XNBR/LDH nanocomposites: Effect of vulcanization and organic modifier on nanofiller dispersion and strain‐induced crystallization

In elastomer/organo clay nanocomposites, the morphological characteristics, and hence the mechanical properties, of the vulcanizates are strongly influenced by the organic modifier and the vulcanization process. When the elastomer itself undergoes strain‐induced crystallization, both the organic modifier and the dispersed filler particles could significantly influence the crystallization process. These phenomena are very common in case of natural rubber‐based vulcanizates. In this study, the similar effects have been demonstrated with carboxylated nitrile rubber (XNBR) and organically modified layered double hydroxide (O‐LDH)‐based nanocomposites. The effect of size of the organic modifier was obviously visible on the interlayer distance of O‐LDH and also on the morphological reorganization of the dispersed O‐LDH particles during vulcanization process. The strain‐induced crystallization of the XNBR was found to be strongly dependent on the morphological change that occurs during vulcanization process. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Generation and characterization of low‐energy structures in atomic clusters

Factors relevant for controlling the structures determined in the local optimization of argon clusters are investigated. In particular, the role of volume and shape for the box where initial structures are generated is assessed. A thorough characterization of the optimization is also presented, based on a nearest‐neighbor analysis, in clusters ranging from 30 to 55 atoms. This includes the assessment of the degree of preservation of aspects of the initial randomly generated structure in the final optimized counterpart, and the correlation between optimized energy and the number of nearest neighbors and average departure from the diatomic reference distance. The usefulness of this analysis to explore the energy landscape of atomic clusters is also highlighted. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010     

Toward multipurpose NMR experiments

Standard phase cycled NMR pulse sequences were generalized such that for each individual step of the pulse phase cycle the free induction decay is stored separately without phase correction. This is in contrast to the usual practice, where pulse responses are phase shifted immediately (by applying a ‘receiver phase’) and co‐added as they are stored. The approach used here allows one to extract different types of NMR information, which are usually referred to as different ‘experiments’, from the same raw data set a posteriori by using complex linear combinations. Storing the free induction decays of individual phase cycle steps separately and using specific linear combinations of these data to obtain a particular type of information increase the overall efficiency of a given set of NMR experiments substantially, because all information can be derived from a single multiplexed data set. This ‘super‐experiment’ requires only as much time as the most complex of the derived specific experiments alone. The principle of this multipurpose approach was demonstrated by performing different multiple‐quantum filtered COSY experiments. It also becomes possible to generate linear combinations, which differ from the conventionally acquired spectra a posteriori. For example, we implemented diagonal peak reduction by using zero‐ and single‐quantum filtered COSY contributions without requiring additional experiment time. Copyright © 2009 John Wiley & Sons, Ltd.     

Advantages of using a modified orthogonal sampling configuration originally designed for LC-ESI-MS to couple CE and MS for the determination of antioxidant phenolic compounds found in virgin olive oil

A ThermoFinnigan sheath liquid flow capillary electrophoresis-mass spectrometry system designed for coupling via a co-axial interface was coupled through an adapted via an alternative, commercially available interface for orthogonal sampling. The affordable, reversible structural alterations made in the commercial LC-MS interface resulted in improved analytical performance.The results of a conventional capillary electrophoresis (CE) method using a commercial co-axial source to determine antioxidant phenolic acids present in virgin olive oil, were compared with those obtained by using a modified orthogonal sampling position. In both cases, separations were done using a 10 mM ammonium acetate/ammonium hydroxide buffer solution at pH 10.0 and a constant applied voltage of 25 kV. The operating variables for the mass spectrometry interface were re-optimized for the modified orthogonal orientation. This allowed the sheath liquid, sheath gas flow rates and capillary voltage to be lowered with respect to the co-axial coupling configuration. In addition, the orthogonal sampling position provided a higher selectivity by effect of ion sampling excluding larger droplets—with an increased momentum along the axis—which were drained through the sink at the bottom of the ion source. Also, the new configuration facilitated sample ionization, improved electrospray stability and led to stronger signals as a result.The new system was validated in terms of precision (repeatability), linearity, and limits of detection and quantification. A comparison of the validation data with the results previously obtained by using a commercial co-axial configuration revealed the adapted orthogonal sampling position to provide better repeatability in both migration times and relative peak areas (<1% and 7% respectively with n = 15 replicates), a good linear range (with levels in the microgram-per-litre region) and lower limits of detection—especially for the compounds detected with the lowest sensitivity when co-axial ESI was used, as HFA, GEN, FER and VAN finding LOD among 24-3.0 μg L⁻¹ respectively.     

Resolution method for overlapping peaks based on the fractional-order differential

Equations between the differential order and the maximum of the fractional-order differential for the specified peak signals are developed based on the variation of the maximum of the specified peak signals at different orders. Also, equations between the differential order and the zero-crossing of the fractional-order differential of the specified peak signals are proposed according to the variation of the zero-crossing of the specified peak signals at different orders. Characteristic paramters of the Gaus- sian peak, Lorentzian peak, and Tsallis peak can be estimated using estimator I and estimator II which are obtained by the equations above. As a result, a new method is presented to resolve the overlapped peaks signal. Firstly, a fractional-order differential of the specified peak signals is obtained with the fractional-order differentiation filter. Then, characteristic paramters of the specified peak signals can be extracted using estimator I and estimator II. Finally, the Tsallis peak is used as a model to assign the overlapping peak signals correctly. Experimental results show that the proposed method is efficient and effective for the simulated overlapping peaks and detected overlapping voltammetric peak signals.     

Morphology,surface roughness,electron inelastic and quasielastic scattering in elastic peak electron spectroscopy of polymers

In elastic peak electron spectroscopy (EPES), the nearest vicinity of elastic peak in the low kinetic energy region reflects electron inelastic and quasielastic processes. Incident electrons produce surface excitations, inducing surface plasmons, with the corresponding loss peaks separated by 1–20 eV energy from the elastic peak. In this work, X‐ray photoelectron spectroscopy (XPS) and helium pycnometry are applied for determining surface atomic composition and bulk density, whereas atomic force microscopy (AFM) is applied for determining surface morphology and roughness. The component due to electron recoil on hydrogen atoms can be observed in EPES spectra for selected primary electron energies. Simulations of EPES predict a larger contribution of the hydrogen component than observed experimentally, where hydrogen deficiency is observed. Elastic peak intensity is influenced more strongly by surface morphology (roughness and porosity) than by surface excitations and quasielastic scattering of electrons by hydrogen atoms. Copyright © 2007 John Wiley & Sons, Ltd.     

~(12)CO_2/~(13)CO_2体系中碳同位素的显微激光拉曼光谱研究

采用自行设计的装置制备了一系列不同比例的12CO2/13 CO2混合物,对混合物样品进行显微激光拉曼测试,获得CO2气体碳同位素分子的拉曼特征峰。对实验数据分析发现,12CO2的摩尔分数[x(12CO2)]与12CO2/13 CO2混合物中拉曼特征峰峰面积比之间存在数学关系式。根据拟合的关系式,利用显微激光拉曼光谱可以预测CO2气体碳同位素的组成,并为以后预测单个流体包裹体中12CO2的摩尔分数奠定了理论基础。     

Crack Toughness Behaviour of Multiwalled Carbon Nanotube (MWNT)/Polycarbonate Nanocomposites

Summary: The morphology and fracture behaviour of polycarbonate (PC)/multiwalled carbon nanotube (MWNT) composites have been studied by AFM and post‐yield fracture mechanics. The essential work of fracture (EWF) method has been used to distinguish between two terms representing the resistance to crack initiation and crack propagation. A maximum in the non‐essential work of fracture was observed at 2 wt.‐% MWNT, demonstrating enhanced resistance to crack propagation compared to pure PC. At 4 wt.‐% MWNT, a tough‐to‐brittle transition has been observed. The time‐resolved in‐situ strain field analysis revealed that the onset of crack initiation was shifted to a shorter time for nanocomposites with 4 wt.‐% MWNT compared to that with 2 wt.‐%, and thus explained the existence of a tough‐to‐brittle transition in these nanocomposites.

     

Modeling of Shape Memory Induction and Recovery in Heat‐Shrinkable Polymers

Summary: A mechanical model was developed to describe qualitatively and quantitatively the stress‐strain‐time behavior of a prepared shape memory crosslinked polyethylene during hot stretching, stress relaxation under 200% strain at high temperature and strain recovery of the heat shrinkable polymer. The stress‐strain, the stress relaxation and the irrecoverable strain behavior of the model were established by driving the constitutive equation, which could qualitatively represent the behavior of the real material. By choosing significant values for the parameters of the proposed model, an excellent fit was obtained between the experimental behavior of the polymer and that predicted by the model. It was also revealed that the main source responsible for the imperfect recovery of the induced strain observed was the stress relaxation occurring during the stretch holding‐cooling time step.

Stress relaxation of crosslinked polyethylene under 200% strain at 160 °C.     

Theoretical study of structure and stability of fullerene derivative: C50O

A total of eight possible isomers of C₅₀O, an oxide of fullerene C₅₀ (D_5h), have been investigated by B3LYP/3‐21G calculations. The isomer, which has an annulene‐like structure with oxygen bridging across a [5,6] type C? C bond at the site between the pole and the equatorial belt, is found being the ground state of C₅₀O. Four isomers are relatively more stable and the energy differences between them are not large. This result indicates that more than one C₅₀O isomer will coexist once C₅₀O is synthesized. The relative stabilities of the C₅₀O isomers may be determined mainly by the strain release and by the formation of the cyclic phenylene substructure at the equatorial belt of the cage. The calculated nucleus independent chemical shifts (NICS) of the C₅₀O isomers will be useful because from them one can expect outstanding NMR properties that can lead to their identification and characterization. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005