Ultrasonically determined thickness of long cortical bones: two-dimensional simulations of in vitro experiments

Previously it has been demonstrated that cortical bone thickness can be estimated from ultrasonic guided-wave measurements, in an axial transmission configuration, together with an appropriate analytical model. This study considers the impact of bone thickness variation within the measurement region on the ultrasonically determined thickness (UTh). To this end, wave velocities and UTh were determined from experiments and from time-domain finite-difference simulations of wave propagation, both performed on a set of ten human radius specimens (29 measurement sites). A two-dimensional numerical bone model was developed with tunable material properties and individualized geometry based on x-ray computed-tomography reconstructions of human radius. Cortical thickness (CTh) was determined from the latter. UTh data for simulations were indeed in a excellent accordance (root-mean-square error was 0.26 mm; r2=0.94, p<0.001) with average CTh within the measurement region. These results indicate that despite variations in cortical thickness along the propagation path, the measured phase velocity can be satisfactorily modeled by a simple analytical model (the A(0) plate mode in this case). Most of the variability (up to 85% when sites were carefully matched) observed in the in vitro ultrasound data was explained through simulations by variability in the cortical thickness alone.     

Kinetics of the CCl2 + Br2 and CCl2 + NO2 reactions in the temperature range 266−365 K and reactivity of the CCl2 biradical

The kinetics of the CCl₂ + Br₂ and CCl₂ + NO₂ reactions have been studied at temperatures between 266 and 365 K using laser photolysis/photoionization mass spectrometry. Dichloromethylene biradicals were produced by the pulsed laser photolysis of CCl₄. The bimolecular rate coefficients of the CCl₂ + Br₂ reaction can be described by the Arrhenius expression k₁ = (7.05 ± 1.75) × 10⁻¹² exp[(3.52 ± 0.63) kJ mol⁻¹/RT] cm³ molecule⁻¹ s⁻¹. CCl₂Br was observed as a primary product of this reaction. Interestingly, the bimolecular rate coefficients of the CCl₂ + NO₂ reaction were observed to depend weakly on the bath gas density and to possess a negative temperature dependence.     

The Effect of Void Structure on the Permeability of Fibrous Networks

A Kozeny–Carman-based model of permeability for fibrous networks is proposed: the original model is extended by incorporating information about the local structure of the void space. Furthermore, it is demonstrated how in practice this added structural information can be retrieved from a three-dimensional digital image of a fibrous material. The proposed model is then validated for both foam- and water-deposited laboratory sheets of bleached kraft pulp (Scots pine) and chemi-thermo-mechanical pulp (CTMP, Norway spruce). The validation is carried out by comparing the model predictions against computationally determined permeability values. The related fluid-flow simulations are executed using the lattice-Boltzmann method together with high-resolution X-ray microtomography images. For both pulp materials, the sample sets had nearly equal porosities, but deviated substantially in their permeabilities. The proposed model was shown to improve prediction of permeability for the fibrous materials considered: the deviation between the predicted and computationally determined values was no more than 8%.     

Kinetics of the reactions of CH2Br and CH2I radicals with molecular oxygen at atmospheric temperatures

The kinetics of the reactions of CH2Br and CH2I radicals with O2 have been studied in direct measurements using a tubular flow reactor coupled to a photoionization mass spectrometer. The radicals have been homogeneously generated by pulsed laser photolysis of appropriate precursors at 193 or 248 nm. Decays of radical concentrations have been monitored in time-resolved measurements to obtain the reaction rate coefficients under pseudo-first-order conditions with the amount of O2 being in large excess over radical concentrations. No buffer gas density dependence was observed for the CH2I + O2 reaction in the range 0.2-15 x 10(17) cm(-3) of He at 298 K. In this same density range the CH2Br + O2 reaction was obtained to be in the third-body and fall-off area. Measured bimolecular rate coefficient of the CH2I + O2 reaction is found to depend on temperature as k(CH2I + O2)=(1.39 +/- 0.01)x 10(-12)(T/300 K)(-1.55 +/- 0.06) cm3 s(-1)(220-450 K). Obtained primary products of this reaction are I atom and IO radical and the yield of I-atom is significant. The rate coefficient and temperature dependence of the CH2Br + O2 reaction in the third-body region is k(CH2Br + O2+ He)=(1.2 +/- 0.2)x 10(-30)(T/300 K)(-4.8 +/- 0.3) cm6 s(-1)(241-363 K), which was obtained by fitting the complete data set simultaneously to a Troe expression with the F(cent) value of 0.4. Estimated overall uncertainties in the measured reaction rate coefficients are about +/-25%.     

Kinetics of the CH3 + HCl/DCl → CH4/CH3D + Cl and CD3 + HCl/DCl → CD3H/CD4 + Cl reactions: An experimental H atom tunneling investigation

The kinetics of the radical reactions of CH₃ with HCl or DCl and CD₃ with HCl or DCl have been investigated in a temperature controlled tubular reactor coupled to a photoionization mass spectrometer. The CH₃ (or CD₃) radical, R, was produced homogeneously in the reactor by a pulsed 193 nm exciplex laser photolysis of CH₃COCH₃ (or CD₃COCD₃). The decay of CH₃/CD₃ was monitored as a function of HCl/DCl concentration under pseudo-first-order conditions to determine the rate constants as a function of temperature, typically from 188 to 500 K. The rate constants of the CH₃ and CD₃ reactions with HCl had strong non-Arrhenius behavior at low temperatures. The rate constants were fitted to a modified Arrhenius expression k = QA exp (−E_a/RT) (error limits stated are 1σ + Students t values, units in cm³ molecule⁻¹ s⁻¹): k(CH₃ + HCl) = [1.004 + 85.64 exp (−0.02438 × T/K)] × (3.3 ± 1.3) × 10⁻¹³ exp [−(4.8 ± 0.6) kJ mol⁻¹/RT] and k(CD₃ + HCl) = [1.002 + 73.31 exp (−0.02505 × T/K)] × (2.7 ± 1.2) × 10⁻¹³ exp [−(3.5 ± 0.5) kJ mol⁻¹/RT]. The radical reactions with DCl were studied separately over a wide ranges of temperatures and in these temperature ranges the rate constants determined were fitted to a conventional Arrhenius expression k = A exp (−E_a/RT) (error limits stated are 1σ + Students t values, units in cm³ molecule⁻¹ s⁻¹): k(CH₃ + DCl) = (2.4 ± 1.6) × 10⁻¹³ exp [−(7.8 ± 1.4) kJ mol⁻¹/RT] and k(CD₃ + DCl) = (1.2 ± 0.4) × 10⁻¹³ exp [−(5.2 ± 0.2) kJ mol⁻¹/RT] cm³ molecule⁻¹ s⁻¹.     

Spontaneous formation of densely packed shear bands of rotating fragments

Appearance of self-similar space-filling ball bearings has been suggested to provide the explanation for seismic gaps, shear weakness, and lack of detectable frictional heat formation in mature tectonic faults (shear zones). As the material in a shear zone fractures and grinds, it could be thought to eventually form a conformation that allows fragments to largely roll against each other without much sliding. This type of space-filling "ball bearing" can be constructed artificially, but so far how such delicate structures may appear spontaneously has remained unexplained. It is demonstrated here that first-principles simulations of granular packing with fragmenting grains indeed display spontaneous formation of shear bands with fragment conformations very similar to those of densely packed ball bearings.     

Quantum dynamics of strongly interacting boson systems: atomic beam splitters and coupled Bose-Einstein condensates

An effective boson Hamiltonian applicable to atomic beam splitters, coupled Bose-Einstein condensates, and optical lattices can be made exactly solvable by including all n-body interactions. The model can include an arbitrary number of boson components. In the strong interaction limit the model becomes a quantum phase model, which also describes a tight-binding lattice particle. Through exact results for dynamic correlation functions, it is shown how the previous weak interaction dynamics of these systems are extended to strong interactions, now becoming relevant in the experiments. The effect of the number of boson components is also analyzed.     

In-situ Monitoring of Photocontrollable Wrinkle Erasure in Azobenzene-based Supramolecular Systems

In this contribution, dynamic photoinduced wrinkle erasure enabled by photomechanical changes in supramolecular polymer-azo complexes was characterized via confocal microscopy. Different photoactive molecules, disperse yellow 7 (DY7) and 4,4′-dihydroxyazobenzene (DHAB), were compared to 4-hydroxy-4′-dimethylaminoazobenzene (OH-azo-DMA). The characteristic erasure times of wrinkles were quickly assessed by using an image processing algorithm. The results confirm that the photoinduced movement on the topmost layer can be successfully transferred to the substrate. Furthermore, the chosen supramolecular strategy allows decoupling the effect of molecular weight of the polymer and photochemistry of the chromophore, allowing quantitative comparison of wrinkling erasure efficiency of different materials and providing a facile way to optimize the system for specific applications.     

Granular packings and fault zones

The failure of a two-dimensional packing of elastic grains is analyzed using a numerical model. The packing fails through formation of shear bands or faults. During failure there is a separation of the system into two grain-packing states. In a shear band, local "rotating bearings" are spontaneously formed. The bearing state is favored in a shear band because it has a low stiffness against shearing. The "seismic activity" distribution in the packing has the same characteristics as that of the earthquake distribution in tectonic faults. The directions of the principal stresses in a bearing are reminiscent of those found at the San Andreas Fault.