基于聚二甲基硅氧烷制备超疏水表面的研究进展

聚二甲基硅氧烷(PDMS),作为一种价格低廉、环境友好的有机硅材料,被广泛作为超疏水修饰剂来使用,并利用其与固化剂混合后可固化成型的特点,用于构建表面结构。综述了PDMS在制备超疏水材料上的研究进展,并对其今后的发展做出了展望。     

IPN中聚氨酯固化反应动力学的FTIR研究

用傅立叶变换红外光谱(FTIR)研究纯聚氨酯弹性体和聚氨酯/聚二甲基硅氧烷IPN中聚氨酯的固化反应动力学。结果表明,在PU/PDMS IPN体系中聚氩酯的交联反应仍为二级反应,聚二甲基硅氧烷的存在大大降低了PU/PDMS IPN的交联速率,并提高了反应活化能。     

Highly hydrophobic hierarchical nanomicro roughness polymer surface created by stamping and laser micromachining

This article describes the design and fabrication of hierarchical nanomicrostructured polymer surfaces with high hydrophobicity. The nanoscale roughness is achieved by stamping a ZnO nanowire film into PDMS. Subsequently, microstructures with different periodicities are created in the stamped PDMS sample by direct laser writing using femtosecond pulses. With this approach, we were able to produce hierarchical surface morphologies, composed of nano and microscale structures that exhibit water contact angles larger than 160°. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42082.     

Femtosecond laser irradiation-induced infrared absorption on silicon surfaces

The near-infrared (NIR) absorption below band gap energy of crystalline silicon is significantly increased after the silicon is irradiated with femtosecond laser pulses at a simple experimental condition. The absorption increase in the NIR range primarily depends on the femtosecond laser pulse energy, pulse number, and pulse duration. The Raman spectroscopy analysis shows that after the laser irradiation, the silicon surface consists of silicon nanostructure and amorphous silicon. The femtosecond laser irradiation leads to the formation of a composite of nanocrystalline, amorphous, and the crystal silicon substrate surface with microstructures. The composite has an optical absorption enhancement at visible wavelengths as well as at NIR wavelength. The composite may be useful for an NIR detector, for example, for gas sensing because of its large surface area.     

Poly dimethylsiloxane/carbon nanofiber nanocomposites: fabrication and characterization of electrical and thermal properties

This article presents the fabrication and characterization of poly dimethylsiloxane/carbon nanofiber (CNF)-based nanocomposites. Although silica and carbon nanoparticles have been traditionally used to reinforce mechanical properties in PDMS matrix nanocomposites, this article focuses on understanding their impacts on electrical and thermal properties. By adjusting both the silica and CNF concentrations, 12 different nanocomposite formulations were studied, and the thermal and electrical properties of these materials were experimentally characterized. The developed nanocomposites were prepared using a solvent-assisted method providing uniform dispersion of the CNFs in the polymer matrix. Scanning electron microscopy was employed to determine the dispersion of the CNFs at different length scales. The thermal properties, such as thermal stability and thermal diffusivity, of the developed nanocomposites were studied using thermogravimetirc and laser flash techniques. Furthermore, the electrical volume conductivity of each type of nanocomposite was tested using the four-probe method to eliminate the effects of contact electrical resistance during measurement. Experimental results showed that both CNFs and silica were able to impact on the overall properties of the synthesized PDMS/CNF nanocomposites. The developed nanocomposites have the potential to be applied to the development of new load sensors in the future.     

静电纺丝法制备图案化纳米纤维集合体的研究进展

综述了静电纺丝法制备图案化纳米纤维集合体的方法。研究进展表明,主要是通过不同的收集装置和飞秒激光法制备图案化纳米纤维集合体,该集合体的形成改变了材料的表面形貌,赋予材料在组织工程支架方面潜在的应用价值。     

Preparation of superhydrophobic surfaces by cauliflower‐like polyaniline

Cauliflower‐like polyaniline (PANI) was successfully prepared using an interfacial polymerization method. By modification with polydimethylsiloxane (PDMS) using chemical vapor deposition method, the surface wettability of cauliflower‐like PANI can be tailored to be superhydrophobic with a water contact angle of 160.4°. The deposition of the low‐surface‐energy silicon coating originated from PDMS pyrolysis on the cauliflower‐like PANI was confirmed by X‐ray photoelectron spectroscopy and Fourier Transform Infrared Spectroscopy. The changes in thermal stability and conductivity of the as‐prepared PANI before and after PDMS treatment were also investigated by thermogravimetric analysis and using a four‐probe method. Compared with nanofiber‐shaped PANI by electrodepositing polymerization, the PDMS‐treated cauliflower‐like PANI has superior surface wettability. Our study may open a new way for fabrication of superhydrophobic surfaces by developing novel nanostructured PANI. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39767.     

A novel approach to interpenetrating networks of epoxy resin and polydimethylsiloxane

A novel methodology for preparing interpenetrating polymer networks (IPNs) between an epoxy resin, diglycidylether of bisphenol A (DGEBA) and polydimethylsiloxane (PDMS) was proposed. The vinyl‐terminated PDMS (vinyl‐PDMS) was partially crosslinked with hydrogen‐containing PDMS (H‐PDMS) and was mixed with DGEBA, modified silica (m‐silica), and a methyl tetrahydrophtalic anhydride (MTHPA) curing agent. Subsequently, the curing reactions of the DGEBA/m‐silica and PDMS were allowed to occur separately and simultaneously leading to an IPN. The m‐silica played a double‐fold role: Cocuring with DGEBA and H‐bonding with the oxygen atoms on the PDMS segments, and thus acted as a compatibilizer between DGEBA and PDMS and promoted the generation of the IPN structure. The resulted partially miscible structure was characterized through the dispersion of silica particles and the glass transition behavior of the samples. The mechanical properties of the IPNs were also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Laser Polymer Tattooing: A Versatile Method for Permanent Marking on Polymer Surfaces

A versatile and efficient method for the permanent marking of polymer surfaces that combines inkjet deposition and near‐infrared (NIR) laser curing is investigated. The NIR laser treatment forces the ink particles to migrate into the upper layers of the polymer. This results in the fixation of a permanent grayscale image that can be applied to various polymers, such as polypropylene, which is widely used in industry but still difficult to mark. The physiochemical processes induced by laser curing are investigated by electronic and optical microscopy. The dependence of the thickness of the deposited ink and the laser power on the contrast of marking are also studied. A mechanism implying fast laser‐induced melting of the polymer surface followed by displacement of carbon nanoparticles by convection is proposed. Finally, a comparison of the aging properties of samples prepared by this process and standard UV ink is proposed to illustrate the interesting nature of this new polymer marking process. Integrating the ink under the surface of the polymer, as in a skin tattooing procedure, by laser curing is an efficient way to generate permanent images on polymer surfaces.     

Patterning of worm-like soft polydimethylsiloxane structures using a TiO2 nanotubular array

Patterned polydimethylsiloxane (PDMS) is an important structure for soft lithography. Various materials have been deployed as mold for patterning PDMS. Anodized nanotubular array has been sought after as cost-effective alternative for textured silicon. An array of TiO₂ nanotubes with characteristic diameter ≈140 nm and the length of ≈1.5 microns, created by anodic oxidation of a titanium substrate, was used here as a template for soft PDMS molding. The optimal molding process was developed by a combination of silanization, use of solvent, application of a vacuum, and hydraulic pressing. The silanization was confirmed by Fourier transform infrared spectroscopy and contact angle measurements while the PDMS structure was examined by scanning electron microscope and energy dispersive X-ray spectroscopy. Hydraulic pressing significantly improved the infiltration of PDMS into the pores of nanotubular array resulting in formation of PDMS nanobumps after separation of the polymer from the template. Complete infiltration of PDMS precursor into the cavity of nanotubes was observed on the hydraulic-pressed sample without toluene impurities. The hydraulic-pressed samples exhibited higher adhesion strength than nonpressed ones. The adhesive strength was measured by a simple experimental arrangement, in which the PDMS layer was stuck on a vertical glass surface followed by pulling it downwards.     

PF/PDMS-OH流变性能对其泡沫材料泡孔结构的影响

分别将质量分数为10%,15%和20%的端羟基聚硅氧烷(PDMS–OH)通过机械共混的方法改性酚醛树脂(PF),进而采用化学发泡的方法制备PF/PDMS–OH泡沫复合材料。采用旋转式流变仪表征共混体系的稳态及动态流变性能,研究黏弹性对树脂发泡过程的影响。傅立叶变换红外光谱表征PDMS–OH与树脂在固化过程中的化学反应。扫描电镜表征不同共混体系下泡孔的结构与形态。结果表明,加入15%PDMS–OH的共混体系具有最利于发泡成型的黏弹性,且可与PF形成化学交联作用,对PF泡沫的泡孔形态影响显著。同时红外表征显示,PDMS–OH与PF在固化过程中发生化学交联,这种互穿交联网状结构为PF及泡沫提供了更多稳定的柔性链段。     

Curing behavior study of polydimethylsiloxane‐modified allylated novolac/4,4′‐bismaleimidodiphenylmethane resin

The curing behavior of polydimethylsiloxane‐modified allylated novolac/4,4′‐bismaleimidodiphenylmethane resin (PDMS‐modified AN/BDM) was investigated by using Fourier transform infrared spectrometry (FTIR) and differential scanning calorimetry. The results of FTIR confirmed that the curing reactions of the PDMS‐modified AN/BDM resins, including “Ene” reaction and Diels–Alder reaction between allyl groups and maleimide groups, should be similar to those of the parent allylated novolac/4,4′‐bismaleimidodiphenylmethane (AN/BDM) resin. The results of dynamic DSC showed that the total curing enthalpy of the PDMS‐modified AN/BDM resins was lower than that of the parent resin. Incorporation of polydimethylsiloxane (PDMS) into the backbone of the allylated novolac (AN) resin favored the Claisen rearrangement reaction of allyl groups. The isothermal DSC method was used to study the kinetics of the curing process. The experimental data for the parent AN/BDM resin and the PDMS‐modified AN/BDM resins exhibited an nth‐order behavior. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Micromolding of PDMS scaffolds and microwells for tissue culture and cell patterning: A new method of microfabrication by the self-assembled micropatterns of diblock copolymer micelles

We introduce an innovative fabrication of the polymer scaffolds for tissue culture by utilizing the evaporation induced self-assembled micropatterns of polystyrene-block-poly(acrylic acid) (PS-b-PAA) diblock copolymer micelles. The microstructures were used as templates for micromolding a silicon elastomer, poly(dimethylsiloxane) (PDMS), into tissue scaffolds and microwells for cell patterning purpose. Cultivation of human epithelial cells (Calu-3 cell line) on the PDMS scaffolds demonstrates potential applications in tissue engineering and cell-based biosensors. The reported method is rapid, simple, economical, and versatile comparing with the existing microfabrication techniques.     

Polymeric curing agent reinforced silicone rubber composites with low viscosity and low volume shrinkage

A new type of polymeric curing agent (PCA) was synthesized to improve processing property, increase mechanical properties, and decrease volume shrinkage of silicone rubber. The PCA was prepared by co‐hydrolysis condensation of dimethyldiethoxysilane (DDS) and polyethoxysiloxane, then modified by hexamethylcyclotrisilazane (D₃^N). Commercial silica and tetraethoxysilane (TEOS) were used as controls simultaneously. The properties of polydimethylsiloxane (PDMS) composites were characterized by shear viscosity measurements, room temperature mass loss, linear volume shrinkage, stress‐strain tests, swelling behaviors and thermogravimetric analysis (TGA). PDMS composites using PCA show lower shear viscosity than those using commercial silica. Compared with the traditional PDMS/TEOS curing systems, PDMS/PCA curing systems behave relatively lower volume shrinkage, better reinforcement and thermal properties. In short, PCA acts as a good compromise in providing the best balance of processing property, volume shrinkage, mechanical properties and thermal stability in silicone rubber composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Organic–inorganic hybrid copolymer fibers and their use in silicone laminate composites

Nonwoven organic–inorganic fiber mats of poly(methyl methacrylate)‐graft‐poly(dimethyl siloxane) copolymers with various PDMS contents were produced by the electrospinning process. The average fiber diameter increased from 0.7 to 3 μm with increasing PDMS content. The fiber mats were used in the preparation of silicone‐laminated composite materials by distributing them (single, double and triple layer mats) in a silicone matrix prior to thermal curing. The composites showed a remarkably good fiber distribution in the silicone matrix. In general the stiffness and strength increased in the presence of fiber, and surprisingly, so did the toughness/extensibility. An interesting feature was that the most silicon‐rich fibers showed clear signs of yielding after tensile testing and failure. This, together with the greater compatibility of the fibers with the matrix because of the higher PDMS content, most probably favored composite toughness. All composite fracture surfaces were characterized by clear signs of fiber pull‐out. Fracture initiation areas were difficult to locate, and this is accredited to an even distribution of the individual fibers in the matrix. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Post Curing as an Effective Means of Ensuring the Long-term Reliability of PDMS Thin Films for Dielectric Elastomer Applications

Post curing can be used to facilitate volatile removal and thus produce polydimethylsiloxane (PDMS) films with stable elastic and electrical properties over time. In this study, the effect of post curing was investigated for commercial silicone elastomer thin films as a means of improving long-term elastomer film reliability. The Young’s moduli and electrical breakdown strengths of commercial (silica-reinforced) PDMS elastomer films, with and without additional 35 parts per hundred rubber titanium dioxide (TiO₂), were investigated after high-temperature (200°C) post curing for various time spans. The elastomers were found to contain less than 2% of volatiles (significantly higher for TiO₂-filled samples), but nevertheless a strong effect from post curing was observed. The young’s moduli as well as the strain-dependent behavior were found to change significantly upon post curing treatment, where Young’s moduli at 5% strain increase with post curing. Furthermore, the determined dielectric breakdown parameters from Weibull analyses showed that greater electrical stability and reliability could be achieved by post curing the PDMS films before usage, and this method therefore paves a way toward more reliable dielectric elastomers.     

Characterization of chain binding to filler in silicone-silica systems

Extraction of polymer from mechanically blended poly(dimethylsiloxane)-silica mixtures was conducted at room temperature using chloroform. The amount of silicon still bound to silica after removal of the polymer solution was studied as a function of the average chain molecular weight. A multiple-link structure of binding sites of PDMS chains onto the plain surface of silica is proposed from the analysis of results.     

Fabrication of covalently bonded nanostructured thin films of epoxy resin and polydimethylsiloxane for oil adsorption

Thin films of architectures PEI(CNER_a/PDMS)_n, PEI(CNER_b/PDMS)_n, (PEI/CNER_b)_n and PEI(CNER_b/NH₂-MMT/PEI)_n have been fabricated via covalent layer-by-layer technique. Different film deposition parameters such as solvent type, polymer concentration, polymer ratio and dipping time have been optimized to achieve a uniform growth of layers. The effect of polymer concentration and dipping time on film thickness was also studied via ellipsometer. The optimized ratio of polymer concentration was 1:1 and 1:2 for PEI(CNER_a/PDMS)_n and PEI(CNER_b/PDMS)_n, respectively. AFM analysis indicated that the films were homogeneous while contact angle measurements revealed that although films were hydrophobic in nature yet they have wetting property due to the presence of hydroxyl groups formed during curing process. These epoxy-based multilayers have shown significant oil adsorption capacity. All the fabricated films qualify scotch tape test and were found resistant towards strong acids, bases and organic solvents.     

Heat‐triggered poly(siloxane‐urethane)s based on disulfide bonds for self‐healing application

Polydimethylsiloxane (PDMS) is one of the most widely employed silicon‐based polymers for its high flexibility, low usage temperature, excellent water resistance, outstanding electrical insulting property, and physiological inert, etc. However, the covalent‐bonded Si? O bonds are unable to heal automatically when damaged, which would result in the failure of the materials and devices. Disulfide bond based polymers show high healing efficiency at moderate temperature and have been investigated intensively. Herein, we report a PDMS‐based polyurethane self‐healing polymer (PDMS‐PU) modified with disulfide bonds, which exhibited a reinforced thermal stability, excellent stretchability, and satisfactory self‐healing ability. The effect of different ratio of PDMS and disulfide bond contents on the elastomer properties was investigated. With the increase of PDMS content, the decomposition temperature of the PDMS‐PU‐3 (332 °C) elastomer with highest content of PDMS was increased by 34 °C compared to PDMS‐PU‐1 (298 °C) with lowest content of PDMS and exhibited a largest elongation at break of 1204%. PDMS‐PU‐1 with highest content of disulfide bond possessed a highest healing efficiency of 97%. The results indicated the PDMS‐PU elastomers can be used as self‐healing flexible substrate for flexible electronics. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46532.