Controlled radical polymerization of styrene with an oxazolidinyl-N-oxyl stable free radical

Summary The bulk polymerization of styrene at 110 °C in the presence of 7-oxo-15-azadispiro[5.2.5.1]pentadecanyl-N-oxyl was investigated. The M _n values of poly(St) formed were increased linearly with conversion, and the M _w/M _n values were 1.48–1.54 at 90% conversion. On the basis of the results it was concluded that 1 controlled radical polymerization of St. Received: 19 October 1998/Revised version: 21 November 1998/Accepted: 26 November 1998     

Preparation of an activated carbon artifact: factors influencing strength when using a thermoplastic polymer as binder

An activated carbon artifact was prepared through mixing, moulding, curing and carbonizing, using polyvinylbutyral resin (PVB) as the binder, dibutyl phthalate (DBP) as a plasticizing agent and isocyanuric acid ester as a cross-linking agent to clarify influential factors on its strength. Preparation conditions such as moulding pressure, temperature and time of curing, carbonization and the amount of cross-linking agent were varied to find their influences on the strength of the resultant form. The form was observed under SEM of wide scope to find correlations between its morphology and strength. The closed packing of the activated carbon filler and the plastic binder was always favorable to develop the strength of the form. The curing extent of PVB, which was influenced by curing atmosphere, temperature and time, and cross-linking agent, was found to govern the strength of the forms. Air or oxygen is very essential for the curing. The optimum temperature was found to be 200°C and longer curing time is beneficial to improve the strength. The cross-linking agent improved the strength of the form up to 7000 kPa through accelerating the cross-linkage of PVB resin. Sufficient curing allows the rapid heating up to 10°C/min for the development of the strength by maintaining the shape of the form. The thermoplastic powders are highly dispersed onto the surface of activated carbons and are cured sufficiently there to adhere the activated carbon grains. Sufficient curing stabilizes the thermoplastic polymer to be thermosetting, anchoring the grains through the carbon bond for higher strength of the carbonized form. PVB resin is cured into heat-resisting cross-linked chains through oxidative condensation onto the activated carbon surface where the oxygen functional groups appear to play important roles in the curing.     

Synthesis of densely grafted copolymers by nitroxide-mediated radical polymerization of styrene using poly(phenylacetylene)s as a macroinitiator

Poly(phenylacetylene)s carrying alkoxyamine moieties in the side chain were prepared by Rh-catalyzed homopolymerization of 1-(4-ethynylphenyl)-1-(2,2,6,6-tetramethyl-1-piperidinyloxyl)ethane (1) and random copolymerization of 1 and 4-methoxy-1-ethynylbenzene (2a) or 4-decyloxy-1-ethynylbenzene (2b). ¹H NMR spectra showed that the poly(phenylacetylene)s adopted a cis-transoid structure. Using the poly(phenylacetylene)s as the macroinitiator the nitroxide-mediated radical polymerization of styrene (St) was carried out at 120 °C to yield densely grafted copolymers as a light yellow powder. The side chain lengths of the graft copolymers were determined by both ¹H NMR and conversion of St, which agreed with each other. The SEC profiles of the graft copolymers were unimodal at low conversions but were not unimodal at high conversion: a shoulder was observed in the high molecular=weight region and a small peak was observed in the low molecular=weight region. ¹H NMR measurements of the graft copolymers indicated that the copolymers adopted a trans-transoid structure, revealing that isomerization from cis-transoid to trans-transoid forms took place during the polymerization of St at 120 °C.     

Structures of two crystal forms of poly(ethylene oxide)-sodium thiocyanate complex with molar ratios of 3:1 and 1:1

The poly(ethylene oxide) (PEO)-sodium thiocyanate system was found to exhibit polymorphism: there exist at least three crystal modifications. Among them, the crystal structures of two kinds of PEO-NaSCN complex with molar ratios (EO:NaSCN) of 3:1 (form I) and 1:1 (form II), respectively, were determined by X-ray diffraction. Crystal data are as follows: form I, monoclinic P2₁/a, a = 16.83, b = 10.64, c(chain axis)=7.19 Å^°

1 Å=10⁻¹ nm, γ=125.5° (c-unique), N=12 EO units (2 chains) and 4 NaSCN ions; form II, monoclinic P2₁/c, a=7.55, b=12.10, c(chain axis)=5.83 Å, β=97.5° (b-unique), N=4 EO units (2 chains) and 4 NaSCN ions. Form I has a crystal structure resembling that of the PEO-NaI complex. The polymer chains have a twofold helical structure of conformation, the chain repeat comprising six EO units. The helical polymer chain coils around an array of Na ions and each Na ion is coordinated by four polymer O atoms and two N of the SCN ions (the coordination number is six). In form II, which exists only under high tension, the polymer chains have a glide structure of conformation, the chain repeat comprising two EO units. Since the PEO chain in form II takes a rather stretched conformation, the Na ions are not wrapped by the polymer chain. The coordination number is again six, but each Na ion is coordinated by two polymer O atoms, two N and two S of the SCN ions. Form II is transformed into form I when the tension is released.     

Machinability of BN free-machining steel in turning

In the past few years, extensive researches have been done to improve the machinability of work materials in order to increase productivity and reduce the effect on the environment. To satisfy these demands, various free-machining steels have been researched and developed. One of them is BN free-machining steel that contains hexagonal boron nitride (h-BN). However, the machinability was not stable. In this study, machining tests were carried out to clarify the machinability of steels and appropriate chemical composition of work material and tool material to achieve high efficient machining. Tested work materials were plane carbon steel JIS S45C and BN free-machining steels. The JIS S45C was used as the standard. The tool wear in turning BN free-machining steel was smaller than that in turning standard steel. In case of turning BN1 with P30 at 200, 300 m/min, the wear progress rate of flank wear and crater depth were about half as much as that in turning standard steel. BN free-machining steel showed slightly lower cutting temperature and smaller cutting force in comparison with standard steel at the tested cutting speeds. Al and N were detected as a layer at the tool wear region of P grade carbide tools after turning BN free-machining steel at high cutting speed. It is thought that one of the main reasons of outstanding machinability of BN free-machining steel is that the deposited layer containing Al and N acts as diffusion barrier at the tool–chip interface. In turning larger Al content BN-added steel with higher Ti content cutting tools, a larger wear reduction was observed. Therefore, it is said that not only added BN but also appropriate Al is necessary in work material.     

Room-temperature mechanical properties of cold-rolled thin foils of binary,stoichiometric Ni3Al

In our previous works, thin foils of boron-free stoichiometric Ni₃Al, with thicknesses ranging from 57 to 315 μm, were fabricated by cold rolling of single-crystalline sheets which were sectioned from directionally solidified ingots. In this article, the room-temperature mechanical properties of the 83 and 95 pct cold-rolled foils were examined. Depending on the initial rolling direction, the foils exhibited two types of deformation microstructures: a banded structure with dual {110} textures and a band-free structure with a single {110} texture. The 83 pct cold-rolled foils showed very high Vickers hardness numbers: 649 and 604 for the banded and band-free structures, respectively. The foils possessed very high tensile fracture stress (1.7 to 2.0 GPa), with no appreciable plastic elongation along the rolling direction. The fracture stress of the 95 pct cold-rolled foils was slightly higher than that of the 83 pct cold-rolled foils. The banded-structure foils showed slightly higher fracture stress than the band-free-structure foils at the 83 pct reduction, but there was no difference between both the structures at the 95 pct reduction. Although there was no appreciable tensile elongation, slip traces were clearly observed on the surfaces of the foil specimens after the tensile test, indicating traces of some plastic deformation. The 95 pct cold-rolled foils possessed bending ductility, which was estimated as about 12 pct elongation on the tension-side surface of the bent specimen.     

Interaction of Nonconservative 1D Continuum and Moving MDOF Oscillator

This paper presents a method for computing the response of a 1D elastic continuum induced by a multi-degree-of-freedom (MDOF) oscillator traveling over it. The continuum and the oscillator are nonconservative systems with proportional damping. Unlike most studies in the field, the solution method does not address a particular type of continuous structure and oscillator. Instead, a rigorous mathematical formulation is presented that can be applied to a broad class of proportionally damped 1D continua and MDOF oscillators, regardless of boundary conditions. The problem is reduced to the integration of a system of linear differential equations with time-dependent coefficients. These coefficients are found to depend on natural frequencies, damping ratios, and eigenfunctions and eigenvectors of the continuum and the oscillator. The method is tested on numerical examples and results are compared to those available in the literature. As a practical application, the method can be used to analyze vehicle-bridge interaction problems.     

Damage Analysis of Hanshin Expressway Viaducts during 1995 Kobe Earthquake. I: Residual Inclination of Reinforced Concrete Piers

The damage suffered by elevated viaducts of the Hanshin Expressway Kobe Route during the 1995 Kobe earthquake is described with emphasis on reinforced concrete (RC) piers. Although many piers were severely damaged, it is also true that the damage to many piers appeared moderate or even mild. On the other hand, a number of piers suffered from large residual inclination in spite of the apparently light damage. By considering that the large residual inclination of piers included severe earthquake-induced damage, it is pointed out that almost all the RC single piers from P35 to P350 received consistently severe damage. The cause of large residual inclination, especially in apparently nondamaged piers, is studied. A dynamic analysis of a single RC pier is conducted to study the relationship between residual inclination and residual deformation of a pier. As a result, we find that the flexural residual deformation of a pier cannot explain the observed large residual inclination, but it is suggested that the pulling out of reinforcing bar from the footing can be a primary cause of the observed large residual inclination.     

Detailed characterization of heteroatom-containing molecules in light distillates derived from Tanito Harum coal and its hydrotreated oil

Heteroatom-containing compounds in as-prepared and hydrotreated distillates produced from Tanito Harum coal were identified by the aid of gas chromatography with atomic emission detector (GC-AED) which can detect all the elements (C, H, N, S, O) contained in the molecules. Alkylated benzothiophenes and dibenzothiophenes were found to be the major sulfur compounds in the original fraction, all of them being completely removed by the hydrotreatment at 350 °C, 10 MPa, and 60 min. Alkylated anilines, quinoline, indoles, and carbazoles were found in the original oil as nitrogen compounds. Two specific nitrogen compounds survived through the hydrotreatment, being identified as C₁₁H₂₀N and C₁₄H₂₃N, respectively, according to the calibrated elemental ratios by GC-AED and molecular weights measured by GC-MS (mass spectrometry). Such empirical formulae were quite similar to C₁₁H₁₉N and C₁₄H₂₃N, respectively, which were detected by high MS and NMR after the concentration by extraction. Some sulfur compounds were observed in the non-aromatic fraction, while all the nitrogen compounds were completely concentrated in the aromatic fraction by the conventional column chromatographic separation. It is also noted that alkylated phenols, benzofurans and dibenzofurans were found as typical oxygen compounds in the distillate. Thus, GC-AED can identify the hetero-atom containing compounds based on the simultaneous multi-element analysis.     

Suppression of Bridge Flutter by Active Deck-Flaps Control System

A theoretical study on an aerodynamic control method for suppression of the wind-induced instabilities of a very long span bridge is presented in this paper. The control system consists of additional control flaps attached to the edges of the bridge deck. Their rotational movement, commanded via feedback control law, is used to modify the aerodynamic forces acting on the deck and provides aerodynamic forces on the flaps used to stabilize the bridge. A time domain formulation of self-excited and buffeting forces is obtained through the rational function approximation of the generalized Theodorsen function. The optimal configuration of the deck-flaps system is found with respect to the performance index based on stability robustness of the system. A control system with the rotational center of the flaps that is located on the edges of the deck was found to be the most effective. It is also shown that this control system can provide sufficient aerodynamic damping and satisfactory stability robustness of the system with a relatively small flap size for the considered range of wind speed.