Evidence of a monoclinic-like amorphous phase in composites of LDPE with spherical, fibrous and laminar nanofillers as studied by infrared spectroscopy

Well-dispersed nanocomposites of LDPE with spherical silica and laminar and fibrous silicates have been prepared by melt compounding with nanofiller compositions ranging from 50 to 5 wt%. Spatial dispersion and size domains of the aggregates in the composites series have been evaluated by electron microscopies (SEM and TEM). The methylene rocking (700-740 cm⁻¹) and bending (1400-1480 cm⁻¹) modes of LDPE in these composites were studied by FTIR spectroscopy. When the nanofiller is present in a 40 or 50 wt%, the amorphous phase of polyethylene adopts a monoclinic arrangement. This arrangement is due to the confinement induced by the nanofillers on the polymer matrix. When the fibrous silicate or the spherical silica are used as nanofillers, a dilution of the concentrated composite or annealing bring about a relaxing of the amorphous structure of the polymer, and the monoclinic-like conformations disappear. When the nanofiller is a laminar silicate, dilution or annealing only partly eliminate the monoclinic-like structure, which remains in all cases an important fraction of the polymeric matrix.     

Dynamical conductivity at the dirty superconductor-metal quantum phase transition

We study the transport properties of ultrathin disordered nanowires in the neighborhood of the superconductor-metal quantum phase transition. To this end we combine numerical calculations with analytical strong-disorder renormalization group results. The quantum critical conductivity at zero temperature diverges logarithmically as a function of frequency. In the metallic phase, it obeys activated scaling associated with an infinite-randomness quantum critical point. We extend the scaling theory to higher dimensions and discuss implications for experiments.     

Experimental Determination of the Burning Velocity of Mixtures of n-Heptane and Toluene in Engine-like Conditions

Although the burning velocities of fuel-air mixtures have been extensively studied at room temperature and pressure, there is relatively little experimental information available for elevated temperatures and pressures (the so-called engine like conditions). Therefore, the main aim of the present work is to generate accurate experimental burning velocities valid over a range of high unburned gas temperatures and pressures of a variety of mixtures of n-heptane and toluene, varying its proportion by 25% in volume each time. Two experimental combustion facilities have been used and their results compared. One facility consists of a constant volume cylindrical bomb in which Schlieren images can be recorded and used to calculate the flame front development. The second facility is a spherical combustion bomb with centred ignition in which burning velocities are calculated from pressure records by means of a two-zone model. In order to check that the pressure method is reliable, experiments with n-heptane at room temperature and pressure for different equivalence ratios carried out in the spherical combustion bomb were compared with the ones obtained at the same conditions in the cylindrical vessel equipped with the Schlieren technique. Once the validity has been checked, extensive experiments have been carried out for widely varying initial conditions of pressure between 0.3 and 0.7?MPa, temperature between 363?K and 453?K and equivalence ratios from 0.8 to 1.1. Over the ranges studied, by removing the influence of the ignition energy at the earliest stages of combustion and the quenching effects at the later ones, the burning velocities are fitted by a correlation of type $ Cc=Cc_{r}\cdot (T_{ub}/T_{r})^{\varepsilon }\cdot (P/P_{r})^{\beta } $ , where Cc _r , ?? and ?? depend on the equivalence ratio. The ranges of validity of the correlations obtained cover from 370?K to 700?K, from 0.3?MPa to 4.5?MPa, and from 0.8 to 1.1 equivalence ratio. A comparison with previous predicted values is also given.     

A linear matrix equation: a criterion for block similarity

In this paper we study a homogeneous linear matrix equation related to the block similarity of rectangular matrices. We obtain the dimension of the vector space of its solutions and we describe these solutions. We give a characterization of the block similarity by rank tests. We extend Roth's criterion to the corresponding non homogeneous equation.     

On void time determination in thermal field-flow fractionation

Because of the temperature dependence of the carrier liquid density, the mass of carrier which is contained in a thermal field-flow fractionation channel depends on the cold wall temperature and on the temperature difference across the channel thickness. It is observed that the void time of the solvent peak decreases when increasing the average temperature in the channel. The void time is found to be directly proportional to the average carrier density in the channel. The determination of the void time from the knowledge of the channel geometrical volume and the measurement of the volumetric flow-rate leads to significant errors if the thermal expansion of the carrier between the temperature of the measurement and the average channel temperature is not taken into account. Recommendations are given for proper void time determinations in thermal FFF.     

Synthesis and Diels-Alder reactions of homochiral 2-sulfinylmaleates with cyclopentadiene

Enantiomerically pure 2-p-tolylsulfinylmaleates 1, 2 and 3 have been readily prepared by Knoevenagel reaction between (S)-menthyl p-toluenesulfinate and glyoxylic acid. Their asymmetric Diels-Alder reactions with cyclopentadiene have been studied under a wide range of uncatalyzed and catalyzed conditions and the stereochemical results have been explained by assuming a steric control approach, in term of S-cis or S-trans favoured conformations. Uncatalyzed Diels-Alder reactions of 1 and some Lewis acid catalyzed Diels-Alder reactions of 2 show high facial and endo selectivities. The facial selectivity of dienophile 2 highly depends on the Lewis acid, whereas reactivity of 1 and 3 is very sensitive to the solvent. These sulfinylmaleates 1, 2 and 3 act as synthetic equivalents of chiral acetylenedicarboxylates in Diels-Alder reactions after basic elimination of the sulfinylic moiety in the resulting adducts.     

Role of the interphase dynamics in the induction time of the thermo-oxidation of isotactic polypropylene

This work completes an earlier study on the influence of molar mass and microstructure on the thermal stability of low molar mass isotactic polypropylenes (iPP). The relative dependence of induction time (t_i) on both parameters has been assessed for new metallocene iPP samples (M-PP) with molar masses from 65,000 to 182,000. The new M-PP series includes one metallocene ethylene-propylene copolymer (M-EP) with an ethylene content of 2.6 mol%.When the new t_i data are considered together with those previously reported, neither the molar mass nor the microstructure, taken as sole parameters, is able to explain the global t_i evolution of the M-PP samples.On the basis of the results corresponding to the M-EP copolymer, it is proposed that local chain dynamics occurring at high free volume regions, associated to propylene segment interruptions, play a main role in the ability of the interphase to initiate the oxidation. The correlation of the characteristic interphase chain dynamics, as measured by DMTA, with t_i data supports this suggestion. This hypothesis provides a more unified insight about the actual origin of the iPP thermo-oxidation, as it integrates the influence of parameters which have been found to drive partially the thermal stability of iPP, in particular, molar mass and microstructure.     

电感耦合等离子体原子发射光谱法测定钛酸钡纳米粉体中7种杂质元素

钛酸钡纳米粉体样品用盐酸溶解,在所得样品溶液中用电感耦合等离子体原子发射光谱法测定了以氧化物存在于样品中的7种杂质元素(包括镁、锶、钾、钠、铝、硅及铁),对测定的光谱条件进行了试验并优化达到上述各元素的测定上限为0.1%(质量分数).测得方法的检出限(3S/b)为(单位μg·L-1):2.0(铝),1.0(铁),20.0(钾),0.2(镁),4.0(钠),3.0(硅)及0.5(锶).应用此方法分析了两件实样,所得结果的相对标准偏差(n=6)小于等于2.0%,对其中4种杂质元素(镁、钾、钠和锶)同时用HG/T 3587-1999标准中的方法作分析校核,所得结果与此方法结果一致.