Maskless Preparation of Spatially-Resolved Plasmonic Nanoparticles on Polydimethylsiloxane via In Situ Fluoride-Assisted Synthesis

Here, a fluoride-assisted route for the controlled in-situ synthesis of metal nanoparticles (NPs) (i.e., AgNPs, AuNPs) on polydimethylsiloxane (PDMS) is reported. The size and coverage of the NPs on the PDMS surface are modulated with time and over space during the synthetic process, leveraging the improved yield (10×) and faster kinetics (100×) of NP formation in the presence of F⁻ ions, compared to fluoride-free approaches. This enables the maskless preparation of both linear and step gradients and patterns of NPs in 1D and 2D on the PDMS surface. As an application in flexible plasmonics/photonics, continuous and step-wise spatial modulations of the plasmonic features of PDMS slabs with 1D and 2D AgNP gradients on the surface are demonstrated. An excellent spatially resolved tuning of key optical parameters, namely, optical density from zero to 5 and extinction ratio up to 100 dB, is achieved with AgNP gradients prepared in AgF solution for 12 minutes; the performance are comparable to those of commercial dielectric/interference filters. When used as a rejection filter in optical fluorescence microscopy, the AgNP-PDMS slabs are able to reject the excitation laser at 405 nm and retain the green fluorescence of microbeads (100 µm) used as test cases.     

含聚二甲基硅氧烷的聚醚聚氨酯膜透气性及表面性质研究

以聚二甲基硅氧烷（ＰＤＭＳ）／聚四氢呋喃（ＰＴＭＯ）为软段，４，４＇－二环己基甲烷二异氰酸酯（ＨＭＤＩ）为硬段（丁二醇ＢＤ为扩链剂）制成的多相嵌段共聚物作为基质材料，进行了气体（Ｏ２和Ｎ２）透过性试验，同时对膜材料进行了ＥＳＣＡ表面分析。结果表明，共聚物膜的透气性能取决于材料中连续相组分，随着软段中ＰＤＭＳ含量的改变而变化。当ＰＤＭＳ含量较高时，共聚物膜显示出ＰＤＭＳ均聚物的特性，具有较高的气体秀     

Synthesis and characterization of poly(siloxane-urethane)s

A series of polyurethane block copolymers based on hydroxy-terminated polydimethylsiloxane and poly(propylene glycol) soft segments of molecular weights 1818 and 2000, respectively, were synthesized. The hard segments consisted of 4,4′-diphenylnethane diisocyanate and 1,4-butanediol as the chain extender. Samples with different molar ratios were prepared. We tried to synthesize polydimethylsiloxane-based polyurethanes (PDMS-PU) containing a hard block as major fraction and a soft block as minor fraction for preparing toughened rigid systems. After a study of the pure polydimethylsiloxane-based polyurethane and poly(propylene glycol)-based polyurethane (PPG-PU), (mixed polyol)-based block copolymers and blends of PDMS-PU and PPG-PU were synthesized, and characterized by means of differential scanning calorimetry, tensile testing and scanning electron microscopy. In (mixed polyol)-based copolymers and lower hard-segment content blends, macro-phase separation occurred, but blends with higher hard-segment contents showed significant reduction in amounts of phase separation.     

有机电沉积涂料的新动向

阴极电沉积涂料是 2 0世纪 70年代以来发展起来的一种新的涂装方法 ,具有挥发性有机物 (VOCs)和有害空气污染物(HAPs)含量低、防蚀能力强、漆膜质量好、涂料利用率高、适合涂装结构复杂的构件和设备等特点。介绍了近年来阴极电沉积涂料研发的新动向。它们主要集中在有机双层电涂和高分子 聚电解质 /低聚物电解质复合物多层电涂体系 ,这些新的电涂体系在涂料的稳定性以及涂层的物理化学性质和力学性能方面具有明显的改进。     

Zirconium-Embedded Polyhedral Oligomeric Silsesquioxane Containing Phosphaphenanthrene-Substituent Group Used as Flame Retardants for Epoxy Resin Composites

A zirconium hybrid polyhedral oligomeric silsesquioxane derivative (Zr–POSS–bisDOPO) is synthesized by the corner-capping and Kabachnik–Fields reactions. It is characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR), and then used as a flame retardant in diglycidyl ether of bisphenol A (DGEBA) to endow epoxy resin (EP) with flame retardancy. The flame retardancy, thermal stability, and mechanical properties of the cured EP/Zr–POSS–bisDOPO composites are investigated. The results show that when Zr–POSS–bisDOPO is added by 5–7 wt%, the EP/Zr–POSS–bisDOPO composites pass the UL-94 V-0 rating test. In addition, they have a better flame-retardant effect than pure EP. The combination of Zr atom embedded in the Si O cubic cage and the two phosphaphenanthrene substituent groups in one corner of cubic cage is expected to realize the Zr/Si/P ternary intramolecular hybrid synergistic effect and achieve the possibility of dispersing metal–POSS cages at a sub-micrometer-scale level into polymer matrix. It also proves that Zr–POSS–bisDOPO produces phosphorus-containing free radicals and terminates the chain reactions in gas phase. Meanwhile the Si O Si and Zr O units are retained in the solid phase, which promote the char formation and enhance the flame retardancy. This kind of Zr-doped POSS will be helpful for developing the new metal–POSS hybrid flame-retardant and polymer composites.     

聚醚多元醇中环状齐聚物的去除(续)

(接上期第 2 3页 )3　膜分离Doraietal[16] 通过超滤除去低相对分子质量级份 ,使聚醚多元醇 ,尤其是聚四氢呋喃多元醇 ,具有较窄的分布 (Mw∶Mn=1 .2～ 1 .8)。该方法通过对多分散的熔融聚合物实施物理分级 ,达到降低相对分子质量分布的目的 ,可使最终产物的相对分子质量为 40 0～ 40 0 0 ,分散度为 1 .2～ 1 .8。该方法首先需要准备 1套交叉流动的膜分离系统 ,采用渗透膜或半渗透膜 ,膜的一边是滞留物 ,另一边是超滤液。然后 ,在起始聚合物的熔点以上 ,分解温度以下 ,且温度不大于膜的熔融和分解温度 ,将起始聚合物熔融 ,并流入该系统中…     

Preparation and thermal property of hybrid nanocomposites by free radical copolymerization of styrene with octavinyl polyhedral oligomeric silsesquioxane

The poly(styrene‐co‐octavinyl‐polyhedral oligomeric silsesquioxane) (PS–POSS) organic–inorganic hybrid nanocomposites containing various percent of POSS were prepared via one‐step free radical polymerization and characterized by FTIR, high‐resolution ¹H NMR, ²⁹Si NMR, GPC, DSC, and TGA technologies. The POSS contents in these nanocomposites were determined using FTIR calibration curve. The result shows that the POSS contents in nanocomposites can be tailored by varying the POSS feed ratios. On the basis of the POSS contents in the nanocomposites and the ¹H NMR spectra, the number of reacted vinyl groups of each octavinyl‐POSS macromonomer were calculated to be 6–8. DSC and TGA measurements indicate that the incorporation of POSS into PS homopolymer can apparently improve the thermal properties of the polymeric materials. The dramatic T_g and T_dec increases are mainly due to the formation of star and low cross‐linking structure of the nanocomposites, where POSS cores behave as the joint points and hinder the motion and degradation of the polymeric chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

（急）PDMS/ZrO2/SiO2超疏水辐射制冷薄膜的制备及性能

被动日间辐射制冷（PDRC）技术由于不需要外部能源、绿色清洁无污染而受到广泛关注。该文通过将聚二甲基硅氧烷（PDMS）和二氧化锆（ZrO2）颗粒进行复合形成分散液，将其浇铸成膜后得到PDMS/ZrO2辐射制冷薄膜材料，然后通过喷涂PDMS/SiO2分散液对其进行疏水化处理制备了一种超疏水辐射制冷薄膜材料。通过优化ZrO2粒径和喷涂液中SiO2用量，薄膜表面接触角可达156.6 ° ± 2 °，滚动角为0.3 ° ± 0.1 °，呈现优异的自清洁性能。其太阳光反射率高达95.3%，红外发射率大于90%。在太阳光直射下，薄膜可实现平均9.99 ℃的降温效果。薄膜的自清洁性能使其表面不受泥土污染从而具有稳定持久的辐射降温功能。除此之外，薄膜具有优异的机械性能、耐摩擦性能以及耐酸/碱溶液和紫外光照稳定性。     

酸酐固化聚二甲基硅氧烷改性环氧树脂体系的研究

合成了聚二甲基硅氧烷与环氧树脂的增容剂，以甲基四氢苯酐为固化剂固化聚二甲基硅氧烷改性环氧树脂体系，通过测定，中击强度、拉伸强度、弯曲强度分析了其增韧增强效果。结果表明，增容剂的加入提高了环氧树脂与聚二甲基硅氧烷的相容性，当聚二甲基硅氧烷的含量为10％时，改性环氧树脂体系的力学性能最好；并通过热失重法、差示扫描量热法测定了固化物的热性能，其耐热稳定性与纯环氧树脂相比有明显提高。     

导热增强聚氨酯基柔性定形相变材料的制备及性能

以聚乙二醇（PEG10000）和氨丙基封端的聚二甲基硅氧烷（APDMS）为软段，以甲苯-2,4-二异氰酸酯（TDI）为硬段，以碳纳米管（CNTs）作为功能性材料，一锅法制备了导热增强的聚氨酯基柔性定形相变材料（PU/APDMS/CNTs）。用FTIR、XRD、DSC和TGA等对材料的结构特征和热性能进行了表征。当APDMS含量为10 wt%时，PU/APDMS/CNTs的相变焓值为88.3 J/g，该相变材料在200℃内不发生热分解，具有良好的热稳定性和定形效果，加入5 wt% CNTs的柔性定形相变材料，能够实现光热转换和热能存储，其光热转换和热能存储效率为62.8%，与未加入CNTs的相变材料相比，导热性能明显增强，其升降温速率提高了2.75倍。