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971.
We address crystal nucleation and fcc-bcc phase selection in alloys using a multiphase field model that relies on Ginzburg-Landau free energies of the liquid-fcc, liquid-bcc, and fcc-bcc subsystems, and determine the properties of the nuclei as a function of composition, temperature, and structure. With a realistic choice for the free energy of the fcc-bcc interface, the model predicts well the fcc-bcc phase-selection boundary in the Fe-Ni system. 相似文献
972.
973.
Cresswell AJ Davies SG Lee JA Morris MJ Roberts PM Thomson JE 《The Journal of organic chemistry》2011,76(11):4617-4627
Treatment of a range of 2,3- and 3,4-epoxy amines with HBF(4)·OEt(2) at room temperature results in fast and efficient S(N)2-type ring-opening hydrofluorination to give stereodefined amino fluorohydrins. Operational simplicity, scalability, and short reaction time at ambient temperature are notable features of this method. The utility of this methodology is exemplified in a concise asymmetric synthesis of (S,S)-3-deoxy-3-fluorosafingol. 相似文献
974.
Examination of the role of base in the activation of our previously reported iron(II) complexes having the general formula [Fe(CO)(Br)(PNNP)][BPh(4)] revealed a five-coordinate iron(II) complex in which the tetradentate PNNP ligand had been doubly deprotonated. The new iron(II) complexes were used in the transfer hydrogenation of acetophenone in isopropanol in the absence of added base, and certain analogues showed catalytic activity. 相似文献
975.
Morris GD Neethling SJ Cilliers JJ 《Langmuir : the ACS journal of surfaces and colloids》2011,27(18):11475-11480
Particle stabilized thin films occur in a range of industrial applications where their properties affect the efficiency of the process concerned. However, due to their dynamic and unstable nature they are difficult to observe experimentally. As such, a tractable way of gaining insight into the fundamental aspects of this complicated system is to use computer simulations of particles at interfaces. This paper presents modeling results of the effect of nonuniform packing of spherical particles on the stability of thin liquid films. Surface Evolver was used to model cells containing up to 20 particles, randomly packed in a thin liquid film. The capillary pressure required to rupture the film for a specific combination of particle arrangement, packing density, and contact angle was identified. The data from the periodic, randomly packed models has been used to find a relationship between particle packing density, contact angle, and critical capillary pressure which is refined to a simple equation that depends on the film loading and contact angle of the particles it contains. The critical capillary pressure for film rupture obeys the same trends observed for particles in regular 2D and 3D packing arrangements. The absolute values of P*(crit), however, are consistently lower than those for regular packing. This is due to the irregular arrangement of the particles, which allows for larger areas of free film to exist, lowering the critical capillary pressure required to rupture the film. 相似文献
976.
Chen ZP Li LM Yu RQ Littlejohn D Nordon A Morris J Dann AS Jeffkins PA Richardson MD Stimpson SL 《The Analyst》2011,136(1):98-106
The development of reliable multivariate calibration models for spectroscopic instruments in on-line/in-line monitoring of chemical and bio-chemical processes is generally difficult, time-consuming and costly. Therefore, it is preferable if calibration models can be used for an extended period, without the need to replace them. However, in many process applications, changes in the instrumental response (e.g. owing to a change of spectrometer) or variations in the measurement conditions (e.g. a change in temperature) can cause a multivariate calibration model to become invalid. In this contribution, a new method, systematic prediction error correction (SPEC), has been developed to maintain the predictive abilities of multivariate calibration models when e.g. the spectrometer or measurement conditions are altered. The performance of the method has been tested on two NIR data sets (one with changes in instrumental responses, the other with variations in experimental conditions) and the outcomes compared with those of some popular methods, i.e. global PLS, univariate slope and bias correction (SBC) and piecewise direct standardization (PDS). The results show that SPEC achieves satisfactory analyte predictions with significantly lower RMSEP values than global PLS and SBC for both data sets, even when only a few standardization samples are used. Furthermore, SPEC is simple to implement and requires less information than PDS, which offers advantages for applications with limited data. 相似文献
977.
During the development of automated computational methods to detect minute compositional changes in fuels, it became apparent that peak selection through the spectral deconvolution of gas chromatography-mass spectrometry (GC-MS) data is limited by the complexity and noise levels inherent in the data. Specifically, current techniques are not capable of detecting minute, chemically relevant compositional differences with sufficient sensitivity. Therefore, an alternative peak selection strategy was developed based on spectral interpretation through interval-oriented parallel factor analysis (PARAFAC). It will be shown that this strategy outperforms the deconvolution-based peak selection strategy as well as two control strategies. Successful application of the PARAFAC-based method to detect minute chemical changes produced during microbiological growth in four different inoculated diesel fuels will be discussed. 相似文献
978.
This paper introduces a simple method for modelling non-spherical particles with a fixed contact angle at an interface whilst also providing a method to fix the particles orientation. It is shown how a wide variety of particle shapes (spherical, ellipsoidal, disc) can be created from a simple initial geometry containing only six vertices. The shapes are made from one continuous surface with edges and corners treated as smooth curves not discontinuities. As such, particles approaching cylindrical and orthorhombic shapes can be simulated but the contact angle crossing the edges will be fixed. Non-spherical particles, when attached to an interface can cause large distortions in the surface which affect the forces acting on the particle. The model presented is capable of resolving this distortion of the surface around the particle at the interface as well as allowing for the particle's orientation to be controlled. It is shown that, when considering orthorhombic particles with rounded edges, the flatter the particle the more energetically stable it is to sit flat at the interface. However, as the particle becomes more cube like, the effects of contact angle have a greater effect on the energetically stable orientations. Results for cylindrical particles with rounded edges are also discussed. The model presented allows the user to define the shape, dimensions, contact angle and orientation of the particle at the interface allowing more in-depth investigation of the complex phenomenon of 3D film distortion around an attached particle and the forces that arise due to it. 相似文献
979.
Patterson DG Welch SM Turner WE Sjödin A Focant JF 《Journal of chromatography. A》2011,1218(21):3274-3281
980.
The selective excitation scheme known as ‘DANTE’ emerged from a confluence of several ideas for new NMR experiments, some more fanciful than others. DANTE offers a simple and effective way to restrict excitation to a very narrow frequency band, usually that of a single resonance line. Initially applied to the study of individual proton-coupled carbon-13 spin multiplets, the method has been extended to water presaturation, relaxation measurements, and chemical exchange studies. Through the imposition of a magnetic field gradient it offers a simple method to enhance resolution by restricting the effective volume of the sample. Multiple DANTE excitation (with Hadamard encoding) can speed up multidimensional spectroscopy by orders of magnitude. Applied to magnetic resonance imaging, the DANTE sequence has been used to superimpose a rectangular grid onto a cardiac image, permitting motional distortions to be monitored in real time. 相似文献