Studies on segmented polyurethane—urea elastomers: Structure of segmented polyurethane—urea based on poly(tetramethylene glycol), 4,4'-diphenylmethane diisocyanate,and 4,4'-diaminodiphenylmethane

Structure studies on the segmented polyurethane-urea based on poly(tetramethylene glycol), 4,4'-diphenylmethane diisocyanate, and 4,4'-diaminodiphenylmethane have been made using wide- and small-angle x-ray diffraction. It was found that the hard segments have a well-defined crystal structure indexed by a monoclinic unit cell with dimensions a = 4.72 Å, b = 11.33 Å, c (chain axis) = 11.64 Å, and γ = 116.5°. Further, the hard segments have an anisotropic supermolecular structure, that is, a spherulitic crystalline texture. The microdomain structure depends on the molecular weight of the soft segments, with phase separation becoming distinct with an increase in the molecular weight of the soft segment. Based on the long period observed in small-angle x-ray patterns of heat-set specimens, the thickness of lamellae was estimated to be about 93 Å. This corresponds to an average hard segment sequence length of 8. On deformation, the hard segment orients preferably transverse to the stretch direction up to high elongations, and it shows a hysteresis of orientation. This phenomenon can be explained in terms of the anisotropic supermolecular structure. Further, deviation from ideal rubber elasticity observed in the stress-strain relationships of the segmented polyure-thane-urea elastomers might also be caused by the anisotropic structure.     

Mark–Houwink–Sakurada constants for carboxylated segmented polyurethane

Carboxylated polyurethane (PEUA) based on methylene-bis-4,4′-phenyl isocyanate, poly(propylene oxide), and 2,2′-hydroxymethyl propionic acid were synthesized. The effect of temperature on the extension stage of the polymerization reaction as well as that of the concentration of reagents on the molecular weight of PEUA were investigated by means of gel permeation chromatography (GPC). The best conditions for obtaining the highest molecular weight polymer correspond to the chain extension reaction temperature of 50°C and to a polymer concentration of 50% w/v. The obtained polymers have been characterized by ¹³C-NMR, Fourier transform infrared spectroscopy and differential scanning calorimetry. It was seen that, in the reaction conditions adopted, the formation of ureic groups does not occur and that the increase of molecular weight causes a lower mobility of the chains, as evidenced by a small increase of T _g. The values of the PEUA Mark–Houwink–Sakurada constants in tetrahydrofuran (THF) at 25°C, determined by GPC and viscosity measurements, indicate that the polymer chain in THF is characterized by a high flexibility.     

224 nm segmented hollow-cathode silver ion laser

The segmented hollow-cathode discharge arrangement is used the first time to excite the 224 nm Ag II laser transition. Quasi-continuous output power of 45 mW is obtained during the 300 s current pulses at optimal discharge conditions (10 hPa of He+4% Ar buffer gas) for discharge current of 3 A. No power saturation is observed up to this current value. An average output power of 0.75 mW is reached using pulse repetition frequency of 190 Hz. The longitudinal mode structure of the TEM₀₀ transversal mode is measured by means of a scanning confocal Fabry–Perot interferometer. Two-mode operation is found to be dominant at high current values. Attempts and suggestions are made to prolong the lifetime of the laser tube. PACS 42.55.Lt; 42.60.Lh; 52.80.-s     

A novel hybrid surface micromachined segmented mirror for large aperture laser applications

A novel hybrid surface micromachined segmented mirror array is described. This device is capable of scaling to large apertures for correcting time-varying aberrations in laser applications. Each mirror is composed of bottom electrode, support pan, and mirror plate, in which a T-shaped beam structure is used to support the mirror plate. It can provide mirror with vertical movement and rotation around two horizontal axes. The test results show that the maximum deflection along the vertical direction of the mirror plate is 2μm, while the rotation angles around x and y axes are±2.3°and±1.45°, respectively.     

Preparation of poly(?-caprolactone)-based polyurethane nanofibers containing silver nanoparticles

In this study, poly(?-caprolactone)-based polyurethane (PCL-PU) nanofibers containing Ag nanoparticles for use in antimicrobial nanofilter applications were prepared by electrospinning 8 wt% PCL-PU solutions containing different amounts of AgNO₃ in a mixed solvent consisting of DMF/THF (7/3 w/w). The average diameter of the pure PCL-PU nanofibers was 560 nm and decreased with increasing concentration of AgNO₃. The PCL-PU nanofiber mats electrospun with AgNO₃ exhibited higher tensile strength, tensile modulus, and lower elongation than the pure PCL-PU nanofiber mats. Small Ag nanoparticles were produced by the reduction of Ag⁺ ions in the PCL-PU solutions. The average size and number of the Ag nanoparticles in the PCL-PU nanofibers were considerably increased after being annealed at 100 °C for 24 h. They were all sphere-shaped and evenly distributed in the PCL-PU nanofibers, indicating that the PCL-PU chains stabilized the Ag nanoparticles well.     

Organic–inorganic nanocomposite films made from polyurethane dispersions and colloidal silica particles

Polyurethane/silica nanocomposites were prepared by solution blending of polyurethane water dispersion (PUD) based on polycarbonate macrodiol with colloidal silica aqueous sol LUDOX TMA. Because of mixing PUDs made from linear polyurethane with the nanofiller, only physical polymer/filler type of interface formed by hydrogen bonds was obtained. As a result the materials were possible to reuse after dissolution in acetone followed by dispersion in water. The effect of colloidal silica content on mechanical, thermal, morphological, and swelling properties of obtained films was tested by tensile test, dynamic mechanical thermal analysis, thermogravimertic analysis, scanning electron microscopy, atomic force microscopy, and swelling analyses. The nanocomposites were classified in three groups differing in the internal structure and functional properties: organic matrix filled with inorganic nanofiller (up to 10 wt% of silica), bicontinous systems (25 and 32 wt% of silica) and inorganic matrix filled with polyurethane (50 and 60 wt% of silica). Only small amount of colloidal silica (up to 10 wt%) improves thermo-mechanical properties, smoothes the materials, and suppresses extent of swelling without changing of the films transparency.     

Surface characteristics of UV-irradiated polyurethane elastomers extended with α, ω-alkane diols

Polyurethane elastomers (PUEs) based on 4,4′-diphenylmethane diisocyanate (MDI), poly (?-caprolactone) (PCL) and extended with series of chain extender (CE) were synthesized via two step polymerization technique. The synthesized samples were irradiated for 50, 100 and 200 h in an UV exposure unit as such the spectral distribution of the light is good match for terrestrial solar radiation. The modifications in the chemical structures of the PU before and after irradiation were characterized using Fourier transform infrared (FT-IR) technique. The effect of irradiation time and chain extenders length on surface properties were studied and investigated. Photo-oxidation of PU surface leads to fast increase in surface free energy and its polar component. Simultaneously, the work of water adhesion to polymer increases significantly during UV-irradiation. The higher changes in surface properties, observed by water absorption (%), equilibrium degree of swelling, as well as monitored by ATR-FT-IR and contact angle measurement, were found for the PU samples extended with higher number of methylene unit and irradiation time.     

Design of segmented cladding fiber for femtosecond laser pulse delivery at 1550 and 1064 nm wavelengths

Segmented cladding fiber (SCF) is capable of single mode operation over an extended range of wavelengths while maintaining large mode area. In this paper we report the design of an SCF with mode area as large as 1,825  $\upmu \hbox {m}^{2}$ , suitable for delivery of high peak power femtosecond laser pulses at 1550 and 1064 nm wavelengths. An SCF with such a large-mode area is a few-moded fiber and its design requires careful choice of design parameters to have robustness against mode-coupling effects and bend loss. In this paper we address these issues and report a design of an SCF showing near distortion-free propagation of 100-fs, 53-kW peak power pulses at 1550-nm wavelength with 1,825- $\upmu \hbox {m}^{2}$ mode area through fundamental mode. The same fiber can also deliver 250-fs, 15-kW peak power pulses at 1064-nm wavelength with 1,793- $\upmu \hbox {m}^{2}$ mode area. The fiber has been analyzed by using the radial effective-index method in conjunction with transfer matrix method and the pulse propagation has been studied by solving the nonlinear Schroedinger equation by split-step Fourier method. Such a fiber would find applications in multiphoton microscopy and in biomedical engineering.     

Measurement of ablative laser propulsion parameters for aluminum, Co–Ni ferrite and polyurethane polymer

Laser ablation propulsion is a form of beam-powered propulsion in which a pulsed laser ablates a target material thus producing thrust. We report in this work the measurements of various parameters related to laser-induced micropropulsion in toluene diisocyanate-based polyurethane polymer, aluminum and Co–Ni ferrite. The targets were irradiated by a Q-switched pulsed Nd–YAG laser at 1064 nm (pulse duration 5 ns) under atmospheric conditions. A contact-free optical triangulation method was used to measure the laser ablation induced thrust in the samples. The measurements and calculations depict that Co–Ni ferrite is better in terms of critical propulsion parameters C _m and I _sp. It has been observed that the propulsion parameters depend on the energy per pulse of the incident laser beam.     

Electrostrictive properties of thermoplastic polyurethane elastomer: Effects of urethane type and soft–hard segment composition

The electromechanical behavior of thermoplastic elastomer polyurethane (TPE-PU) is investigated under the effects of urethane type (ester and ether-types) and soft–hard segments at various electric field strengths and temperatures. The highest dielectric constant, electrical breakdown strength, and specific conductivity belong to the ester-type polyurethane (LPR matrix), while the lowest values are obtained from the ether-type polyurethane composing predominantly with the soft-segment (E 80A matrix). Under the electric field strength in the range between 0 and 2 kV/mm, the LPR matrix attains the storage modulus sensitivity (ΔG′/G′₀) up to 2 at 2 kV/mm. For the temporal response, the polyurethanes behave with good reproductively (number of cycles >10⁵ times) and with very good recoverability. The steady state behavior can be attained at the first actuation and at the electric field strength of 1 kV/mm. Furthermore, the storage modulus (G′) shows linearly negative responses with increasing temperature. In the deflection experiments, the deflection distance and the dielectrophoresis force increase monotonically with increasing electric field strength. All of the TPE-PU possesses very fast response times for activation (<10 s.) and deactivation (<5 s.). TPE-PU material is systematically shown here to be a potentially good actuator material with high efficiency based on the electrostrictive performance data obtained.     

Y—Ba—Cu—Sn—O高温超导体

用Sn分别部分替代Y-Ba-Cu-O系超导体中的Y或Cu,制备了Y-Ba-Cu-Sn-O系超导体,实验结果表明,在相当大的替代范围(30%的 Y,40%的 Cu)内,超导体仍保持正交结构,其零电阻转变温度基本上稳定在90K左右.     

1—(4—吡啶甲酰)—4—芳基氨基硫脲类和3—(4—吡啶基)—4—芳基—1,2,4—三唑啉—5—硫酮类化合物~(13)C—NMR谱研究

本文测定了新合成的,具有生理活性的1-(4-吡啶甲酰)-4 -苯基氨基硫脲,1-(4-吡啶甲酰)-4-对氯苯基氨基硫脲,1-(4 -吡啶甲酰)-4-对溴苯基氨基硫脲3-(4-吡啶基)-4-苯基-1,2,4,-三唑啉-5-硫酮,3-(4-吡啶基)-4-对氯苯基-1,2,4,-三唑啉-5-硫酮,3-(4-吡啶基)-4-对溴苯基-1,2,4-三唑啉-5-硫酮六个新化合物的~(13)C-NMR谱,并通过~(13)C-NMR谱中的宽带去偶,偏共振及APT技术,模型化合物对照,讯号强度对比及芳基取代基常数计算等方法,进行了上述化合物~(13)C-NMR谱峰的归属,并得到了甲酰肼基在吡啶环4位取代后对吡啶环各碳所产生的取代基效应.     

1—(3—吡啶甲酰)—4—芳基氨基硫脲类和3—(3—吡啶基)—4—芳基—1,2,4—三唑啉—5—硫酮类化合物~(13)C—NMR谱研究

本文测定了1-(3—吡啶甲酰)—4—苯基氨基硫脲、3—(3—吡啶基)—4—苯基—1,2,4—三唑啉—5—硫酮等8个新化合物的~(13)C NMR谱,运用质子宽带去偶、偏共振去偶,结合信号强度对比、苯基取代基效应的计算,同时与模型化合物对照,一一归属了其谱峰。本文对这两类化合物之间的~(13)C NMR谱差异进行了探讨,并得到了在吡啶环3位取代的甲酰肼基对吡啶环各碳取代基效应的数据。     

铀—Br—PADAP—磺基水杨酸—表面活性剂体系的研究

本文研究了铀（Ⅵ）－Br－PADAP－磺基水杨酸三元络合物分别与阳离子表面活性剂溴化十六烷基吡啶（CPB）、溴化十六烷基三甲基铵（CTAB），非离子表面活性剂聚乙二醇辛基苯基醚（OP）、Triton X-100的反应条件、生成物的性质和其组成，对反应机理进行了初步讨论。     

Copper Defects and Conductivity in Bi—Pb—Sr—Ca—Cu—O Glasses

Glass ceramics of the composition (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O₈ prepared by the melt quenching technique and the crystalline phases produced by the rapid thermal annealing have been studied by electrical resistivity and electron paramagnetic resonance (EPR) measurements in the temperature range from liquid helium up to room temperature. The concentration of the EPR active Cu^2? paramagnetic centers decreases as conductivity increases for the glass ceramics and disappears after crystallization and the growth of superconducting phases, similar to bulk high-T_c superconductors. The KPR spectra of both glass and crystallized ceramics after short-time annealing indicate the coexistence of Cu^2? paramagnetic ions and the exchange coupled clusters.