X-ray evidence for the absence of 90°-domains in polycrystalline PbTiO3 thin films with grains below a critical size

3 thin films is systematically studied by using X-ray diffraction (XRD). The PbTiO₃ thin films with different average grain sizes were prepared on various substrates by a sol-gel process. The films on NaCl and fused glass are randomly grain-oriented, while those on (111)Pt/Ti/SiO₂/Si are highly {100} cubic index grain-oriented . It is found from the XRD patterns of the films on NaCl that with decreasing average grain size from 230 to 80 nm, the intensities of high h index (h>l) peaks (hkl), such as (100), (110), (200), (201), (210), (211), etc., decrease rapidly and ultimately disappear, whereas another set of peaks (lkh), including (001), (002), (102), (112), etc., are still intense. This interesting result suggests that at grain size below a certain critical size an increasing number of grains no longer show 90°-domains, which is confirmed by TEM observations. Meanwhile, X-ray evidence of such a grain-size-related absence of 90°-domains is also found for PbTiO₃ films on Pt(111) and fused-glass substrates. The volume fractions of single-domain grains (without 90°-domains) in the films are estimated from their XRD patterns. By combining SEM and TEM investigations, the critical grain size for the formation of 90°-domains is further determined to be near 200 nm. Received: 19 December 1996/Accepted: 24 March 1997     

Identification of peroxyacetic acid uroporphyrin I in the urine of patients with congenital erythropoietic porphyria by liquid chromatography and mass spectrometry

A new porphyrin, peroxyacetic acid uroporphyrin I, has been isolated from the urine of patients with congenital erythropoietic porphyria by reversed phase high performance liquid chromatography. The porphyrin was characterized by high resolution mass spectrometry and by typical chemical reactions of a peroxyacid.     

Preparation of dye-loaded SiO2 nanoparticles

A room temperature method for the encapsulation of pyrene in SiO₂ nanoparticles is described. The relation between alkoxysilane surfactant chain length, reactant molar ratios and the uptake of dye, sample morphology, photophysical properties, and the ability of the silicate matrix to protect the encapsulated dye was examined. The synthesis can easily be adapted for the encapsulation of other hydrophobic and thermolabile substances, and used in the development of nanostructured optically active coatings, films and monoliths.     

Synthesis of optically active poly(N‐propargylsulfamides) with helical conformation

A novel chiral N‐propargylsulfamide monomer ( 1a ) and its enantiomer ( 1b ) were synthesized and polymerized with (nbd)Rh⁺B^?(C₆H₅)₄ as a catalyst providing poly(1) (poly( 1a ) and poly( 1b )) in high yields (≥99%). Poly(1) could take stable helices in less polar solvents (chloroform and THF), demonstrated by strong circular dichroism signals and UV–vis absorption peaks at about 415 nm and the large specific rotations; but in more polar solvents including DMF and DMSO, poly(1) failed to form helix. Quantitative evaluation with anisotropy factor showed that the helical screw sense had a relatively high thermal stability. These results together with the IR spectra measured in solvents showed that hydrogen bonding between the neighboring sulfamide groups is one of the main driving forces for poly(1) to adopt stable helices. In addition, copolymerization of monomer 1a and monomer 2 was conducted, the solubility of poly(1) was improved drastically. However, the copolymerization had adverse effects on the formation of stable helices in the copolymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 500–508, 2007     

Synthesis of grafted poly(p‐phenyleneethynylene) with energy donor–acceptor architecture via atom transfer radical polymerization: Towards nonaggregating and hole‐facilitating light‐emitting material

In this contribution, we demonstrate a new effective methodology for constructing highly efficient and durable poly(p‐phenyleneethynylene) (PPE) containing emissive material with nonaggregating and hole‐facilitating properties through the introduction of hole‐transporting blocks into the PPE system as the grafting coils as well as building the energy donor–acceptor architecture between the grafting coils and the PPE backbone. Poly(2‐(carbazol‐9‐yl)ethyl methacrylate) (PCzEMA), herein, is chosen as the hole‐transporting blocks, and incorporated into the PPE system as the grafting coils via atom transfer radical polymerization. The chemical structure of the resultant copolymer, PPE‐g‐PCzEMA, was characterized by NMR and gel permeation chromatography, showing that the desirable copolymer was obtained with the narrow polydispersity. The increased thermal stability of PPE‐g‐PCzEMA was confirmed by thermogravimetric analysis and differential scanning calorimetry along with its macroinitiator. The optoelectronic properties of this copolymer were studied in detail by ultraviolet‐visible absorption, photoluminescence emission and excitation spectra, and cyclic voltammogram (CV). The results indicate that PPE‐g‐PCzEMA exhibits the solid‐state luminescent property dominated by individual lumophores, and also the energy transfer process from the PCzEMA blocks to the PPE backbone with a relatively higher energy transfer efficiency in the solid‐state compared to that of the solution state. Additionally, the hole‐injection property is greatly facilitated due to the presence of PCzEMA, as confirmed by CV profiles. All these data indicate that PPE‐g‐PCzEMA is a good candidate for use in optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3776–3787, 2007     

Synthesis and nuclear magnetic resonance analysis of starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers

A new biodegradable starch graft copolymer, starch‐g‐poly(1,4‐dioxan‐2‐one), was synthesized through the ring‐opening graft polymerization of 1,4‐dioxan‐2‐one onto a starch backbone. The grafting reactions were conducted with various 1,4‐dioxan‐2‐one/starch feed ratios to obtain starch‐g‐poly(1,4‐dioxan‐2‐one) copolymers with various poly(1,4‐dioxan‐2‐one) graft structures. The microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was characterized in detail with one‐ and two‐dimensional NMR spectroscopy. The effect of the feed composition on the resulting microstructure of starch‐g‐poly(1,4‐dioxan‐2‐one) was investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3417–3422, 2004     

狭义相对论效应──运动时钟变慢的计算机模拟演示实验

利用精炼的C语言进行程序设计，定量模拟狭义相结论的运动时钟变慢，并对处于两种不同时空观的时钟运行进行对比，使得时间膨胀效应变得直观。     

Thermally stimulated current and DSC studies of the broadened glass transition in liquid crystalline polymers

The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main T_g, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that T_g is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc.     

WAXS studies on block copolymers of ethylene and propylene

Wide-angle X-ray scattering from presumed block copolymers of polypropylene (PP) and ethylene-propylene copolymer (EPR), i.e., PP-EPR and PP-EPR-PP, synthesized by sequential polymerization with δ-TiCl₃? Et₂AlCl, was examined and compared with WAXS of mechanical blends and chain-transfer mixtures of PP and EPR with comparable compositions. The peak at 2θ = 20° for both the copolymers and the mixtures was attributed to the γ modification of PP in EPR. A strong variation in the ratio of diffraction intensities I₀₄₀/I₁₁₀ of PP in block copolymers and mixtures was explained in terms of crystallite growth in different directions. Analysis of the patterns and calculation of crystallinity, crystallite size, and lattice parameters led to the conclusion that block structure existed in the prepared copolymers.     

Ethylene–propylene copolymerization with bis(β‐enaminoketonato) titanium complexes activated with modified methylaluminoxane

Ethylene–propylene copolymerization, using [(Ph)NC(R₂)CHC(R₁)O]₂TiCl₂ (R₁ = CF₃, Ph, or t‐Bu; R₂ = CH₃ or CF₃) titanium complexes activated with modified methylaluminoxane as a cocatalyst, was investigated. High‐molecular‐weight ethylene–propylene copolymers with relatively narrow molecular weight distributions and a broad range of chemical compositions were obtained. Substituents R₁ and R₂ influenced the copolymerization behavior, including the copolymerization activity, methylene sequence distribution, molecular weight, and polydispersity. With small steric hindrance at R₁ and R₂, one complex (R₁ = CF₃; R₂ = CH₃) displayed high catalytic activity and produced copolymers with high propylene incorporation but low molecular weight. The microstructures of the copolymers were analyzed with ¹³C NMR to determine the methylene sequence distribution and number‐average sequence lengths of uninterrupted methylene carbons. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5846–5854, 2006