Friction and normal forces of model friction modifier additives in simulations of boundary lubrication

ABSTRACT

Interaction forces between solid surfaces are often mitigated by adsorbed molecules that control normal and friction forces at nanoscale separations. Molecular dynamics simulations were conducted of opposing semi-ordered monolayers of united-atom chains on sliding surfaces to relate friction and normal forces to imposed sliding velocity and inter-surface separation. Practical examples include adsorbed friction-modifier molecules in automatic transmission fluids. Friction scenarios in the simulations had zero, one, or two fluid layers trapped between adsorbed monolayers. Sliding friction forces increased with sliding velocity at each stable separation. Lower normal forces were obtained than in most previous nanotribology molecular simulations and were relatively independent of sliding speed. Distinguishing average frictional force from its fluctuations showed the importance of system size. Uniform velocities were obtained in the sliding direction across each adsorbed film, with a gradient across the gap containing trapped fluid. The calculated friction stress was consistent with measurements reported using a surface forces apparatus, indicating that drag between an adsorbed layer and trapped fluid can account sufficiently for sliding friction in friction modifier systems. An example is shown in which changes in molecular organisation parallel to the surface led to a large change in normal force but no change in friction force.     

A Redox-Active Microporous Organosiloxane Containing a Stable Neutral Radical,Trioxotriangulene

A new silyl-substituted trioxotriangulene ( TOT ) neutral radical and corresponding porous organosiloxanes (POSs) were synthesized. The neutral radical exhibited a peculiarly high stability and formed a diamagnetic π-dimer characteristic to TOT neutral radicals stabilized by the strong multiple SOMO-SOMO interaction in both solution and solid states. POSs including TOT units within the organosiloxane-wall were prepared by polycondensation of the silyl groups and formed microporous structures with ∼1 nm-size diameters. Redox ability of TOT units in the POS was demonstrated by the treatment of oxidant/reductant in heterogeneous suspension condition, where the TOT units were reversibly converted between reduced and neutral radical species. Furthermore, the solid-state electrochemical measurements of the POS revealed the reversible multi-stage redox ability of TOT units involving polyanionic species within the organosiloxane-wall.     

Organozinc-aided,HMPA-free,stoichiometric three-component coupling for the general synthesis of prostaglandins and stable prostacyclin analogs with biological significance

A three-component coupling procedure was developed to construct the entire prostaglandin (PG) skeleton under HMPA-free and stoichiometric conditions via a combination of dimethylzinc-aided conjugate addition of an ω-side-chain vinyllithium with (R)-4-hydroxy-2-cyclopentenone and the direct trapping of the resulting enolate with an α-side-chain propargyl triflate. Dimethylzinc effectively regulated both the conjugate addition and alkynylation reactions. Thus, the method afforded protected 5,6-didehydro-PGE₂, a common intermediate for the general synthesis of natural PGs and the stable artificial prostacyclin (PGI₂) analog isocarbacyclin in 88% yield. The utility of the method was further applied to the syntheses of novel intermediates, which are useful for the straightforward synthesis of 15R-TIC and 15-deoxy-TIC in 79% and 86% yield, respectively.     

Separate vaporisation of boric acid and inorganic boron from tungsten sample cuvette-tungsten boat furnace followed by the detection of boron species by inductively coupled plasma mass spectrometry and atomic emission spectrometry (ICP-MS and ICP-AES)

Utilising extremely different vaporisation properties of boron compounds, the determination procedures of volatile boric acid and total boron using tungsten boat furnace (TBF) ICP-MS and TBF-ICP-AES have been investigated. For the determination of volatile boric acid by TBF-ICP-MS, tetramethylammonium hydroxide (TMAH, Me₄NOH) was used as a chemical modifier to retain it during drying and ashing stages. As for the total boron, not only non-volatile inorganic boron such as boron nitride (BN), boron carbide (B₄C), etc. but also boric acid (B(OH)₃) was decomposed by a furnace-fusion digestion with NaOH to produce sodium salt of boron, a suitable species for the electrothermal vaporisation (ETV) procedure. The proposed method was applied to the analysis of various standard reference materials. The analytical results for various biological and steel samples are described.     

Structure and dynamics of silk fibroin studied with 13C, 15N and 2H solid state NMR

[1-¹³C]Gly, L-[1-¹³C]Ala, [¹⁵N]Gly, L-[¹⁵N]Ala, [2,2-²H₂]Gly, L-[3,3-²H₂]Ser and [3,3,3-²H₃]Ala labeled silk fibroin fibers from Bombyx mori and Samia cynthia ricini silkworms were prepared in order to analyze structure of backbone and dynamics of side chain. The torsion angles ϕ and Ψ were determined from the angular dependent ¹³C and ¹⁵N solid state NMR spectra for uniaxially oriented fiber samples. In addition, the characteristic side chain dynamics of Ser residue determined from solid state ²H NMR measurements was compared with those of Ala and Gly residues.     

Living radical polymerization of methyl methacrylate with a zerovalent nickel complex,Ni(PPh3)

A zerovalent nickel complex, Ni(PPh₃)₄, induced living radical polymerization of methyl methacrylate (MMA) in conjunction with an organic bromide as an initiator [R–Br: CCl₃Br, (CH₃)₂C(CO₂Et)Br, (CH₃)₂C(COPh)Br] in the presence of Al(Oi-Pr)₃ additive. The molecular weight distributions were narrow (M̄_w/M̄_n ∼ 1.2) throughout the reactions, and the number-average molecular weights (M̄_n) increased in direct proportion to monomer conversion. In contrast, the polymers obtained with CCl₄ in place of R–Br had broader MWDs (M̄_w/M̄_n > 2). The Al(Oi-Pr)₃ additive should be added for the smooth polymerizations of MMA to occur, similarly to those with a divalent nickel bromide, NiBr₂(PPh₃)₂. The Ni(PPh₃)₄-mediated living polymerization apparently proceeds via the activation of the C Br bond from the initiators R Br, assisted by the redox reaction of the complex between Ni(0) and Ni(I) species. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3003–3009, 1999     

Effect of Input Waveform to Vibration Speaker on Sound Quality of Electric Artificial Voice

A number of studies have been conducted on the improvement of the sound quality of electrical artificial laryngeal speech, the speech produced has been difficult to hear compared to a natural voice. For this reason, it is necessary to effectively improve the frequency characteristics of the input signal. In the present study, to improve the sound quality of vocalization using an electrical artifi- cial larynx, first, a comparison of the frequency characteristics between the real and artificial voices was conducted, and three filters that can make the frequency characteristics of the artificial voice closer to those of a real voice were generated. Then, the influence of these filters on the quality of the artificial voice was investigated via physical measurement and a subjective evaluation experiment targeted at Japanese five vowels. It was found that the intelligibility of artificial /a/ and /o/ sounds was improved, whereas little improvement was observed in the case of /i/, /u/, and /e/. The obtained results confirmed the effect of optimizing the input signal into the vibration speaker and indicated areas for further improvement.     

Fractal Roughness Retrieval by Integrated Wavelet Transform

An integrated-wavelet-transform (IWT) approach is proposed for the study of scattering from slightly rough surfaces that manifest scaling properties over a finite domain of correlation lengths. Instead of collecting angle-resolved intensities, values of the irradiance integrated over increasing areas are used to enhance the contributions of small irradiances at large scattering angles and to reduce the coherent noise. In the case of self-similar surfaces, the scaling behavior of IWT allows investigation of the surface roughness at various length scales. For the realistic case of self-affine surfaces, IWT permits the evaluation of the scaling exponent of the autocorrelation and also offers a direct way to evaluate the necessary length scale of the surface profile.