UV curing-assisted 3D plotting of ceramic feedstock containing thermo-regulated phase-separable,photocurable vehicle for dual-scale porosity structure

We propose a novel approach for manufacturing dual-scale porosity alumina structures by UV curing-assisted 3D plotting of a specially formulated alumina feedstock using a thermo-regulated phase separable, photocurable camphene/triethylene glycol dimethacrylate (TEGDMA) vehicle. In particular, 3D plotting process was conducted at - 5 °C, and thus an alumina suspension prepared using liquid camphene/TEGDMA at room temperature could undergo phase separation, resulting in camphene crystals surrounded by walls comprised of liquid photopolymer enclosing alumina particles. To enhance the shape retention ability of extruded filaments, polystyrene (PS) polymer was used as the tackifier. The phase-separated feedrod could be extruded favorably through a nozzle and rapidly photopolymerized by UV light during the 3D plotting process. Three-dimensionally interconnected macropores were tightly constructed, which were separated by microporous alumina filaments, where micropores were created by the removal of camphene crystals via freeze-dying. The macroporosity of porous alumina ceramics was controlled by adjusting the distance between deposited filaments, while their microporosity was kept constant, leading to tightly tailored overall porosity and mechanical properties.     

一种新型的室温快速固化胶黏剂的研制

本文开发了一种新型的方舱夹芯板用室温固化高强度环氧结构胶黏剂,验证了其物化特性、相关力学性能和环境适应性。结果表明此胶黏剂具有优良性能,可以满足方舱用大板胶黏剂的使用需求。     

Annealing temperature dependent structural and optical properties of electrodeposited CdSe thin films

Cadmium selenide films were synthesized using simple electrodeposition method on indium tin oxide coated glass substrates. The synthesized films were post annealed at 200 °C, 300 °C and 400 °C. X-ray diffraction of the films showed the hexagonal structure with crystallite size <3 nm for as deposited films and 3–25 nm for annealed films. The surface morphology of films using field emission scanning electron microscopy showed granular surface. The high resolution transmission electron microscopy of a crystallite of the film revealed lattice fringes which measured lattice spacing of 3.13 Å corresponding to (002) plane, indicating the lattice contraction effect, due to small size of CdSe nanocrystallite. The calculation of optical band gap using UV–visible absorption spectrum showed strong red-shift with increase in crystallite size, indicating to the charge confinement in CdSe nanocrystallite.     

Transparent and flexible films of new segmented polyurethane nanocomposites incorporated by NH2-functionalized TiO2 nanoparticles

In this work, TiO₂ nanoparticles are surface modified by NH₂-terminated organic moieties arised from 4,4′-methylene diphenyl diisocyanate (MDI). These nanoparticles are incorporated into ether-based segmented polyurethane (SPU) matrix. MDI is utilized as monomer together with poly(tetramethylene oxide) (PTMO) comonomer for preparing the final polymer as well. The NH₂-functionalized TiO₂ nanoparticles are covalently linked to the NCO terminals of the resulting SPU macromolecules during film preparation stage. Therefore, in addition to butylene glycol, these surface modified nanoparticles with enhanced organophilicity could play the role of the second chain extender of NCO-capped SPU macromolecules through formation of urea linkages. Optical and thermal behaviors of the transparent and flexible film (SPU/TiO₂–MDI) is compared with those of unmodified TiO₂ (SPU/TiO₂) and TiO₂-unloaded SPU films. Though the particle loading is only 5 wt.%, incorporation of TiO₂ and TiO₂–MDI nanoparticles into the SPU polymer enhances significantly the light absorption in UV region at 300–400 nm. SEM images of the prepared films clearly show a considerable decrease in particle aggregation for TiO₂–MDI into SPU matrix compared to that of unmodified TiO₂. TG analyses indicate a one-step decomposition pattern with onset temperatures of about 360 and 380 °C for neat SPU and SPU/TiO₂–MDI, respectively. Moreover, DTA thermograms of both nanocomposites show obviously two exothermic phase transitions in the thermal range of 330–440 °C.     

Spreading and Curing Behaviors of a Thermosetting Droplet-Silicone on a Heated Surface

Thermosetting materials are widely used as encapsulation in the electrical packaging to protect the core electronic components from external force, moisture, dust, and other factors. However, the spreading and curing behaviors of such kind of fluid on a heated surface have been rarely explored. In this study, we experimentally and numerically investigated the spreading and curing behaviors of the silicone(OE6550 A/B, which is widely used in the light-emitting diode packaging) droplet with diameter of ～2.2 mm on a heated surface with temperature ranging from 25 ℃ to 250 ℃. For the experiments, we established a setup with high-speed camera and heating unit to capture the fast spreading process of the silicone droplet on the heated surface. For the numerical simulation, we built a viscosity model of the silicone by using the Kiuna's model and combined the viscosity model with the Volume of Fluid(VOF) model by the User Defined Function(UDF) method. The results show that the surface temperature significantly affected the spreading behaviors of the silicone droplet since it determines the temperature and viscosity distribution inside the droplet. For surface temperature varied from 25 ℃ to 250 ℃, the final contact radius changed from ～2.95 mm to ～1.78 mm and the total spreading time changed from ～511 s to ～0.15 s. By further analyzing the viscosity evolution of the droplet, we found that the decreasing of the total spreading time was caused by the decrease of the viscosity under high surface temperature at initial spreading stage, while the reduction of the final contact radius was caused by the curing of the precursor film. This study supplies a strategy to tuning the spreading and curing behavior of silicone by imposing high surface temperature, which is of great importance to the electronic packaging.     

A novel bio‐based phthalonitrile resin derived from catechin: synthesis and comparison of curing behavior with petroleum‐based counterpart

The development of bio‐based thermosetting resins with good thermal stability can potentially afford sustainable polymers as replacements for petroleum‐based polymers. We report a practical route to a novel catechin‐based phthalonitrile resin precursor (CA‐Ph), which contains free phenolic hydroxyl groups that result in ‘self‐curing’ at elevated temperatures to afford a thermostable polymer. Comparison of the performance of this CA‐Ph resin with that of a conventional petroleum‐based bisphenol A phthalonitrile resin (BPA‐Ph; containing 5 wt% of the curing agent 4,4′‐diaminodiphenylsulfone) revealed that CA‐Ph exhibits a lower melting point and curing temperature. Cured CA‐Ph resin retains 95% of its weight at 520 °C under a nitrogen atmosphere, which compares favorably with results obtained for BPA‐Ph resin that retains 95% of its weight at a lower temperature of 484 °C. Kinetic results indicated that the curing reactions of both CA‐Ph and BPA‐Ph systems follow an autocatalytic mechanism. These results suggest that catechin is a useful bio‐based feedstock for the preparation of self‐curing and thermally stable phthalonitrile resins for advanced technological applications. © 2017 Society of Chemical Industry     

Chloride migration in concrete with superabsorbent polymers

Superabsorbent polymers (SAP) can be used as a means for internal curing of concrete. In the present study, the development of transport properties of concrete with SAP is investigated. The chloride migration coefficient according to NT BUILD 492 is used as a measure of this. Twenty concrete mixtures are tested 7, 14, and 28 days after casting. The development of degree of hydration is followed for 20 corresponding paste mixtures.Both when SAP is added with extra water to compensate the SAP water absorption in fresh concrete and without extra water, the internal curing water held by SAP may contribute to increase the degree of hydration. No matter if SAP is added with or without extra water, it appears that the so-called gel space ratio can be used as a key parameter to link age and mixture proportions (water-to-cement ratio and SAP dosage) to the resulting chloride migration coefficient; the higher the volume of gel solid relative to the space available for it, the lower the chloride migration coefficient, because the pore system becomes more tortuous and the porosity becomes less.     

含磷固化剂及固化环氧树脂的合成及表征

以4,4′-二氨基二苯基甲烷(DDM)、苯甲醛和亚磷酸二乙酯为原料,合成了两种含磷固化剂PM1和PM2,用红外光谱、核磁共振氢谱对PM1和PM2的结构进行了表征。用DDM,PM1,PM2分别固化双酚A型(DGEBA)环氧树脂,得到DGEBA-DDM,DGEBA-PM1,DGEBA-PM2树脂,采用示差扫描量热法、热重分析(TGA)和极限氧指数(LO I)对DGEBA-DDM,DGEBA-PM1,DGEBA-PM2树脂的玻璃化转变温度(Tg)、反应活性、热稳定性和阻燃性能进行了表征。实验结果表明,PM2的反应活性比PM1低;DGEBA-DDM,DGEBA-PM1,DGEBA-PM2树脂的Tg分别为178,112,145℃;TGA结果表明,700℃时DGEBA-PM1和DGEBA-PM2树脂的成炭率分别为29%和35%,而700℃时DGEBA-DDM树脂的成炭率只有19%;DGEBA-PM1和DGEBA-PM2树脂的LO I值由DGEBA-DDM树脂的24%分别增至30%和35%,且阻燃性能大幅度提高。     

Rheological cure characterization of phosphazene–triazine polymers

Cyclomatrix phosphazene–triazine network polymers were synthesized by co‐curing a blend of tris(2‐allylphenoxy), triphenoxy cyclotriphosphazene (TAP), and tris(2‐allylphenoxy) s‐triazine (TAT) with bis(4‐maleimido phenyl) methane (BMM). The co‐curing of the three‐component resin was investigated by dynamic mechanical analysis using rheometry. The cure kinetics of the Diels–Alder step was studied by examining the evolution of the rheological parameters, such as storage modulus (G′), loss modulus (G″), and complex viscosity (η*), for resins of varying compositions at different temperatures. The curing conformed to an overall second‐order phenomenological equation, taking into account a self‐acceleration effect. The kinetic parameters were evaluated by multiple‐regression analysis. The absence of a definite trend in the cure process with blend composition ratio was attributed to the occurrence of a multitude of competitive reactions whose relative rates depend on the reactant ratio and the concentration of the products formed from the initial phase of reaction. The cure was accelerated by temperature for a given composition, whereas the self‐acceleration became less prominent at higher temperature. Gelation was accelerated by temperature. The gel conversion decreased with increase in maleimide concentration and, for a given composition, it was independent of the cure temperature. The activation energy for the initial reaction and the crosslinking process were estimated for a composition with a maleimide‐to‐allyl ratio of 2 : 1. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 908–914, 2003     

Processing and microstructure of non-oxide ceramic fibres

Research and development efforts on high-temperature, oxidation-resistant fibres have increased over the past decade due to the demand for light-weight, stiff and strong composite materials in aerospace applications. Varieties of ‘high-performance’, continuous, non-oxide fibres with low-density, high tensile strength and tensile modulus have been developed either from organic precursors or via chemical vapour deposition for fabrication of ceramic matrix composites. Fibres derived from polymer precursors (e.g. Nicalon, Tyranno, HPZ) are small in diameter (compared to CVD monofilaments) and are ideally suited for ceramic composites. Processing, microstructural stability and mechanical properties of these newly developed SiC and Si₃N₄ base fibres are briefly reviewed in this paper.