大非线性相移下光学非线性Z扫描特性的研究

采用高斯分解法(GD)对大非线性相移下的Z扫描特性进行了分析，通过对数值算法的优化，将GD推广到对脉冲入射激光下大非线性相移下的Z扫描理论分析.对不同条件下大非线性相移Z扫描曲线峰谷结构的比较，发现在大非线性相移的情况下，Z扫描曲线的峰和谷随透过光阑或入射光强变化表现出某些新的特性.随着透过光阑孔径的增加，Z扫描曲线峰的变化要明显快于谷的变化，而且在谷明显存在的情况下，峰很快消失.采用皮秒脉冲激光下的纯二硫化碳实验对理论结果加以验证，实验结果和理论分析相一致.我们的分析结果对大非线性相移下Z扫描测量有一定的指导性意义，避免在大非线性相移下对Z扫描结果产生错误的分析. 关键词： 大非线性相移 高斯分解法 Z扫描     

Smaller Output Beam Divergence in the Slowly Opened Q-Switch Operation

The mechanism of the slowly opened Q-switch operation was investigated thoroughly. Maximum energy extraction from the resonator could be optimized, and the smallest output beam divergence could be achieved. In this article, we present a detailed analysis that has numerically verified the mode-selection mechanism in the slowly opened Q-switch operation, and the degree of the smaller output laser beam divergence that has been achieved. The mechanism of the slowly opened Q-switch operation is the inherent advantage of the passive saturable absorber in this operation. We can use the maximum energy extraction and the smallest output beam divergence results of the slowly opened Q-switch operation to design and optimize various passive saturable absorbers: plastic dye sheets, LiF:F₂⁻ color center crystals, Cr4⁺: YAG crystals, RG1000 color glass filters, and the single crystal semiconductor saturable absorber wafers that are in developed in our microchip laser systems.     

Synthesis and light emitting properties of polyacetylenes having pendent fluorene groups

Five novel fluorene‐containing polymers, poly[(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA1 ), poly[(1‐pentyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene) ( PFA2 ), poly[1‐decyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA3 ), poly[1‐phenyl‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA4 ), and poly[1‐(3,4‐difluorophenyl)‐2‐(9,9‐dimethylfluoren‐2‐yl)acetylene] ( PFA5 ) were synthesized by the polymerization of the corresponding fluorene‐substituted acetylenic monomers ( M1–M5), using WCl₆, MoCl_5, and TaCl₅ as catalysts and n‐Bu₄Sn as a cocatalyst. The synthesized polymers were thermally stable and readily soluble in common organic solvents. The degradation temperatures for a 5% weight loss of the polymers were ∼352–503 °C under nitrogen. PFA1–PFA5 show emission peaks from 402 to 590 nm. Besides, their electroluminescent properties were studied in heterostructure light‐emitting diodes (LEDs), using PFA2–PFA5 as an emitting layer. The PFA5 device revealed an orange‐red emission peak at 602 nm with a maximum luminescence of 923 cd/m² at 8 V. A device with the ITO/PEDOT/ a mixture of PFA2 (98 wt %) and PFA5 (2 wt %)/Ca/Al showed near white emission. Its maximum luminance and current efficiency are 450 cd/m² at 15 V and 1.3 cd/A, respectively. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 519–531, 2006     

Synthesis of poly(p‐phenylene sulfide) from bis(4‐bromophenyl) disulfide

Improved reaction conditions for the preparation of poly(p‐phenylene sulfide) (PPS) directly from bis(4‐bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 °C was obtained from BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc–BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1‐chloronaphthalene and have properties comparable to commercial PPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 900–904, 2006     

A copper‐based reverse atom‐transfer radical polymerization process for the living radical polymerization of polyacrylonitrile

The reverse atom‐transfer radical polymerization (RATRP) technique using CuCl₂/2,2′‐bipyridine (bipy) complex as a catalyst was applied to the living radical polymerization of acrylonitrile (AN). A hexasubstituted ethane thermal iniferter, diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS), was firstly used as the initiator in this copper‐based RATRP initiation system. A CuCl₂ to bipy ratio of 0.5 not only gives the best control of molecular weight and its distribution, but also provides rather rapid reaction rate. The rate of polymerization increases with increasing the polymerization temperature, and the apparent activation energy was calculated to be 57.4 kJ mol^?1. Because the polymers obtained were end‐functionalized by chlorine atoms, they were used as macroinitiators to proceed the chain extension polymerization in the presence of CuCl/bipy catalyst system via a conventional ATRP process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 226–231, 2006     

Synthesis and application as polymer electrolyte of hyperbranched polyether made by cationic ring‐opening polymerization of 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxymethyl}‐3′‐methyl‐oxetane

A novel cyclic ether monomer 3‐{2‐[2‐(2‐hydroxyethoxy)ethoxy]ethoxy‐methyl}‐3′‐methyloxetane (HEMO) was prepared from the reaction of 3‐hydroxymethyl‐3′‐methyloxetane tosylate with triethylene glycol. The corresponding hyperbranched polyether (PHEMO) was synthesized using BF₃·Et₂O as initiator through cationic ring‐opening polymerization. The evidence from ¹H and ¹³C NMR analyses revealed that the hyperbranched structure is constructed by the competition between two chain propagation mechanisms, i.e. active chain end and activated monomer mechanism. The terminal structure of PHEMO with a cyclic fragment was definitely detected by MALDI‐TOF measurement. A DSC test implied that the resulting polyether has excellent segment motion performance potentially beneficial for the ion transport of polymer electrolytes. Moreover, a TGA assay showed that this hyperbranched polymer possesses high thermostability as compared to its liquid counterpart. The ion conductivity was measured to reach 5.6 × 10^?5 S/cm at room temperature and 6.3 × 10^?4 S/cm at 80 °C after doped with LiTFSI at a ratio of Li:O = 0.05, presenting the promise to meet the practical requirement of lithium ion batteries for polymer electrolytes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3650–3665, 2006     

Atom transfer radical polymerization directly from poly(vinylidene fluoride): Surface and antifouling properties

The direct preparation of grafting polymer brushes from commercial poly (vinylidene fluoride) (PVDF) films with surface‐initiated atom transfer radical polymerization (ATRP) is demonstrated. The direct initiation of the secondary fluorinated site of PVDF facilitated grafting of the hydrophilic monomers from the PVDF surface. Homopolymer brushes of 2‐(N,N‐dimethylamino)ethyl methacrylate (DMAEMA) and poly (ethylene glycol) monomethacrylate (PEGMA) were prepared by ATRP from the PVDF surface. The chemical composition and surface topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy, attenuated total reflectance/Fourier transform infrared spectroscopy, and atomic force microscopy. A kinetic study revealed a linear increase in the graft concentration of poly[2‐(N,N‐dimethylamino)ethyl methacrylate] (PDMAEMA) and poly[poly(ethylene glycol) monomethacrylate] (PPEGMA) with the reaction time, indicating that the chain growth from the surface was consistent with a controlled or living process. The living chain ends were used as macroinitiators for the synthesis of diblock copolymer brushes. The water contact angles on PVDF films were reduced by the surface grafting of DMAEMA and PEGMA. Protein adsorption experiments revealed a substantial antifouling property of PPEGMA‐grafted PVDF films and PDMAEMA‐grafted PVDF films in comparison with the pristine PVDF surface. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3434–3443, 2006     

Synthesis of polyacrylonitrile via reverse atom transfer radical polymerization catalyzed by FeCl3/isophthalic acid

FeCl₃ coordinated by isophthalic acid was first used as a catalyst in the azobisisobutyronitrile‐initiated reverse atom transfer radical polymerization of acrylonitrile. N,N‐Dimethylformamide was used as a solvent to improve the solubility of the ligand. An FeCl₃‐to‐isophthalic acid ratio of 0.5 not only gave the best control of the molecular weight and its distribution but also provided rather a rapid reaction rate. The effects of different solvents on the polymerization of acrylonitrile were also investigated. The rate of the polymerization in N,N‐dimethylformamide was faster than that in propylene carbonate and toluene. The molecular weight of polyacrylonitrile agreed reasonably well with the theoretical molecular weight in N,N‐dimethylformamide. The rate of polymerization increased with increasing polymerization temperature, and the apparent activation energy was calculated to be 59.9 kJ mol^?1. Reverse atom transfer radical polymerization was first used to successfully synthesize acrylonitrile polymers with a molecular weight higher than 80,000 and a narrow polydispersity as low as 1.22. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 219–225, 2006