Automotive disc brake squeal

Disc brake squeal remains an elusive problem in the automotive industry. Since the early 20th century, many investigators have examined the problem with experimental, analytical, and computational techniques, but there is as yet no method to completely suppress disc brake squeal. This paper provides a comprehensive review and bibliography of works on disc brake squeal. In an effort to make this review accessible to a large audience, background sections on vibrations, contact and disc brake systems are also included.     

1-mJ, sub-5-fs carrier–envelope phase-locked pulses

We report the routine generation of sub-5-fs laser pulses with 1-mJ energy and stable carrier–envelope phase at 1-kHz repetition rate, obtained by compressing the multi-mJ output from a phase-locked Ti:sapphire amplifier in a rare-gas-filled hollow fiber. The dual-stage amplifier features a hybrid transmission grating/chirped mirror compressor providing 2.2-mJ, 26-fs pulses at 1 kHz with standard phase deviation of 190 mrad rms. We demonstrate hour-long phase stability without feedback control of grating position or rigorous control of the laser environment, simply by using small pulse stretching factors in the amplifier, which minimize the beam pathway in the compressor. The amplifier also integrates a versatile AOPDF (acousto-optic programmable dispersive filter) for closed-loop spectral phase optimization. The various factors influencing the overall phase stability of the system are discussed in detail. Using the optimized output, 1-mJ, 4.5-fs pulses are generated by seeding the neon gas filled hollow fiber with a circularly polarized input beam. A standard phase deviation of 230 mrad after the HCF is obtained by direct f-to-2f detection and slow-loop feedback to the oscillator locking electronics without any additional spectral broadening.     

Synthesis,thermal analysis,and spectroscopic and structural characterizations of tetranuclear nickel(II) cubane-type clusters with 2-hydroxybenzaldehydes or 2-hydroxyphenones

In this study, three novel tetranuclear nickel(II) cubane-type clusters with the general formula [Ni₄(L)₄(μ₃-CH₃O)₄(CH₃OH)₄] [L: the anion of 5-methyl-2-hydroxybenzaldehyde (1), 2-hydroxypropiophenone (2), and 2-hydroxybenzophenone (3)] were synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal structure of each compound contains a tetranuclear cubane core [Ni₄O₄] based on an approximately cubic array of altering nickel and oxygen atoms with intracluster metal–metal separations of 3.04–3.14 Å. Each Ni(II) atom is surrounded by two oxygen atoms from the ligand (L) and by the μ₃-CH₃O oxygen atom that bridges three Ni atoms of the cubane core. The coordination sphere of Ni is completed with one methanol molecule and making six-coordinate with a distorted octahedral geometry. These complexes were characterized also by spectroscopy (IR and UV–Vis). Simultaneous TG/DTG–DTA techniques were used to analyze their thermal behavior under inert atmosphere, with particular attention to determine their thermal degradation pathways, which was found to be a multi-step decomposition accompanied by the release of the ligand molecules. Finally, the kinetic analysis of the decomposition processes was performed for the first step of complex (3), since only this verifies the requirement of applying an isoconversional method like Kissinger–Akahira–Sunose (KAS). For this step, we found the average value E _a = 107.8 ± 4.5 kJ mol^?1.     

High pressure [4+2] and [2+2+2] reactions between cycloheptatriene and methyl propiolate

Under high pressure conditions, cycloheptatriene reacts with methyl propiolate to afford mono-, bis- and trisadducts all retaining, the norcaradiene structure. The four new compounds are formed via [4+21] and [2+2+2] cycloadditions. The latter are examples for the high pressure extension of the scope of homo-Diels-Alder reactions.     

Neutron activation analysis for determination of metal ions in biological fluids of patients after CoCrMo arthroplasty

Determination of metals and trace elements in patients with total knee or hip arthroplasty with CoCrMo alloy was performed. Blood, urine and cerebrospinal fluid (CSF) samples were analyzed and compared with samples from healthy people. Levels of Co, Cr as well as Na, Ca, Fe, Zn, Se, Rb, Sb and Br were determined by means of neutron activation analysis. The values of Cr and Co of the blood and urine measurements were elevated in patients with replacement, and according to the statistical analysis, significant differences of the elements Zn, Br, Co and Sb were found in the CSF (p?<?0.05).

     

Performance of density functional theory in computing nonresonant vibrational (hyper)polarizabilities

A set of exchange‐correlation functionals, including BLYP, PBE0, B3LYP, BHandHLYP, CAM‐B3LYP, LC‐BLYP, and HSE, has been used to determine static and dynamic nonresonant (nuclear relaxation) vibrational (hyper)polarizabilities for a series of all‐trans polymethineimine (PMI) oligomers containing up to eight monomer units. These functionals are assessed against reference values obtained using the Møller–Plesset second‐order perturbation theory (MP2) and CCSD methods. For the smallest oligomer, CCSD(T) calculations confirm the choice of MP2 and CCSD as appropriate for assessing the density functionals. By and large, CAM‐B3LYP is the most successful, because it is best for the nuclear relaxation contribution to the static linear polarizability, intensity‐dependent refractive index second hyperpolarizability, static second hyperpolarizability, and is close to the best for the electro‐optical Pockels effect first hyperpolarizability. However, none of the functionals perform satisfactorily for all the vibrational (hyper)polarizabilities studied. In fact, in the case of electric field‐induced second harmonic generation all of them, as well as the Hartree–Fock approximation, yield the wrong sign. We have also found that the Pople 6–31+G(d) basis set is unreliable for computing nuclear relaxation (hyper)polarizabilities of PMI oligomers due to the spurious prediction of a nonplanar equilibrium geometry. © 2013 Wiley Periodicals, Inc.     

Theoretical Modelling of Photoswitching of Hyperpolarisabilities in Ruthenium Complexes

Static excited‐state polarisabilities and hyperpolarisabilities of three Ru^II ammine complexes are computed at the density functional theory (DFT) and several correlated ab initio levels. Most accurate modelling of the low energy electronic absorption spectrum is obtained with the hybrid functionals B3LYP, B3P86 or M06 for the complex [Ru^II(NH₃)₅(MeQ⁺)]³⁺ (MeQ⁺=N‐methyl‐4,4′‐bipyridinium, 3 ) in acetonitrile. The match with experimental data is less good for [Ru^II(NH₃)₅L]³⁺ (L=N‐methylpyrazinium, 2 ; N‐methyl‐4‐{E,E‐4‐(4‐pyridyl)buta‐1,3‐dienyl}pyridinium, 4 ). These calculations confirm that the first dipole‐ allowed excited state (FDAES) has metal‐to‐ligand charge‐transfer (MLCT) character. Both the solution and gas‐phase results obtained for 3 by using B3LYP, B3P86 or M06 are very similar to those from restricted active‐space SCF second‐order perturbation theory (RASPT2) with a very large basis set and large active space. However, the time‐dependent DFT λ_max predictions from the long‐range corrected functionals CAM‐B3LYP, LC‐ωPBE and wB97XB and also the fully ab initio resolution of identity approximate coupled‐cluster method (gas‐phase only) are less accurate for all three complexes. The ground state (GS) two‐state approximation first hyperpolarisability β_2SA for 3 from RASPT2 is very close to that derived experimentally via hyper‐Rayleigh scattering, whereas the corresponding DFT‐based values are considerably larger. The β responses calculated by using B3LYP, B3P86 or M06 increase markedly as the π‐conjugation extends on moving along the series 2 → 4 , for both the GS and FDAES species. All three functionals predict substantial FDAES β enhancements for each complex, increasing with the π‐conjugation, up to about sevenfold for 4 . Also, the computed second hyperpolarisabilities γ generally increase in the FDAES, but the results vary between the different functionals.