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.     

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。     

Synthesis and surface characterization of poly(methyl methacrylate)‐block‐polydimethylsiloxane copolymers from macroazoinitiator

Poly(methyl methyacrylate)‐block‐polydimethylsiloxane (PMMA‐b‐PDMS) copolymers with various compositions were synthesized with PDMS‐containing macroazoinitiator (MAI), which was first prepared by a facile one‐step method in our lab. Results from the characterizations of X‐ray photoelectron spectroscopy (XPS), contact angle measurements, and atomic force microscopy (AFM) showed that the copolymer films took on a gradient of composition and more PDMS segments enriched at the film surfaces, which then resulted in the low surface free energy and little microphase separation at the film surfaces. By contrast, transmission electron microscopy (TEM) analysis demonstrated that distinct microphase separation occurred in bulk. Slight crosslinking of the block copolymers led to much steady morphology and more distinct microphase separation, in particularly for copolymers with low content of PDMS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

发动机进气系统高通量富氧膜的研制

采用交联改性的方法对较低分子量的乙烯基硅橡胶进行了改性研究,制备了高通量的富氧膜,结合单因素实验法和Design-expert正交实验设计,考察了原料配比、交联反应时间、固化温度和固化时间等因素对富氧膜性能的影响,确定了最佳富氧性能膜的制备条件:原料配比4.3,反应时间2.15h,固化温度86.25℃,固化时间1.75h;获得了富氧浓度为28.68%,透气量为4696.33 barrer的富氧膜,该膜的富氧浓度与常规商品化膜相当,透气量为常规商品化膜的2~4倍,有应用于发动机富氧进气系统的前景。通过扫描电镜检测、机械性能检测等手段对复合膜进行了进一步表征。     

双锥形管液压成形过程中破裂和起皱的力学条件

针对双锥形管液压成形过程,分析了破裂和皱纹产生的几何及力学原因,并用数值模拟和工艺实验进行了验证。研究结果表明,有益皱纹需要同时满足几何条件和力学条件。几何条件是补料结束时形成的局部皱纹表面积略小于零件相应的表面积。力学条件是皱纹形状参数G不小于中间皱峰半径R,皱峰在后续高压整形过程中壁厚无减薄。当几何条件不满足时,即坯料任一段表面积大于零件相应表面积会起皱,过小会破裂:当力学条件不满足时,整形过程中中间皱峰发生开裂。     

Modeling Self-Rollable Elastomeric Films for Building Bioinspired Hierarchical 3D Structures

In this work, an innovative model is proposed as a design tool to predict both the inner and outer radii in rolled structures based on polydimethylsiloxane bilayers. The model represents an improvement of Timoshenko’s formula taking into account the friction arising from contacts between layers arising from rolling by more than one turn, hence broadening its application field towards materials based on elastomeric bilayers capable of large deformations. The fabricated structures were also provided with surface topographical features that would make them potentially usable in different application scenarios, including cell/tissue engineering ones. The bilayer design parameters were varied, such as the initial strain (from 20 to 60%) and the bilayer thickness (from 373 to 93 µm). The model matched experimental data on the inner and outer radii nicely, especially when a high friction condition was implemented in the model, particularly reducing the error below 2% for the outer diameter while varying the strain. The model outperformed the current literature, where self-penetration is not excluded, and a single value of the radius of spontaneous rolling is used to describe multiple rolls. A complex 3D bioinspired hierarchical elastomeric microstructure made of seven spirals arranged like a hexagon inscribed in a circumference, similar to typical biological architectures (e.g., myofibrils within a sarcolemma), was also developed. In this case also, the model effectively predicted the spirals’ features (error smaller than 18%), opening interesting application scenarios in the modeling and fabrication of bioinspired materials.     

关于带钢拉矫纹的探讨

对拉矫机组在生产中带钢出现皱纹（折纹）、拉矫纹的现象进行了理论分析，并提出了解决办法。