Evolution of Localized Damage Zone in Heterogeneous Media

Evolution of localized damage zone is a key to catastrophic rupture in heterogeneous materials. In the present article, the evolutions of strain fields of rock specimens are investigated experimentally. The observed evolution of fluctuations and autocorrelations of strain fields under uniaxial compression demonstrates that the localization of deformation always appears ahead of catastrophic rupture. In particular, the localization evolves pronouncedly with increasing deformation in the rock experiments. By means of the definition of the zone with high strain rate and likely damage localization, it is found that the size of the localized zone decreases from the sample size at peak load to an eventual value. Actually, the deformation field beyond peak load is bound to suffer bifurcation, namely an elastic unloading part and a continuing but localized damage part will co-exist in series in a specimen. To describe this continuous bifurcation and localization process observed in experiments, a model on continuum mechanics is developed. The model can explain why the decreasing width of localized zone can lead stable deformation to unstable, but it still has not provided the complete equations governing the evolution of the localized zone.

Dislocation nucleation governed softening and maximum strength in nano-twinned metals

In conventional metals, there is plenty of space for dislocations-line defects whose motion results in permanent material deformation-to multiply, so that the metal strengths are controlled by dislocation interactions with grain boundaries(1,2) and other obstacles(3,4). For nano-structured materials, in contrast, dislocation multiplication is severely confined by the nanometre-scale geometries so that continued plasticity can be expected to be source-controlled. Nano-grained polycrystalline materials were found to be strong but brittle(5-9), because both nucleation and motion of dislocations are effectively suppressed by the nanoscale crystallites. Here we report a dislocation-nucleation-controlled mechanism in nano-twinned metals(10,11) in which there are plenty of dislocation nucleation sites but dislocation motion is not confined. We show that dislocation nucleation governs the strength of such materials, resulting in their softening below a critical twin thickness. Large-scale molecular dynamics simulations and a kinetic theory of dislocation nucleation in nano-twinned metals show that there exists a transition in deformation mechanism, occurring at a critical twin-boundary spacing for which strength is maximized. At this point, the classical Hall-Petch type of strengthening due to dislocation pile-up and cutting through twin planes switches to a dislocation-nucleation-controlled softening mechanism with twin-boundary migration resulting from nucleation and motion of partial dislocations parallel to the twin planes. Most previous studies(12,13) did not consider a sufficient range of twin thickness and therefore missed this strength-softening regime. The simulations indicate that the critical twin-boundary spacing for the onset of softening in nano-twinned copper and the maximum strength depend on the grain size: the smaller the grain size, the smaller the critical twin-boundary spacing, and the higher the maximum strength of the material.

Catastrophic rupture of heterogeneous brittle materials under impact loading

The catastrophic failure of heterogeneous brittle materials under impact loading is not fully understood. To describe the catastrophic failure behavior of heterogeneous brittle materials under impact loading, an elasto-statistical-brittle (ESB) model is proposed in this paper. The ESB model characterizes the disordered inhomogeneity of material at mesoscopic scale with the statistical description of the shear strength of mesoscopic units. If the applied shear stress reaches the strength, the mesoscopic unit fails, which causes degradation in the shear modulus of the material. With a simplified ESB model, the failure wave in brittle material under uni-axial compression is analyzed. It is shown that the failure wave is a wave of strain or particle velocity resulted from the catastrophic fracture in an elastically stressed brittle media when the impact velocity reaches a critical value. In addition, the failure wave causes an increase in the rear surface velocity, which agrees well with experimental observations. The critical condition to generate failure wave and the speed of failure wave are also obtained.

Enhanced nucleation of Ag nanoparticles by vacancy-type defects in Ar-ions implanted spinel

Vacancy-type defects are introduced into magnesium aluminate spine] (MgAl2O4 (1 1 0)) by Ar-ions implantation, and then Ag-ions are implanted into the depth rich in vacancy-type defects. The ultraviolet-visible spectrometry (UV-VIS) and positron annihilation spectroscopy (PAS) are used to study the influence of vacancy-type defects on nucleation of Ag nanoparticles. After introduction of vacancy-type defects the pronounced increase of surface plasmon resonance (SPR) absorbance intensity indicates that defects enhance the nucleation of Ag nanoparticles. The PAS results reveal that vacancy-type defects provide pre-nucleating centers for Ag nanoparticles nucleation and growth. (C) 2010 Elsevier B.V. All rights reserved.

Recyclable heterogeneous Rh/SiO2 catalyst enhanced by organic PPh3 ligand

Heterogeneous PPh3-Rh/SiO2 catalysts for hydroformylation of olefins, prepared by direct doping of phosphine onto the heterogeneous Rh/SiO2 precursor, exhibited high activity and selectivity towards aldehydes, which originated from chemical coordination bond between the phosphine and Rh metal nantoparticles on the SiO2 support.

High-throughput characterization of heterogeneous catalysts by temperature-programmed analysis method

A multistream reactor for high-throughput examining the surface acidity by NH3-TPD method by application of multistream mass spectrometer screening (MSMSS) technique has been developed. This method allows for examining the surface acidity of 10 catalyst samples in about 6 h, which is an improvement over the traditional process. The demonstration of the feasibility of high-throughput TPD can be significant in convincing the hardened traditionalists in the heterogeneous catalysis community that, combinatorial methods indeed should have an important place in scientific catalyst research and development. The developed method could also be used for almost all the temperature-programmed analysis theoretically with careful designed multistream reactors. (C) 2003 Elsevier B.V. All rights reserved.

Cyclopropanation on a highly active heterogeneous catalyst: CuO/TiO2-Al2O3

Some heterogeneous catalysts, cupric oxide supported on different supports, were prepared and employed to catalyze the cyclopropanation of styrene and 2,5-dimethyl-2,4-hexadiene with ethyl diazoacetate (EDA). The catalytic performance for cyclopropanation strongly depends on the nature of the support. A novel catalyst, CUO/TiO2-Al2O3, in which Al2O3 is modified with a monolayer TiO2, is found to be most active and selective for the cyclopropanation reaction. The yields of 93 and 94% cyclopropanes are obtained for styrene and 2,5-dimethyl-2,4-hexadiene at 40 degreesC as the substrates, respectively. The activity and selectivity in cyclopropanes are optimized with a monolayer dispersion of cupric oxide on the corresponding supports. (C) 2002 Elsevier Science B.V. All rights reserved.

Quantified MS analysis applied to combinatorial heterogeneous catalyst libraries

A high-throughput screening system for secondary catalyst libraries has been developed by incorporation of an 80-pass reactor and a quantified multistream mass spectrometer screening (MSMSS) technique. With a low-melting alloy as the heating medium, a uniform reaction temperature could be obtained in the multistream reactor (maximum temperature differences are less than 1 K at 673 K). Quantification of the results was realized by combination of a gas chromatogram with the MSMSS, which could provide the product selectivities of each catalyst in a heterogeneous catalyst library. Because the catalyst loading of each reaction tube is comparable to that of the conventional microreaction system and because the parallel reactions could be operated under identical conditions (homogeneous temperature, same pressure and WHSV), the reaction results of a promising catalyst selected from the library could be reasonably applied to the further scale-up of the system. The aldol condensation of acetone, with obvious differences in the product distribution over different kind of catalysts, was selected as a model reaction to validate the screening system.

Nucleation and growth of CUSO4 center dot 5H(2)O crystals on the liquid state stearic acid Langmuir-Blodgett film

Oriented crystallization of CUSO4 center dot 5H(2)O on a Langmuir-Blodgett (LB) film of stearic acid has been studied in the temperature ranges of 73-68 degrees C and 53-20 degrees C, respectively. This is the first time that the LB film at temperature above its melting point has been served as a template to induce nucleation and growth of crystals. The experimental results demonstrated that the LB film in the liquid state has the ability of directing the nucleation and growth of crystals. Moreover, X-ray diffraction patterns of the as prepared crystals revealed that the orientation of the attached crystals on the LB film is affected by temperature greatly.