Eu3+/Sm3+共掺聚合物PMMA中敏化效应的研究

研究了Eu3+/Sm3+共掺聚合物PMMA中Sm3+对Eu3+发光的敏化效应,实验采用改进的本体聚合法制备得到了Eu3+/Sm3+共掺聚合物PMMA,并对其荧光光谱和荧光寿命进行了分析.荧光光谱分析发现,Sm(TTFA)3的加入大大增强了Eu3+的特征发光,表明Sm3+对Eu3+的荧光有很强的敏化效应,文中对其敏化过程进行了探讨与分析,提出了两种可能的敏化机理.荧光寿命分析表明,在共掺情况下,掺杂浓度对荧光寿命没有明显的影响,寿命范围在300~400 μs之间.     

Ionic conductivity and interfacial resistance of electrospun poly(acrylonitrile)/poly(methyl methacrylate) fibrous membrane-based polymer electrolytes for lithium ion batteries

Electrospun poly(acrylonitrile) fibrous membrane (PAN-EFM) is prepared and enhanced by adding poly(methyl methacrylate)(PMMA) and subsequently minimizing the average diameter of the PAN/PMMA blend fibers. Electrospinning of the 50/50 wt% PAN/PMMA solution is carried out with the aim of the simultaneous presence of both polymers on the fiber surface. Their presence in exterior surface is confirmed using the Fourier transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) technique next to the leaching of PMMA with acetone. The process parameters are optimized in four stable modes with the average diameter decreasing from 445 to 150 nm. Mechanical strength of the membrane is measured and reported. Comparing the sample electrochemical properties of the EFMs reveals that the addition of PMMA increases ionic conductivity from 1.02 to 3.31 mS cm^?1 and reduces interfacial resistance from ~1000 to ~400?Ω. It is also demonstrated that the ~300-nm reduction in average diameter of the blend fibers increases ionic conductivity from 3.31 to 5.81 mS cm^?1 and reduces interfacial resistance from ~400 to ~200?Ω.     

用于高速数据通信的梯度塑料光纤

概述了梯度塑料光纤的开发历史和现状。从应用于高速数据通信的角度 ,介绍了聚甲基丙烯酸甲酯(PMMA)、全氘化和全氟化梯度塑料光纤的损耗、带宽、稳定性和寿命。详细介绍了梯度塑料光纤的损耗光谱和损耗机制 ,介绍了制作梯度塑料光纤的界面凝胶聚合技术和两种扩散法 ,分析了梯度塑料光纤的制作方法同折射率剖面和带宽的关系 ,讨论了梯度塑料光纤的稳定性同掺杂物质的关系。同时介绍了高稳定性梯度塑料光纤的研究进展及今后的发展动向     

Eu3+配合物掺杂聚合物的制备与光谱性能研究

以噻吩甲酰三氟丙酮(2-thenoyltrifluoroacetone , TTFA), 六氟乙酰丙酮(hexafluoro- acetylacetone, HFA)和甲基联苯甲酰(dibenzoylmethide, DBM) 分别为配体合成了Eu3+的三种β-二酮类配合物Eu(TTFA)3、Eu(HFA)3和 Eu(DBM)3,以及掺杂这三种配合物的聚合物（聚甲基丙烯酸甲酯,PMMA）,并用分光光度计对它们的荧光光谱特性进行了分析研究.结果表明,三种配合物中Eu(TTFA)3荧光强度最强,并分析了其原因,发现能级匹配、配体取代基、配体结构对称性等均对配合物发光效率有重要的影响.通过比对,证明了TTFA是Eu3+发红色荧光的优良配体.进一步研究还发现,Eu(TTFA)3掺杂PMMA中稀土离子的荧光强度和荧光寿命均随掺杂浓度（质量分数为0.08～0.5）的增加而增大.     

A new solution of reducing polymer optical fiber losses

Polymethyl methacrylate (PMMA) is one of the most commonly used optical materials. However, the application of it in the area of optical communication is strongly limited by the intrinsic absorption loss of carbon-hydrogen stretching vibration. In this paper, we present a method to solve the problem by adopting the hollow-core fibers with cobweb cladding structure. The fibers use a single dielectric material and may solve the problem of structural support. Thus the feasibility of the “OmniGuide” fibers is improved, while a series of advantages of the “OmniGuide” hollow-core fiber are retained. It is promising that a fiber with low transmission loss, high bandwidth, large-core, and low costs can be designed and fabricated using PMMA. At the same time, a very broad range of the wavelengths (from visible to near infrared region, for instance, wavelengths at 0.65-1.12 μm, and even 1.30 μm, 1.54 μm and their neighbors) may be adopted for signal wavelength.     

新型光学聚合物——Topas环烯烃共聚物微结构光纤的设计及特性分析

以新型光学聚合物Topas 环烯烃共聚物（折射率为1.53）为基质,设计了四种微结构聚合物光纤.应用有限元方法对各种光纤在波长0.5—2.0 μm范围内的基模有效折射率、模场面积和数值孔径进行了计算.研究了结构参数对模场分布、单模特性和色散特性的影响.得出了具有极大/小模场面积、无限单模传输和平坦近零色散的光纤结构参数.与石英、聚甲基丙烯酸甲酯基质的微结构光纤相比,该光纤具有更大的数值孔径和较宽的平坦近零色散范围.为光纤的制备提供了理论指导. 关键词： 微结构聚合物光纤 有限元方法 传输特性 Topas 环烯烃共聚物     

Millimeter-long nanofibers of PMMA spun at super-high speed by ablation with a single pulse of a KrF excimer laser

A new form of matter removal in laser ablation is reported. Polymethylmethacrylate (PMMA) nanofibers are obtained when a PMMA target is irradiated with a single pulse of a KrF excimer laser, whose beam is sharply imaged on a square of side the order of 140 μm, so that a strong intensity gradient is produced. The fluence threshold at which fibers appear, 3 J/cm², is much larger than the ablation threshold, approximately 0.8–1 J/cm². Above this fluence, the melt depth is then large enough and the temperature profile is such that explosive boiling is obtained. The model suggests an expulsion of energetic droplets from the intense pressure of the plume to the exterior of the spot. For the transient melt of a polymeric viscoelastic liquid resulting from UV-laser excitation, such droplets provide the heads of the jets pulled from the melt bath, giving rise, after solidification, to nanofibers. The speed of fiber spinning is extremely high (∼800 m/s) and unusual properties of the laser-produced nanofibers may be expected. Received: 16 April 2002 / Accepted: 17 April 2002 / Published online: 19 July 2002     

Eu(DBM)_3Phen掺杂聚甲基丙烯酸甲酯静电纺丝荧光纤维

通过静电纺丝技术获得直径约为700 nm,均匀且随机取向的亚微米级Eu(DBM)3Phen/PMMA纤维。在紫外光辐射下,亚微米级荧光纤维发出明亮的红色荧光。其激发光谱表明,荧光纤维有效激发波长范围为200~400 nm。利用积分球配以CCD探测器,在367 nm长波紫外LED激发下对荧光纤维开展绝对光谱功率测试。当LED泵浦功率为535.76#W时,厚度80#m的Eu(DBM)3Phen/PMMA纤维薄层对紫外辐射的吸收率高达89%,350~850 nm范围内发射的总绝对光谱功率、总光子数和总荧光量子产率分别为36.56#W、11.46×10~(13)cps和12.94%。亚微米级Eu(DBM)_3Phen/PMMA纤维薄层中,Eu~(3+)较高的跃迁发射几率及较大的发射截面使得纤维可以高效吸收紫外辐射并转变为可见光,在提高太阳能电池光电转换效率方面具有潜在应用价值。     

椭圆芯非六角对称高双折射聚合物PCFs

采用全矢量平面波展开法,以聚合物PMMA为基材,研究了椭圆芯非六角对称聚合物光子晶体光纤（Photonic Crystal Fibers,PCFs）的传输模场和偏振特性,从理论上分析了其模式双折射和光纤结构参量的关系.研究结果表明,该PCFs基模的两个正交偏振态不再简并,模场呈现明显的椭圆并具有较强的线偏振特性;另外,该光纤的模式双折射强烈地依赖于光纤的结构参量,通过适当调节光纤的相对孔间距比,有望在给定波长范围内实现更高双折射单模运行.     

Fluorescence characterization and gain studies on a dye-doped graded index polymer optical-fiber preform

Preparation of an appropriate optical-fiber preform is vital for the fabrication of graded-index polymer optical fibers (GIPOF), which are considered to be a good choice for providing inexpensive high bandwidth data links, for local area networks and telecommunication applications. Recent development of the interfacial gel polymerization technique has caused a dramatic reduction in the total attenuation in GIPOF, and this is one of the potential methods to prepare fiber preforms for the fabrication of dye-doped polymer-fiber amplifiers. In this paper, the preparation of a dye-doped graded-index poly(methyl methacrylate) (PMMA) rod by the interfacial gel polymerization method using a PMMA tube is reported. An organic compound of high-refractive index, viz., diphenyl phthalate (DPP), was used to obtain a graded-index distribution, and Rhodamine B (Rh B), was used to dope the PMMA rod. The refractive index profile of the rod was measured using an interferometric technique and the index exponent was estimated. The single pass gain of the rod was measured at a pump wavelength of 532 nm. The extent of doping of the Rh B in the preform was studied by axially exciting a thin slice of the rod with white light and measuring the spatial variation of the fluorescence intensity across the sample.     

双核铼配合物复合电纺纤维的制备和氧传感性能的研究

合成了亲脂性双核铼配合物fac-[{Re(CO)₃(d19 phen)}₂(4,4′ bipyridylacetylene)](OTf_⁾2^,将此配合物均匀地分散到聚苯乙烯(PS)和聚甲基丙烯酸甲酯(PMMA)中,通过电纺方法,得到复合材料纤维,并系统地研究了它们的氧传感性能。分别用线性Stern Volmer模型,Demas双格位模型以及Lehrer模型对所得到的Stern Volmer曲线进行了拟合,实验结果表明,这种复合纤维氧传感材料显示了短的响应时间,可逆的氧传感信号,而且由于含有亲脂性的长链烷烃配体的存在,使得铼配合物在聚合物中分散均匀,从而得到线性关系较好的Stern Volmer曲线。     

聚合物光纤辐照特性的实验研究

分析了聚合物受辐照后发生物理化学变化的机理,实验研究了聚苯乙烯（PS）、聚碳酸脂（PC）、聚甲级丙烯酸甲脂（PMMA）三种聚合物光纤在不同辐照剂量下光传输性能的变化以及其恢复特性.在各种辐照剂量下,光透过率有不同程度的下降,经过一段时间后也有不同程度的回复,并且恢复主要发生在停止辐照后的较短时间内.在102 Gy以下,辐照造成的光损伤经过一段时间基本可以恢复,在更高剂量的辐照下(超过5*10³ Gy),辐照对光纤造成了永久损伤,经过很长时间也只能恢复一部分.实验结果表明,PS光纤的抗辐照特性最好,PC光纤优于PMMA光纤.     

Responses of "lower-spontaneous-rate" auditory-nerve fibers to speech syllables presented in noise. I: General characteristics.

Responses of auditory-nerve fibers in anesthetized cats to nine different spoken stop- and nasal-consonant/vowel syllables presented at 70 dB SPL in various levels of speech-shaped noise [signal-to-noise (S/N) ratios of 30, 20, 10, and 0 dB] are reported. The temporal aspects of speech encoding were analyzed using spectrograms. The responses of the "lower-spontaneous-rate" fibers (less than 20/s) were found to be more limited than those of the high-spontaneous-rate fibers. The lower-spontaneous-rate fibers did not encode noise-only portions of the stimulus at the lowest noise level (S/N = 30 dB) and only responded to the consonant if there was a formant or major spectral peak near its characteristic frequency. The fibers' responses at the higher noise levels were compared to those obtained at the lowest noise level using the covariance as a quantitative measure of signal degradation. The lower-spontaneous-rate fibers were found to preserve more of their initial temporal encoding than high-spontaneous-rate fibers of the same characteristic frequency. The auditory-nerve fibers' responses were also analyzed for rate-place encoding of the stimuli. The results are similar to those found for temporal encoding.     

PMMA基底CdSe量子点光纤材料的制备及其光谱

塑料光纤在成本、光纤到户和短距离通信等方面与石英光纤相比具有优越性.在塑料光纤基底中掺人某些光放大介质(如量子点),可以制备出塑料光纤放大器.目前,对于量子点掺杂的塑料光纤材料的光学性能的研究还很少.报导了一种以聚甲基丙烯酸甲酯(PMMA)为基底的CdSe量子点光纤材料CdSe/PMMA.紫外-可见-近红外吸收谱以及荧...     

Charge transport properties of composites of multiwalled carbon nanotube with metal catalyst and polymer: application to electromagnetic interference shielding

We report charge transport properties such as d.c. conductivity (σ_DC) and its temperature dependence for composites of poly(methyl methacrylate) (PMMA) and multiwalled carbon nanotubes (MWCNTs). The MWCNTs were synthesized through chemical vapor deposition with Fe or Co as catalyst. The MWCNTs were homogeneously dispersed in PMMA matrix through sonication to prepare MWCNT–PMMA composite films. We controlled mass concentration of MWCNTs in the composites, and the thickness of MWCNT–PMMA composite films was 20–400 μm. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectroscopy were used to study structure and homogeneity of the composites. The σ_DC at room temperature of MWCNT–PMMA composites increased as mass concentration of MWCNTs increased, which followed percolation theory. Electromagnetic interference (EMI) shielding efficiency (SE) of MWCNT–PMMA composites was measured in the frequency range of 50 MHz–3.5 GHz. We observed the increase of EMI SE of MWCNT–PMMA composites with increasing the concentration of MWCNTs.     

Synchrotron Radiation Tomography for Reconstruction of Layer Structures and Internal Defects of Composite Materials

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Reversible UV degradation of PMMA plastic optical fibers

Laser-induced fluorescence, Raman and absorption spectroscopy are used to investigate reversible degradation of transmission in PMMA optical fibers. When exposed to 254 nm UV light, optical transmission of PMMA plastic optical fiber in 400-800 nm range shows a significant increase in attenuation for shorter wavelengths. Over a period of 10 days following UV exposure, the transmittance of the plastic fiber recovers to a significant fraction of its pre-exposure value. UV-exposed fiber exhibits strong laser-induced fluorescence with 488 nm argon-ion laser. This fluorescence spans a spectral region between 450 nm and 750 nm with a peak around 580 nm. The fluorescence intensity decreases over several days following UV exposure. Likewise, Raman is also used to investigate degradation process. Freshly UV-exposed fiber shows total absence of Raman spectrum of PMMA. Following UV exposure, recovery of Raman signal over several days is correlated to the recovery of fiber transmittance as well as the decay of laser-induced fluorescence. A widely believed plausible explanation for UV-induced increase of attenuation involves formation of different macro radicals which recombine progressively after UV is stopped. Laser-induced fluorescence over several days is reported here providing direct evidence for molecular-level deterioration and recovery of PMMA.     

Parametric Studies on the Grafting of Poly(Methyl Methacrylate) onto Organophilic Montmorillonite Using Silylated Clay Platelets

Poly(methyl methacrylate) (PMMA)/organophilic montmorillonite (Cloisite 30B) nanocomposites were synthesized by the chemical grafting of PMMA onto Cloisite 30B via solution polymerization of methyl methacrylate (MMA) with vinyl-modified organoclay. The effects of different parameters such as clay weight percent (CWP), solvent per monomer volume ratio, and dispersion time on the properties of the PMMA grafted Cloisite 30B were investigated using the Taguchi experimental design method. This method gives a much-reduced variance for the experiments with optimum setting of control parameters and provides a set of minimum experiments compared to the conventional methods. Qualitative evidence for the chemical grafting of the PMMA onto Cloisite 30B was confirmed by Fourier transform infrared spectroscopy (FT-IR). X-ray diffraction (XRD) was used to investigate interlayer changes of the clay in the grafted nanoplatelets. The exfoliated/intercalated morphology of the nanocomposites was confirmed by XRD. Furthermore, thermal properties were measured by thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). Statistical analysis of results revealed that clay weight percent and solvent per monomer ratio had significant effects on the properties of final products. The percent of grafted PMMA and storage modulus of PMMA/30B nanocomposites decreased with increasing clay content due to better dispersion of the clay at lower loadings. On the other hand, because of a tendency to formation of homopolymer and oligomers at higher solvent loadings; the percent of grafted PMMA, storage modulus and glass transition temperature of PMMA/30B nanocomposites decreased with an increase in solvent per monomer volume ratio. However, the obtained PMMA/30B nanocomposites at the optimum conditions, was exhibited a higher glass transition temperature, higher storage modulus and better thermal stability than the pure PMMA.     

Development of One-dimensional Fiber-Optic Radiation Sensor for Measuring Dose Distributions of High Energy Photon Beams

The purpose of this study was to develop a method for measuring the one-dimensional dose distribution of a high-energy photon beam using a miniaturized high-resolution fiber-optic radiation sensor array. The measurements were made by thin plastic optical fibers with organic scintillating fiber sensor probes that emit the visible wavelength of light. The scintillating light is guided to a silicon photodiode array by plastic optical fibers in order to convert light output to an electrical signal. The one-dimensional spatial dependence of photon beam is measured by a one-dimensional fiberoptic sensor array in a poly(methyl methacrylate) (PMMA) phantom. It is shown that this fiber-optic radiation sensor has better spatial resolution than a conventional ionization chamber and much less time is required to measure one-dimensional dose distribution in the high radiation fields. The real-time and the high spatial resolution measurements due to the small detector volume make this system suitable for dosimetry in radiation therapy.