Analysis and modeling for time-dependent behavior of polymers exhibited in nanoindentation tests

Through the arrangement of the applied load, experimental nanoindentation results of polymethylmethacrylate (PMMA) and polyurethane (PU) employed to establish a mechanical model. The proposed model consists of irreversible delayed plastic (viscoplastic) deformation, irreversible viscous deformation, and reversible delayed elastic (viscoelastic) deformations. The phase lag exhibited between the responding depth and the oscillating load is found to be linear proportional to frequency in the range of 1-50 Hz. The residual cavity profile of the PMMA scanned by an atomic force microscope gives a validity of accommodation assumption applied in the present model. The effects of overshooting, which occurred in the dwelling process, are also discussed.     

A novel capacitive pressure sensor structure with high sensitivity and quasi-linear responseUne nouvelle structure de capteur de pression capacitif avec haute sensibilitée et réponse quasi-linéaire

This paper describes a new capacitive structure of pressure sensor to increase simultaneously the sensitivity and the linearity of the transducer. This structure contains two capacitors which change in response to pressure, but in opposite senses. To increase even more the sensitivity of each capacitor, the pressure sensitive diaphragm carries a central boss. The optimal position and the length of the boss are also calculated. To cite this article: A. Ettouhami et al., C. R. Mecanique 332 (2004).     

Une méthode de calcul des coefficients de réflexion et de transmission d'une houle bidimensionnelle en milieu confinéA new method for the calculation of transmission and reflection coefficients for water waves in a small basin

This paper presents a method to estimate reflected and transmitted wave amplitude spectra in a bounded domain such as a wave tank, when available data signals must be shortened due to interferences and wall effects. This paper extends the well known Goda and Suzuki two-probe method to three probes. The paper also suggests solutions to compute reliable transmission and reflection coefficients in spite of problems linked to higher harmonics and to the interference between different wave trains propagating in the tank. To cite this article: G. Duclos, A.H. Clément, C. R. Mecanique 331 (2003).     

COSMIC(90): An improved molecular mechanics treatment of hydrocarbons and conjugated systems

Summary Four modifications to the COSMIC molecular mechanics force field are described, which greatly increase both its versatility and the accuracy of calculated conformational energies. The Hill non-bonded van der Waals potential function has been replaced by a two-parameter Morse curve and a new H-H potential, similar to that in MM3, incorporated. Hydrocarbon energies in particular are much improved.A simple iterative Hückel pi-electron molecular orbital calculation allows modelling of conjugated systems. Calculated bond lengths and rotational barriers for a series of conjugated hydrocarbons and nitrogen heterocycles are shown to be as accurate as those determined by the MM2 SCF method.Explicit hydrogen-bonding potentials for H-bond acceptor-donor atom pairs have been included to give better hydrogen bond energies and lengths. The van der Waals radii of protonic hydrogens are reduced to 0.5 Å and the energy well depth is increased to 1.0 kcal mol^-1.Two new general atom types, N⁺ _sp ² and O^- _sp ³ , have been introduced which allow a wide variety of charged conjugated systems to be studied. A minimum of parameterisation is required, as the new types are easily included in the Hückel scheme which automatically adjusts bond and torsional parameters according to the defined bond-order relationships.     

One-pot synthesis of an ionic half-sandwich complex of neodymium. Application to isoprene polymerisation catalysis

The reaction of one equivalent of Nd(BH₄)₃(THF)₃ with an half equivalent of dialkylmagnesium in the presence of a stoichiometric amount of pentamethylcyclopentadiene cleanly affords a new kind of half-sandwich of neodymium that is stable toward comproportionation. This strategy can be advantageously applied to generate in situ catalysts allowing the controlled polymerisation of isoprene.     

Infrared combination and difference bands of the NO dimer

The mid-infrared (1500-3800 cm⁻¹) absorption spectrum of gaseous nitric oxide has been studied at low temperature (99 K) with a long absorption path (160 m) in order to observe weak combination, difference, and overtone bands of the NO dimer. About ten new bands were assigned with greater or lesser certainty. Combined with previous results, they lead to a set of 12 secure and 7 tentative vibrational term values for (NO)₂, essentially doubling our knowledge of NO dimer vibrational states. The strongest non-fundamental bands in this region, other than the ν₁ (symmetric N-O stretch) + ν₅ (asymmetric N-O stretch) overtone, involve combinations of ν₅ with ν₃ (intermolecular stretch). Excitation of ν₅ results in increased frequencies for the intermolecular modes ν₂, ν₃, and ν₄. A new value of 155.5 cm⁻¹ was obtained for ν₄, the elusive infrared-inactive out-of-plane fundamental vibration.     

π-Bindungsbeitrag in Boranen, 2. Mitt.:Ab initio- und Kraftfeld-Rechnungen von Vinyldifluorboran

Ab initio calculations on vinyldifluoroborane yield a -contribution of 23 kJ/mol (5.5 kcal/mol) mainly due to the C=C bond and not to the lone pairs of the fluorine atoms. The rotational barrier was also determined. The force field calculations favour the interpretation of the bond structure derived from the theab initio results.

     

Unnatural multidentate metal ligating α-amino acids

A family of penta- and hexadentate metal ligating α-amino acids, suitably protected for Fmoc solid-phase chemistry, has been prepared. These residues incorporate the mono-amides of ethanolaminetriacetic acid, ethylenediaminetriacetic acid, and ethylenediaminetetraacetic acid as side chains. Side chains are tethered varying distances (n) from the Cα-carbon to allow metal binding events to occur at distinct distances from the peptide backbone. These residues are designed to allow the facile installation of metal chelates along a peptide backbone.     

Force Constants and Bond Orders of Nitrogen Bonds

The force constants and the corresponding bond orders of nitrogen bonds have been calculated from the vibrational spectra (infrared and Raman spectra) of a great number of nitrogen compounds. Plotting the maximum bond order of stable nitrogen bonds against the sum of Pauling's electronegativities of the bonding partners (Σx) leads to one continuous curve for the N? X bonds where X represents elements of the first and the second short period of the periodic table. Furthermore, when the bonds formed between these elements are arranged in a coordinate system in such a way that the position of each bond is determined by the difference between the electronegativities of the bonding partners (Δx along the ordinate) and the sum of the electronegativities of the bonding partners (Σx along the abscissa), the bonding partners capable of forming multiple bonds all lie within a closed domain, where their position can be correlated with their polymerizability and other reactivities of the multiple bonds. Also discussed are the orders of bonds between nitrogen and some transition elements. In an appendix, the present methods used to calculate force constants and bond orders are surveyed.     

Crystal structure and magnetic structure of TbOOH

The monoclinic modification of terbium oxide hydroxide, TbOOH, was prepared using hydrothermal technique. The crystal structure was investigated by three-dimensional single-crystal X-ray analysis and was refined to a conventional R-value of 8.1%. The space group is $\text{P2}{}_1\text{m}$, No. 11, with a = 6.04 Å, b = 3.69 Å, c = 4.33 Å, and β = 109.0°. The terbium atom is seven coordinated with oxygen atoms, and the structure is not hydrogen bonded.The compound is antiferromagnetic with a Néel temperature of 10°K. Neutron diffraction powder patterns were measured at 300°K and 4.2°K. The magnetic super lattice reflections were indexed on the basis of a monoclinic unit cell with the dimensions a_M = 2a, b_M = b, c_M = c, and β_M = β, where a, b, c, and β are the dimensions of the chemical unit cell. The structure contains two independent magnetic atoms. A nonclinear antiferromagnetic arrangement of the spins describes the magnetic structure. The spin at one atom has an angle of 43° with the ac plane and the projection of the spin on the ac plane has an angle of 59° with the a axis. The spin on the other atom has an angle of ?43° with the ac plane, the projection having the same angle of 59° with the a axis.