltd.     

Reentrant isotropic-calamitic nematic phase transition in potassium laurate-decanol- D<Subscript>2</Subscript>O mixtures

The phase diagram is an interesting field of research, particularly in lyotropic liquid crystals (LLC). In this way, one of the most important phase diagrams of this LLC system was reported by Yu and Saupe. Two uniaxial (calamitic--N(C) and discotic--N(D)) and one biaxial nematic (N(B)) phases were determined by these authors. Furthermore, in this phase diagram the classical isotropic phase (I was observed at high temperature as well as a reentrant isotropic phase (I(RE)) which takes place at lower temperature. Later, this phase diagram was also studied by several authors and in all cases the I(RE)-N(C)-I phase transitions were not observed. In this work, we present a study of this phase diagram through digital image processing and refractometry optical techniques. The occurrence of these phase transitions is investigated and characterized. In addition, the order parameter is obtained based on the Vuks hypothesis from a particular point, in the range of the N(C) phase, where the absolute value of the optical birefringence (Deltan is maximum.     

聚四氟乙烯的辐射效应及其ESR研究

该文回顾了从上世纪50年代中期至近年来人们在聚四氟乙烯（PTFE）辐射效应方面的研究工作,初步总结了辐射PTFE产生的自由基及其相应的过氧化自由基的电子自旋共振（ESR）波谱学应用研究,总结并讨论了实验温度、辐射剂量、PTFE粉末形式、结晶度和交联等因素对辐射PTFE自由基ESR信号的影响. 同时还简要介绍了辐射PTFE后的自由基反应以及辐射交联的进展情况.     

Degradation of 4-chloro 2-aminophenol using combined strategies based on ultrasound,photolysis and ozone

The present work investigates the degradation of 4-chloro 2-aminophenol (4C2AP), a highly toxic organic compound, using ultrasonic reactors and combination of ultrasound with photolysis and ozonation for the first time. Two types of ultrasonic reactors viz. ultrasonic horn and ultrasonic bath operating at frequency of 20 kHz and 36 kHz respectively have been used in the work. The effect of initial pH, temperature and power dissipation of the ultrasonic horn on the degradation rate has been investigated. The established optimum parameters of initial pH as 6 (natural pH of the aqueous solution) and temperature as 30 ± 2 °C were then used in the degradation studies using the combined approaches. Kinetic study revealed that degradation of 4C2AP followed first order kinetics for all the treatment approaches investigated in the present work. It has been established that US + UV + O₃ combined process was the most promising method giving maximum degradation of 4C2AP in both ultrasonic horn (complete removal) and bath (89.9%) with synergistic index as 1.98 and 1.29 respectively. The cavitational yield of ultrasonic bath was found to be eighteen times higher as compared to ultrasonic horn implying that configurations with higher overall areas of transducers would be better selection for large scale treatment. Overall, the work has clearly demonstrated that combined approaches could synergistically remove the toxic pollutant (4C2AP).     

Ultrasonic-assisted degradation of phenazopyridine with a combination of Sm-doped ZnO nanoparticles and inorganic oxidants

Pure and samarium doped ZnO nanoparticles were synthesized by a sonochemical method and characterized by TEM, SEM, EDX, XRD, Pl, and DRS techniques. The average crystallite size of pure and Sm-doped ZnO nanoparticles was about 20 nm. The sonocatalytic activity of pure and Sm-doped ZnO nanoparticles was considered toward degradation of phenazopyridine as a model organic contaminant. The Sm-doped ZnO nanoparticles with Sm concentration of 0.4 mol% indicated a higher sonocatalytic activity (59%) than the pure ZnO (51%) and other Sm-doped ZnO nanoparticles. It was believed that Sm³⁺ ion with optimal concentration (0.4 mol%) can act as superficial trapping for electrons in the conduction band of ZnO and delayed the recombination of charge carriers. The influence of the nature and concentration of various oxidants, including periodate, hydrogen peroxide, peroxymonosulfate, and peroxydisulfate on the sonocatalytic activity of Sm-doped ZnO nanoparticles was studied. The influence of the oxidants concentration (0.2–1.4 g L⁻¹) on the degradation rate was established by the 3D response surface and the 2D contour plots. The results demonstrated that the utilizing of oxidants in combination with Sm-doped ZnO resulting in rapid removal of contaminant, which can be referable to a dual role of oxidants; (i) scavenging the generated electrons in the conduction band of ZnO and (ii) creating highly reactive radical species under ultrasonic irradiation. It was found that the Sm-doped ZnO and periodate combination is the most efficient catalytic system under ultrasonic irradiation.     

Domain wall delocalization,dynamics and fluctuations in an exclusion process with two internal states

We investigate the delocalization transition appearing in an exclusion process with two internal states, respectively on two parallel lanes. At the transition, delocalized domain walls form in the density profiles of both internal states, in agreement with a mean-field approach. Remarkably, the topology of the system’s phase diagram allows for the delocalization of a (localized) domain wall when approaching the transition. We quantify the domain wall’s delocalization close to the transition by analytic results obtained within the framework of the domain wall picture. Power law dependences of the domain wall width on the distance to the delocalization transition as well as on the system size are uncovered, they agree with numerical results.