Efficient Visible-to-UV Photon Upconversion Systems Based on CdS Nanocrystals Modified with Triplet Energy Mediators

Developing high-performance visible-to-UV photon upconversion systems based on triplet–triplet annihilation photon upconversion (TTA-UC) is highly desired, as it provides a potential approach for UV light-induced photosynthesis and photocatalysis. However, the quantum yield and spectral range of visible-to-UV TTA-UC based on nanocrystals (NCs) are still far from satisfactory. Here, three different sized CdS NCs are systematically investigated with triplet energy transfer to four mediators and four annihilators, thus substantially expanding the available materials for visible-to-UV TTA-UC. By improving the quality of CdS NCs, introducing the mediator via a direct mixing fashion, and matching the energy levels, a high TTA-UC quantum yield of 10.4% (out of a 50% maximum) is achieved in one case, which represents a record performance in TTA-UC based on NCs without doping. In another case, TTA-UC photons approaching 4 eV are observed, which is on par with the highest energies observed in optimized organic systems. Importantly, the in-depth investigation reveals that the direct mixing approach to introduce the mediator is a key factor that leads to close to unity efficiencies of triplet energy transfer, which ultimately governs the performance of NC-based TTA-UC systems. These findings provide guidelines for the design of high-performance TTA-UC systems toward solar energy harvesting.     

Improved thermosets obtained from diglycidyl ether of bisphenol A/4,4′‐diaminodiphenylsulfone based on a new epoxy‐terminated hyperbranched polymer

A new hyperbranched polymer (HBP) with a flexible aromatic skeleton and terminal epoxy groups was synthesized to improve the toughness of diglycidyl ether of bisphenol A. The HBP was characterized using nuclear magnetic resonance, Fourier transfer infrared spectroscopy and gel permeation chromatography. The effect of HBP on the thermomechanical and mechanical properties of modified epoxy systems was studied. For evaluating the efficiency of the modified epoxy systems, composite samples using glass fiber cloth were molded and tested. Using dynamic mechanical analysis, a slight reduction in glass transition temperature (T_g) with increasing HBP content was observed. Analysis of fracture surfaces revealed a possible effect of HBP as a toughener and showed no phase separation in the modified resin systems. The results showed that the addition of 15 phr HBP maximized the toughness of the modified resin systems with 215 and 40% increases in impact and flexural strengths, respectively. T_g and heat resistance of cured modified resin systems decreased slightly with an increase in HBP content and, at 15 phr HBP, only a 2.6% decrease in thermomechanical properties was observed. Meanwhile, a molded composite with HBP showed improved mechanical properties and retention rate at 150 °C as compared to that made with neat resin. © 2015 Society of Chemical Industry     

Properties and curing behavior of reactive blended allyl novolak with bismaleimide using dicumyl peroxide as a novel curing agent

For reducing the cure temperature and improving the thermal stability and mechanical properties, a thermosetting resin system composed of novolak and bismaleimide (BMI) was developed by reactive blending and using dicumyl peroxide (DCP) as a novel curing agent. Novolak was allylated and reacted with BMI to produce bismaleimide allylated novolak (BAN), and the effect of DCP on flexural, impact and heat distortion temperature of cured resin were investigated. On the basis of improved mechanical and thermal properties at 0.5% DCP contents, the curing behavior of DCP/BAN resin system was evaluated by DSC analysis. Ene, Diels‐Alder, homo‐polymerization and alternating copolymerization which occurred in DCP/BAN resin system were further verified using FTIR at sequential cure conditions from 140 to 200°C. Kissinger and Ozawa‐Flynn‐wall methods were used to optimize the process and curing reactions of DCP/BAN resin system. The results showed that the addition of 0.5% DCP in BAN reduced the curing temperature and time of the modified resin. For evaluating process ability of the modified system, composite samples using polyvinyl acetyl fiber were molded and tested for flexural properties. The resulting samples showed better flexural properties when compared with the composite made with neat BAN. The modified 0.5% DCP/BAN resin system with good mechanical properties and manufacturability can be used for making bulk molding compounds and fiber reinforced composites required in various commercial and aerospace applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41829.     

烯丙基酚氧树脂改性双马来酰亚胺体系的优化

通过环氧树脂与二烯丙基双酚A合成了一种烯丙基酚氧树脂,用以增韧双马来酰亚胺。在单因素试验的基础上,根据Box-Benhnken的中心组合试验设计原理,选取改性树脂体系组分为影响因子,应用响应面法进行3因素3水平的18组的设计试验,改性树脂性能(弯曲强度,冲击强度,热变形温度)为响应值,对改性树脂组分配比进行优化。结果表明,改性树脂组分配比BMI、DDS、APO、DABPA、DAP为2∶1∶0.2∶0.84∶0.1(物质的量比)时,综合2性能最好,此时改性双马树脂体系的冲击强度可达到21.4 k J/m,弯曲强度为200.5 MPa,热变形温度为195.8℃。     

Properties of dicumyl peroxide initiated bismaleimide modified allyl novolac and its molded composites

A thermosetting resin system, bismaleimide (BMI) modified allyl novolac (BAN), was developed via reactive blending of formaldehyde and catalyst drop wise to improve the extent of reaction between BMI and phenol‐carbenium ions. For improving the curing behavior and mechanical properties, dicumyl peroxide (DCP) was selected as a novel curing initiator to compare with hexamethylenetetramine (HTMA) which is the most common curing initiator used in the manufacture of phenolic resins. BAN was characterized by ¹H nuclear magnetic resonance and Fourier transfer infrared spectroscopy. Curing behavior with initiators was analyzed by differential scanning calorimetry and glass transition temperature of the cured resins was examined by dynamic mechanical analysis. For evaluating efficiency of the modified system, composite samples using polyvinyl acetyl fiber were molded and tested for flexural properties before and after ageing at 150°C for 1,000 h. The morphology of composite samples was examined by scanning electron microscope, and the effects of the incorporated initiators on the mechanical and thermal properties of composite were investigated. The results indicated that the initiators reduced the curing temperature effectively and improved the curing process. DCP proved to be more effective in crosslinking and heat resistance than HTMA. Meanwhile, the molded composite with DCP showed higher mechanical properties before and after ageing when compared with HTMA curing initiator. Therefore, DCP/BAN resin system with good heat resistance, higher mechanical properties, and better process ability can be applied as matrix resin for the manufacturing of advanced fiber reinforced composites. POLYM. COMPOS., 37:2260–2271, 2016. © 2015 Society of Plastics Engineers     

Physical and electromagnetic shielding properties of green carbon foam prepared from biomaterials

100% green carbon foam from the fibrous fruits of Platanus Orientalis-L (Plane) along with the tar oil as binder has been prepared using a powder molding technique. The objective was to develop a porous monolithic carbon from biomaterials with a considerable strength necessary for various physical, thermal and electromagnetic shielding applications. Fast carbonization was carried out at 1000 °C under the cover of Plane tree pyrolyzed seeds without using any external protective gas. For comparative analysis, some samples were mixed with 5% (mass fraction) iron chloride during the molding process. Iron chloride being a graphitization catalyst and activating agent helped in increasing the specific surface area from 88 to 294 m²/g with a 25% decrease in flexural strength. Thermal stability was improved due to the incorporation of more graphitic phases in the sample resulting in a little higher thermal conductivity from 0.22 to 0.67 W/(m·K). The catalytic carbon foam exhibited shielding effectiveness of more than 20 dB over the X-band frequency. Absorption was dominant with only 8.26%–10.33% reflectance, indicating an absorption dominant shielding mechanism. The new material is quite suitable for high temperature thermal insulation being lightweight, highly porous with interconnected porous morphology most of which is preserved from the original biomaterial.     

密度和纤维取向对炭/炭复合材料烧蚀性能的影响(英文)

采用不同的预制体和致密化方法制备了密度不同的5种炭/炭复合材料(密度范围1.77g/cm3～1.85g/cm3)。用氧-乙炔焰对试样进行了烧蚀试验,并用SEM表征了烧蚀后材料的形貌。结果表明:烧蚀后,与乙炔焰成30o角的纤维变成楔形,而与火焰平行的纤维变成直径为3.5μm～4.5μm的针状,针状纤维更易被火焰烧蚀而钝化。部分宏观孔(直径为1.0mm～1.26mm)、针状微孔及界面裂纹等缺陷处更易被烧蚀而变成烧蚀坑。包裹纤维的沥青炭层由于热解炭基体的不连续而出现了严重的剥蚀。高密度材料(1.85g/cm3)具有良好的抗烧蚀性能。     

Curing behavior and thermal and mechanical properties enhancement of tetraglycidyl‐4,4′‐diaminodiphenylmethane/4,4′‐diaminodiphenylsulfone using a liquid crystalline epoxy

A thermosetting resin system, based on tetraglycidyl‐4,4′‐diaminodiphenylmethane, has been developed via copolymerization with 4,4′‐diaminodiphenylsulfone in the presence of a newly synthesized liquid crystalline epoxy (LCE). The curing behavior of LCE‐containing resin system was evaluated using curing kinetics method and Fourier transform infrared spectroscopy. The effect of LCE on the thermal and mechanical properties of modified epoxy systems was studied. Thermogravimetric analysis indicated that the modified resin systems displayed a high T_0.05 and char yield at lower concentrations of LCE (≤5 wt%), suggesting an improved thermal stability. As determined using dynamic mechanical analysis and differential scanning calorimetry, the glass transition value increased by 9.7% compared to that of the neat resin when the LCE content was 5 wt%. Meanwhile, the addition of 5 wt% of LCE maximized the toughness with a 175% increase in impact strength. The analysis of fracture surfaces revealed a possible effect of LCE as a toughener and showed no phase separation in the modified resin system, which was also confirmed by dynamic mechanical analysis. © 2016 Society of Chemical Industry     

Anisotropic compressive properties of porous CNT/SiC composites produced by direct matrix infiltration of CNT aerogel

Carbon nanotube‐reinforced silicon carbide composites (CNT/SiC) produced by direct infiltration of matrix into a porous CNT arrays have been demonstrated to possess a unique microstructure and excellent micro‐mechanical properties. However, the thickness of the array preforms is usually very small, typically less than 2 mm. Therefore, fabrication of macroscopic CNT/SiC composites by chemical vapor infiltration (CVI) process requires that the nanoscale fillers could form macroscopic architectures with an open pore network. Here, this study reports an experimental strategy for the fabrication of SiC matrix composites reinforced by CNT based on an ice‐segregation‐induced self‐assembly (ISISA) technique. Macroscopic CNT aerogel with well‐defined macroporous network was produced by ISISA technique and was subsequently infiltrated by SiC in a CVI reactor. After five CVI cycles, the porosity of as‐fabricated composites was 11.6±0.3% and the machined specimens exhibited lamellar structure with parallel lamellaes intersected at discrete angles. By observed, there are in fact five different representative anisotropic macrostructures, the compressive strengths of these five different loading modes with respect to lamella orientation were 933±55, 619±34, 200±45, 199±21, and 297±41 MPa, respectively, and the failure mechanisms were attributed to the anisotropic nature of the macrostructures. Energy dissipation toughening mechanism at the nanoscale such as CNT pull‐out was observed and the phase composition of the fabricated materials included β‐SiC, CNT, and SiO₂.