Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

Synthesis of functional polymers—Vinylidene fluoride based fluorinated copolymers and terpolymers bearing bromoaromatic side‐group

The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF₂), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by ¹⁹F and ¹H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004     

Reversible addition–fragmentation transfer (RAFT) copolymerization of methyl methacrylate and styrene in miniemulsion

In the reversible addition–fragmentation transfer (RAFT) copolymerization of two monomers, even with the simple terminal model, there are two kinds of macroradical and two kinds of polymeric RAFT agent with different R groups. Because the structure of the R group could exert a significant influence on the RAFT process, RAFT copolymerization may behave differently from RAFT homopolymerization. The RAFT copolymerization of methyl methacrylate (MMA) and styrene (St) in miniemulsion was investigated. The performance of the RAFT copolymerization of MMA/St in miniemulsion was found to be dependent on the feed monomer compositions. When St is dominant in the feed monomer composition, RAFT copolymerization is well controlled in the whole range of monomer conversion. However, when MMA is dominant, RAFT copolymerization may be, in some cases, out of control in the late stage of copolymerization, and characterized by a fast increase in the polydispersity index (PDI). The RAFT process was found to have little influence on composition evolution during copolymerization. The synthesis of the well‐defined gradient copolymers and poly[St‐b‐(St‐co‐MMA)] block copolymer by RAFT miniemulsion copolymerization was also demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6248–6258, 2004     

Near-field thermoelastic imaging coupled with infrared detection

Near-field thermoelastic imaging is a simple way to investigate the thermal and coupled thermoelastic properties of materials. A few microscopes, deriving from the atomic force microscope, have been used to observe and to quantify the samples observed. But the main problem is the absolute measurement of the temperature, because surface topography and thermal expansion contributions are not easily discernible. In the proposed SThEM (scanning thermoelastic microscope), the tip is excited at the resonance frequency of the cantilever and the sample is periodically heated by the Joule effect. Thus the static contributions (drift, topography) are reduced. Moreover, a radiometric sensor, operating in the far field, has been added in order to quantify the temperature. This multi-acquisition microscope enables one to investigate small objects at the nanoscale with complementary information at the micrometric scale.     

Magnetic pole pinning at rectangular defects on MnAs/GaAs(0 0 1)

Strong magnetic poles at characteristic rectangular defects have been observed using a magnetic force microscope on a MnAs(  1 0 0) thin film with the thickness of 30 nm. The MnAs thin film was epitaxially grown on a GaAs(0 0 1) substrate. The magnetic poles were in one-arranging direction, being independent of the magnetization direction of the film. The poles were pinned at the edges of the rectangular defects until just below the Curie temperature, and formed a stable magnetic-field loop on the MnAs surface. The stability of the magnetic pole pinning shows the distinctive feature of the magnetic domain structure on the surface with a strong anisotropy, which was built in the heterostructure of MnAs and GaAs.     

Light Scattering by Cylindrical Fibers with High Aspect Ratio Using the Null‐Field Method with Discrete Sources

The problem of computing light scattering by cylindrical fibers with high aspect ratio in the framework of the Null‐Field method with discrete sources is treated. Numerical experiments for investigating the scattering properties of two fiber geometries are performed using distributed spherical vector wave functions as discrete sources.     

Synthesis and Crystal Structure of Di-n-butyltin(IV) Complex with 2-Oxo-propionic Acid (4-Pyridinecarbonyl) Hydrazone

Introduction The studies of diorganotin(IV) complexes are of current interest owing to their wide range of applica-tions such as biocides and homogeneous catalysts in industry.1 In recent years there have been more and more reports on the synthesis, antitumour activities and structural elucidation of various diorganotin(IV) deriva-tives of carboxylic acid.2-5 In particular, people take considerable interest in structural studies of diorgano-tin(IV) complexes of carboxylic acid, because there…     

有限体积KFVS方法在二维溃坝中的应用

本文采用了基于KFVS格式的有限体积方法 (FVM)求解了控制水流运动的二维浅水方程 ,建立了二维水坝瞬间溃坝的洪水演进模型 .并应用此模型模拟了二维非对称溃坝和对称溃坝情形下坝左下角有障碍物时的洪水波演进过程 .模拟结果表明该数学模型对二维浅水运动的模拟很有效 .     

关于RNP和SCS的若干等价条件

使用切片方法，讨论了Banach空间中有界闭凸子集的RNP和SCS的若干等价条件．     

Modification to the Fringe Component of Diffraction Coefficient in TD-EEC Method

A modified formulation for fringe component of diffraction coefficient is implemented to TD-EEC method. An example of diffraction by perfectly conducting plate is used to illustrate our scheme. Comparing with the FDTD results we observe that the improved expression for fringe component is more accurate than that of Michaeli's formulation. This high frequency time domain technique is available for treating the bistatic scattering problems for millimeter waves.