Synthesis,characterization, and curing kinetics of novel ladder‐like polysilsesquioxanes containing side‐chain maleimide groups

Two ladder‐like polysilsesquioxanes (LPS) containing side‐chain maleimide groups have been synthesized successfully by reacting N‐(4‐hydroxyphenyl)maleimide (HPM) with LPS containing 100 mol % of chloropropyl groups (Ladder A ) and 50 mol % of each methyl and chloropropyl group (Ladder B ). HPM was synthesized by reacting maleic anhydride with 4‐aminophenol, and the resulting amic acid was imidized using p‐toluenesulfonic acid as a catalyst (Scheme 1 ). The LPSs were characterized by Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance (NMR), proton‐decoupled ¹³C NMR, ²⁹Si NMR, wide‐angle X‐ray diffraction (WAXD), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Characterization indicated that these polymers had ordered ladder‐like structures with possible defects. These polymers were soluble in common solvents at ambient temperature, which suggested that they were not crosslinked. Both the polymers and the HPM were cured, and their kinetics were followed by dynamic DSC. The Ozawa and Kissinger methods were used to calculate activation energies for curing. Curing increased the temperature at which both 5% weight loss and maximum rate of weight loss were observed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4036–4046, 2004     

Dielectric relaxation analysis of starch oligomers and polymers with respect to their chain length

Starch belongs to the polyglucan group. This type of polysaccharide shows a broad β-relaxation process in dielectric spectra at low temperatures, which has its molecular origin in orientational motions of sugar rings via glucosidic linkages. This chain dynamic was investigated for α(1,4)-linked starch oligomers with well-defined chain lengths of 2, 3, 4, 6, and 7 anhydroglucose units (AGUs) and for α(1,4)-polyglucans with average degrees of polymerization of 5, 10, 56, 70, and so forth (up to 3000; calculated from the mean molecular weight). The activation energy (E_a) of the segmental chain motion was lowest for dimeric maltose (E_a = 49.4 ± 1.3 kJ/mol), and this was followed by passage through a maximum at a degree of polymerization of 6 (E_a = 60.8 ± 1.8 kJ/mol). Subsequently, E_a leveled off at a value of about 52 ± 1.5 kJ/mol for chains containing more than 100 repeating units. The results were compared with the values of cellulose-like oligomers and polymers bearing a β(1,4)-linkage. Interestingly, the shape of the E_a dependency on the chain length of the molecules was qualitatively the same for both systems, whereas quantitatively the starch-like substances generally showed higher E_a values. Additionally, and for comparison, three cyclodextrins were measured by dielectric relaxation spectroscopy. The ringlike molecules, with 6, 7, and 8 α(1,4)-linked AGUs, showed moderately different types of dielectric spectra. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 188–197, 2004     

Potential for micromachined actuation of ultra-wide continuously tunable optoelectronic devices

Tailored scaling represents a principle of success that, both in nature and in technology, allows the effectiveness of physical effects to be enhanced. Mutation and selection in nature are imitated in technology, e.g. by model calculation and design. Proper scaling of dimensions in natural photonic crystals and our fabricated artificial 1D photonic crystals (DBRs, distributed Bragg reflectors) enable efficient diffractive interaction in a specific spectral range. For our optical microsystems we illustrate that tailored miniaturization may also increase the mechanical stability and the effectiveness of spectral tuning by thermal and electrostatic actuation, since the relative significance of the fundamental physical forces involved considerably changes with scaling. These basic physical principles are rigorously applied in micromachined 1.55-μm vertical-resonator-based devices. We modeled, implemented and characterized 1.55-μm micromachined optical filters and vertical-cavity surface-emitting laser devices capable of wide, monotonic and kink-free tuning by a single control parameter. Tuning is achieved by mechanical actuation of one or several air-gaps that are part of the vertical resonator including two ultra-highly reflective DBR mirrors of strong refractive index contrast: (i) Δn=2.17 for InP/air-gap DBRs (3.5 periods) using GaInAs sacrificial layers and (ii) Δn=0.5 for Si₃N₄/SiO₂ DBRs (12 periods) with a polymer sacrificial layer to implement the air-cavity. In semiconductor multiple air-gap filters, a continuous tuning of >8% of the absolute wavelength is obtained. Varying the reverse voltage (U=0–5 V) between the membranes (electrostatic actuation), a tuning range of >110 nm was obtained for a large number of devices. The correlation of the wavelength and the applied voltage is accurately reproducible without any hysteresis. In two filters, tuning of 127 and 130 nm was observed for about ΔU=7 V. The extremely wide tuning range and the very small voltage required are record values to the best of our knowledge. For thermally actuated dielectric filters based on polymer sacrificial layers, Δλ/ΔU=-7 nm/V is found. Received: 10 May 2002 / Published online: 8 August 2002     

A covariant quasipotential operator for a composite system of two scaler particles

A quasipotential operator for a system of two scalar particles, and also an integral equation and a normalization condition for the wave function of the connected state, are obtained by the method of two-time Green's functions in an explicitly covariant form. The cases are considered of scalar and electromagnetic interactions of particles of the system.Frantsiska Skoriny Gomel' State University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 112–118, June, 1993.     

Runge–Kutta Methods for Itô Stochastic Differential Equations with Scalar Noise

A general class of stochastic Runge–Kutta methods for Itô stochastic differential equation systems w.r.t. a one-dimensional Wiener process is introduced. The colored rooted tree analysis is applied to derive conditions for the coefficients of the stochastic Runge–Kutta method assuring convergence in the weak sense with a prescribed order. Some coefficients for new stochastic Runge–Kutta schemes of order two are calculated explicitly and a simulation study reveals their good performance.     

Study of the spontaneous formation of organic layers on carbon and metal surfaces from diazonium salts

This study investigates the spontaneous grafting of different para-substituted phenyl groups on carbon and metallic surfaces from diazonium salts solutions. Glassy carbon, nickel, zinc and iron plates were allowed to react with an acetonitrile solution of aryldiazonium tetrafluoroborate salt by simple dipping. The surfaces were characterized before and after their immersion by XPS and AFM to evidence the formation of a coating on the different materials. The results are indicative of the presence of substituted phenyl groups on all the investigated surfaces. This study also aims at correlating grafting efficiency with metal reactivities and diazonium salt electronic properties by means of AFM and FT-IRRAS. For this purpose, zinc and nickel were chosen due to their opposite reducing properties and two diazonium salts were selected with electron-donor or -withdrawing para-substituents. The results tend to indicate that redox properties of both partners (diazonium + metal) are of prime importance for grafting to occur.     

Resonant-cavity-enhanced photodetectors and LEDs in the mid-infrared

In this paper we outline the use of resonant-cavity enhancement for increasing the exterior coupling efficiency of photodetectors and light-emitting diodes (LEDs) in the mid-infrared (MIR) spectral region. This method is potentially very important in the MIR because encapsulation is not presently feasible due to the lack of suitable materials. Among other potential applications, resonant-cavity-enhanced (RCE) photodetectors and LEDs could be particularly suitable for greenhouse gas detection because of their ‘pre-tunable’ spectrally narrowed resonantly enhanced peaks. We also present the optical characterization of an InAs RCE photodetector aimed at the detection of methane gas (λ≈3.3 μm), and an InAs/InAs_0.91Sb_0.09 resonant-cavity LED (RCLED) aimed at carbon dioxide gas (λ≈4.2 μm). The high peak responsivity of the RCE photodetector was 34.7 A/W at λ=3.14 μm, and the RCLED peaked at λ=3.96 μm. These are among the longest operating wavelengths for III–V RCE photodetectors and RCLEDs reported in the literature.