Polymerization of 1,3‐dienes with functional groups. III. Free‐radical polymerization of N,N‐diethyl‐2‐methylene‐3‐butenamide

Free‐radical homo‐ and copolymerization behavior of N,N‐diethyl‐2‐methylene‐3‐butenamide (DEA) was investigated. When the monomer was heated in bulk at 60 °C for 25 h without initiator, rubbery, solid gel was formed by the thermal polymerization. No such reaction was observed when the polymerization was carried out in 2 mol/L of benzene solution with with 1 mol % of azobisisobutyronitrile (AIBN) as an initiator. The polymerization rate (R_p) equation was R_p ∝ [DEA]^1.1[AIBN]^0.51, and the overall activation energy of polymerization was calculated 84.1 kJ/mol. The microstructure of the resulting polymer was exclusively a 1,4‐structure where both 1,4‐E and 1,4‐Z structures were included. From the product analysis of the telomerization with tert‐butylmercaptan as a telogen, the modes of monomer addition were estimated to be both 1,4‐ and 4,1‐addition. The copolymerizations of this monomer with styrene and/or chloroprene as comonomers were also carried out in benzene solution at 60 °C. In the copolymerization with styrene, the monomer reactivity ratios obtained were r₁ = 5.83 and r₂ = 0.05, and the Q and e values were Q = 8.4 and e = 0.33, respectively. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 999–1007, 2004     

Application of novel SIMS technique for imaging the active sites of oxygen reduction at the SOFC cathode/electrolyte interfaces

The oxygen reduction active sites were visualized around the O₂/SOFC cathode/electrolyte triple phase boundaries (TPB) by the¹⁶O/¹⁸O exchange techniques and secondary ion mass spectrometry (SIMS) analysis. The higher¹⁸O concentration is observed on the cathode top surfaces (La_0.9Sr_0.1MnO₃-mesh, Au-mesh, and Ag-porous), which suggested the promotion of oxygen adsorption and oxygen surface exchange at the cathode. The oxygen diffusion through the bulk of cathode occurred at the La_0.9Sr_0.1MnO₃-mesh and the Ag-porous cathodes, not at the Au-mesh cathode. On the YSZ surfaces after removing the cathode, the active sites for oxygen incorporation were analyzed by SIMS. The active sites for oxygen incorporation were at the La_0.9Sr_0.1MnO₃/YSZ interface as well as the TPB. On the other hand, the active sites for oxygen incorporation are limited to the TPB in the case of the Au-mesh removed YSZ surface. From the SIMS analysis, the expansion of the active sites for oxygen incorporation is less than a few μm from the TPB lines. Paper presented at the 8th EuroConference on Ionics, Carvoeiro, Algarve, Portugal, Sept. 16–22, 2001.     

Reconstruction of the Point-Spread Function of the Human Eye Using a New Phase-Retrieval Algorithm

The double-pass method is thought to obtain the point spread function (PSF) in human eyes based on two techniques: the symmetric double-pass method using the same pupil size and the asymmetric double-pass method using a different pupil size. The symmetric double-pass method provides autocorrelation of the retinal PSF and, thus, the modulation transfer function. The asymmetric double-pass method provides low-frequency partial-phase information and the partial phase-retrieval algorithm is applied to obtain the complete-phase information, and to estimate the PSF. The partial phase-retrieval algorithm is based on the iteration method proposed by Fineup and Kowalczyk and requires a lengthy computation. In this study, we propose a new high-speed phase-retrieval algorithm based on the property that the real and imaginary parts of optical transfer functions (OTFs) continuously change in value.     

Elastic friction drive of surface acoustic wave motor

Importance of elastic deformation control to obtain large output force with a surface acoustic wave (SAW) motor is discussed in this paper. By adding pre-load to slider, stator and slider surfaces are deformed in a few tens nanometer. Appropriate deformation in normal direction against normal vibration displacement amplitude of SAW existed. By moderate deformation, the output force of the SAW motor was enlarged up to about 10 N and no-load speed was 0.7 m/s. To produce this performance, the transducer weight and slider size were only 4.2 g and 4 x 4 mm(2).By traveling wave propagation, surface particles of the SAW device move in elliptical motion. Due to the amplitude of the elliptical motion is 10 or 20 nm order, the contact condition of the slider is very critical. To control the contact condition, namely, the elastic deformation of the slider and stator surface in nanometer order, a lot of projections were fabricated on the slider surface. The projection diameter was 20 micro m. In static condition, the elastic deformation and stress were evaluated with the FEM analysis. From this calculation and the simulation result, it is consider that the wave crest is distorted, hence the elasticity has influence on the friction drive condition.Elastic deformation of the stator surface beneath the projection from the initial position were evaluated. In 4 x 4 mm(2) square area, the sliders had from 1089 to 23,409 projections. Depression was independent to the contact pressure. However, the output force depended on the depression although the projection density were different. From the view point of the output power of the motor, the proper depression was independent to the projection density. Around 25 nm depression, the output force and output power were maximized. This depression value was almost same as the vibration displacement amplitude of the stator transducer.     

Widely tunable terahertz-wave generation using an N-benzyl-2-methyl-4-nitroaniline crystal

Widely tunable terahertz (THz)-wave generation using difference frequency generation (DFG) in an organic N-benzyl-2-methyl-4-nitroaniline (BNA) crystal was demonstrated. To our knowledge, this is the first report of THz-wave generation by BNA DFG. Large, high-quality single crystals of BNA (phi 8 mm x 30 mm) were grown using the vertical Bridgman method. The nonlinear optical (NLO) coefficient d(33) of the BNA crystal is approximately 234 pm/V, which is the largest value reported for any yellow NLO material. The collinear phase-matching condition of the type-0 configuration is satisfied using a 0.7-1 microm band pump wavelength. We generated THz waves using an organic BNA crystal; the generation range is 0.1-15 THz.     

Synthesis and Optical Properties of SiO2-Coated CeO2 Nanoparticles

Silica (SiO₂)-coated ceria (CeO₂) nanoparticles were prepared using water-in-oil microemulsion. Polyoxyethylene (15) cetylether and cyclohexane were used as a surfactant and organic solvent. SiO₂-coated CeO₂ nanoparticles were obtained by hydrolysis of metal alkoxide (tetraethylorthosilicate, TEOS) in the solution containing CeO₂ precursor nanoparticles. The effects of CeO₂ sources (Ce metal salt) and CeO₂ particle-forming agents on the morphology of SiO₂–CeO₂ particles were investigated. Observation via transmission electron microscopy revealed that the type of particle-forming agent affected the nanoparticles' morphology and that CeO₂ nanoparticles were spherically coated with SiO₂ when using oxalic acid ((COOH)₂) as a particle-forming agent of CeO₂. Furthermore, the transmittance of the particles was high in the visible region (above 400 nm) and decreased in the ultraviolet region.     

Chemical component mapping of pulverized toner by scanning transmission X-ray microscopy

Toners are micron scale polymer particles constructed of several kinds of resin, pigment, wax, etc. Transmission electron microscopy (TEM) is used for observation of the dispersion of the component materials in toners, but TEM images cannot identify simultaneously all components. Scanning transmission X-ray microscopy (STXM) not only provides simultaneous observation of spatial distributions of wax, resin and carbon black in toners, but it also provides detailed, quantitative, chemical information about the wax and resin environments through chemical component maps derived from multiple energy image sequences. The capabilities of STXM for toner analysis are illustrated by results of a study of a toner for black/white copy/print applications.     

Enrichment of surfactant from its aqueous solution using ultrasonic atomization

Dilute aqueous solutions of dodecyl-benzenesulfonic acid sodium salt (DBS-Na) and polyoxyethylenenonylphenyl ethers (PONPEs) were ultrasonically atomized. The surfactants were concentrated in collected mist droplets. The enrichment ratio increased with decreasing surfactant concentration. Depending on the surfactant’s molecular weight and affinity to water, different enrichment ratio was observed in the range of low feed concentrations. For anionic surfactant, DBS-Na, the enrichment ratio was significantly improved by KCl addition and a peak appeared on the plot of the ratio against KCl concentration. Addition of NaCl or CaCl₂ · 2H₂O to the surfactant solution also enhanced the enrichment ratio; however, the effect was relatively small. Such behaviors of the ratio were interpreted as enhanced interfacial adsorption of the surfactant and a lack of supply of surfactant monomers from liquid bulk because of slow breaking of surfactant micelles. Time required for collecting an amount of mist was also observed. Among the three salt systems, the time for KCl system was twice as long as others. This fact suggested that the formation of smaller droplets in KCl system.