Morphology and properties of poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene]/silica nanoparticle hybrid films

Poly[2‐methoxy‐5‐(2′‐ethyl‐hexyloxy)‐para‐phenylene vinylene] (MEH‐PPV)/silica nanoparticle hybrid films were prepared and characterised. Three kinds of materials were compared: parent MEH‐PPV, MEH‐PPV/silica (hybrid A films), and MEH‐PPV/coupling agent MSMA/silica (hybrid B films), in which MSMA is 3‐(trimethoxysilyl) propyl methacrylate. It was found that the hybrid B films could significantly prevent macrophase separation, as evidenced by scanning electron and fluorescence microscopy. Furthermore, the thermal characteristics of the hybrid films were largely improved in comparison with the parent MEH‐PPV. The UV‐visible absorption spectra suggested that the incorporation of MSMA‐modified silica into MEH‐PPV could confine the polymer chain between nanoparticles and thus increase the conjugation length. The photoluminescence (PL) studies also indicated enhancement of the PL intensity and quantum efficiency by incorporating just 2 wt% of MSMA‐modified silica into MEH‐PPV. However, hybrid A films did not show such enhancement of optoelectronic properties as the hybrid B films. The present study suggests the importance of the interface between the luminescent organic polymers and the inorganic silica on morphology and optoelectronic properties. Copyright © 2004 Society of Chemical Industry     

Properties of nanoporous organosilicate hybrid thin films with a bimodal pore size distribution

Low dielectric poly[methylsilsesquioxane‐ran‐trifluoropropylsilsesquioxane‐ran‐(2,4,6,8‐tetramethyl‐2,4,6,8‐tetraethylenecyclotetrasiloxane)silsesquioxane]s {P[M‐ran‐TFP‐ran‐(TCS)]SSQs} having various compositions were synthesized using trifluoropropyl trimethoxysilane, methyl trimethoxysilane and 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane. The chemical composition of the polymers and the content of SiOH end‐groups were controlled by adjusting the reaction conditions, and they were characterized by ¹H‐NMR. The thermally decomposable trifluoropropyl groups on the P[M‐ran‐TFP‐ran‐(TCS)]SSQ backbone and heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin (CD) were employed as pore generators. The dielectric constants of the porous CD/P[M‐ran‐TFP‐ran‐(TCS)]SSQ films were in the range 2.0–2.7 (at 100 kHz) depending on the concentration of the porogens, and showed no change over 4 days under aqueous conditions. The pore size of the films showed a bimodal distribution, with diameters of ca 0.5–1.0 nm for those originating from the trifluoropropyl groups and 1.7 nm from the CD. The elastic modulus and hardness of the 30 vol% CD‐blended film with a dielectric constant of 2.26 were 2.40 and 0.38 GPa, respectively, as determined by a nanoindenter. Copyright © 2005 Society of Chemical Industry     

Direct adaptive control of nonminimum phase systems using integralaction

A direct adaptive control scheme is proposed for nonminimum-phase systems in which controller parameters are estimated from the recursive least-squares algorithm and additional auxiliary parameters are obtained from the proposed polynomial identity. A local convergence is guaranteed without any extra condition. Integral action is incorporated into the adaptive controller to eliminate the steady-state error and to satisfy a condition of the unique solution for the polynomial identity. The control law used in this scheme is based on the set-point-on-I-only proportional-integral-derivative (PID) structure     

Evaluating the transfer of technology between application domains: a critical evaluation of the human component in the system

Technology can take many forms from the development of sophisticated electronics to the application of basic procedural principles. Technology transfer can also take several forms, however, in this case, it is the transfer of technological principles between application domains that is of primary interest. This paper presents a framework (the Five ‘M’s framework) that can be used to consider the likely success of technology transfer. The framework is based upon a sociotechnical system approach. The framework is illustrated with an evaluation of the introduction of intelligent cruise control into motor vehicles. It is argued that this is a technological concept first developed as an aerospace application in the form of the autopilot. In this case, it is argued that the transfer of this technology in its current form may potentially compromise safety.     

Effects of gallia additions on sintering behavior of gadolinia-doped ceria

The effects of gallia additions on the sintering behavior of gadolinia-doped ceria were systematically investigated from the following aspects: the variation in sintered density, the variation in grain size, and the existing forms of Ga₂O₃ in CeO₂.Sintered density increased with increasing Ga₂O₃ content up to 5 mol.% and then it decreased with further addition of Ga₂O₃. Grain size also increased with increasing Ga₂O₃ content up to 5 mol.% and then decreased with further addition of Ga₂O₃. Decrease in grain size was caused by a pinning effect of Ga₂O₃ precipitation at grain boundaries. Lattice constant decreased with increasing Ga₂O₃ content up to 5 mol.%. This decrease will be due to the substitution of smaller Ga³⁺ ions for Ce⁴⁺ ions in the CeO₂ structure. According to the results obtained from scanning electron microscope (SEM) and X-ray diffraction (XRD) analyses, the solubility limit of Ga₂O₃ in Ce_0.8Gd_0.2O_1.9 ceramics can be estimated to be nearly 5 mol.%. The addition of Ga₂O₃ up to the solubility limit was found to promote the sintering properties of Gd₂O₃-doped CeO₂.     

Synthesis and characterization of a series of star-branched poly(ε-caprolactone)s with the variation in arm numbers and lengths

A series of star-branched poly(ε-caprolactone)s (SPCLs) was synthesized with structural variation of the arm numbers and lengths through ring-opening polymerization under bulk condition. Arm numbers were varied to be 3, 4, and 6 by using multifunctional initiating cores such as trimethylol propane, pentaerythritol, and dipentaerythritol, respectively. The lengths of the poly(ε-caprolactone) arms were varied by controlling the molar ratio of monomer-to-initiating hydroxyl group molar ratio ([CL]₀/[-OH]₀=5, 10, 15). Molecular weights were determined by both ¹H NMR end-group analysis and MALDI-TOF mass spectrometry, which gave reasonably consistent values. On the contrary, the GPC method failed to give accurate values of molecular weight of SPCLs due to the discrepancy with the linear standard. The branching architecture of SPCLs was evaluated by the branching ratio, g, which is the ratio of the mean-square radius of SPCL to that of liner counterpart, linear poly(ε-caprolactone) (LPCL), which is of the same chemistry and having the same molecular weight. The radii of gyration of SPCLs and LPCLs were determined using small-angle X-ray scattering (SAXS) from the initial slopes of Zimm plots, represented as 1/I(q) vs q² with I(q) and q being the scattered intensity and scattering vector, respectively. The g values were observed to decrease with increasing arm numbers, indicating more compact molecular structure for SPCLs with higher arm numbers, while no such effect was observed for arm length variation. Thermal properties as well as the degree of crystallinity of SPCLs were found to be also dependent on structural variations. The melting points and the degradation temperatures were observed to increase with increasing arm lengths but with constant arm number. On the other hand, arm number variation with constant arm length gave no such changes to the thermal transitions of SPCLs. However, for the SPCLs with equivalent molecular weights, the degree of crystallinity was found to decrease with increasing arm numbers.     

Protein binding study of isoflavone, perillyl alcohol and S-ibuprofen by high-performance frontal analysis

High-performance frontal analysis (HPFA) was used for a protein binding study of isoflavones (daidzein, genistin, and genistein), enantiomers of perillyl alcohol and S-ibuprofen to human serum albumin (HSA). The analyses were performed on a Develosil and Inertsil 100-Diol-5 column (10 cm×4.6mm). Sodium phosphate solution (pH 7.4, ionic strength 0.17) was used as the mobile phase at a flow rate of 1 ml/min. To ensure the drug to be eluted as a trapezoidal peak with a plateau, injection volumes were each fixed up the zonal profile with an evident plateau appears. The unbound drug concentration was determined from a plateau height of the plateau region after that experimental data were fitted by Scatchard equation. The binding constants (K) and total binding affinities (nK) of drugs to HSA were calculated, respectively.     

Design and practical implementation of multifrequency RF front ends using direct RF sampling

The use of direct RF sampling has been explored as a means of designing multifrequency RF front ends. Such front ends will be useful to multifrequency RF applications such as global navigation satellite system receivers that use global positioning system (GPS) L1, L2, and L5 signals and Galileo signals. The design of a practical multifrequency direct RF sampling front end is dependent on having an analog-to-digital converter whose input bandwidth accommodates the highest carrier frequency and whose maximum sampling frequency is more than twice the cumulative bandwidth about the multiple carrier signals. The principle of direct RF sampling is used to alias all frequency bands of interest onto portions of the Nyquist bandwidth that do not overlap. This paper presents a new algorithm that finds the minimum sampling frequency that avoids overlap. This design approach requires a multifrequency bandpass filter for the frequency bands of interest. A prototype front end has been designed, built, and tested. It receives a GPS coarse/acquisition code at the L1 frequency and GPS antispoofing precision code at both L1 and L2. Dual-frequency signals with received carrier-to-noise ratios in excess of 52 dB-Hz have been acquired and tracked using this system.     

Mechanical improvement of concrete by irradiated polypropylene fibers

Fiber reinforced concrete (FRC) contains fibers physically mixed with gravel, sand, cement, and water. So far, adequate mechanical performance of FRC has been obtained at high cost and using complex technologies; important here is the geometry and surface characteristics of the polymers. We have modified polymeric‐fiber surfaces by using gamma radiation. Irradiated polypropylene (PP) fibers were submitted to 0, 5, 10, 50, and 100 kGy of gamma irradiation dosages. First, tensile strength of PP fibers was evaluated, and then fibers blended at 0, 1.0, 1.5, and 2.0% in volume with Portland cement, gravel, sand, and water. The highest values of compressive strength were obtained with irradiated‐fibers at 10 kGy and 1.5% in volume of fiber. The result is 101 MPa, as compared to 35 MPa for simple concrete without fibers. POLYM. ENG. SCI., 45:1426–1431, 2005. © 2005 Society of Plastics Engineers