Single-phase (Hf0.84Ta0.16)C solid solution nanowires growth via catalyst-assisted chemical vapor deposition

Fabricating one-dimensional (1D) ceramic nanostructure with superior performance is an important approach to broaden their applications. In this paper, the synthesis of single-phase (Hf_0.84Ta_0.16)C solid solution nanowires via catalyst-assisted chemical vapor deposition was proposed for the first time. The [0 1 1̄] growth direction of (Hf_0.84Ta_0.16)C solid solution nanowires was discussed in detail and its corresponding growth mechanism was identified to be top-type vapor–liquid–solid mechanism. More impressively, our work could widen the application ranges of ceramic nanowires and propose the new thinking of fabricating ultrahigh melting point nanostructure.     

Influence of reaction parameters on the synthesis of hyperbranched polymers via reversible addition fragmentation chain transfer (RAFT) polymerization

The synthesis of hyperbranched poly(methyl methacrylate) (PMMA) via reversible addition fragmentation chain transfer (RAFT) polymerization was investigated by varying the ratio chain transfer agent (CTA): monomer (methyl methacrylate, MMA): brancher (ethylene glycol dimethyl methacrylate, EGDMA): free radical initiator (AIBN) at various temperatures (50, 55, 60, 65, 70 °C). The rate of polymerization was observed to increase with temperature and concentration in brancher, whilst it was lowered by an increase in chain transfer agent concentration. The molecular weight of the samples increased with the ratios brancher: CTA and monomer: CTA. The polydispersity of the samples increase with conversion, as the level of branching increases. At fixed concentration in brancher, an increase of CTA concentration led to polymers with lower PDI. The variation of enthalpy and entropy relative to the monomer reaction were calculated, and it was observed that an increase in the brancher concentration induced an increase in both and , whilst lower CTA concentrations led to an increase in . The variation in Gibbs energy for the monomer reaction was calculated at 60 °C, and results confirmed the presence of a retardation effect when increasing CTA concentration generally observed in RAFT polymerization.     

Synthesis of hyperbranched polymers via a facile self-condensing vinyl polymerization system - Glycidyl methacrylate/Cp2TiCl2/Zn

A facile self-condensing vinyl polymerization (SCVP) system, the combination of glycidyl methacrylate, Cp₂TiCl₂ and Zn, has been firstly used to prepare novel hyperbranched polymers, consisting of vinyl polymers as the backbone, and cyclic ester polymers (poly(?-caprolactone) or poly(l-lactide)) as the side chains. The polymerizations are initiated by the epoxide radical ring-opening catalyzed by Cp₂Ti(III)Cl which is generated in situ via the reaction of Cp₂TiCl₂ with Zn. The key to success is that the polymerizations can proceed concurrently via two dissimilar chemistries possessing the opposite active initiating species, including ring-opening polymerization (ROP) and controlled/living radical polymerization (CRP). We have demonstrated that this facile one-step polymerization technique can be applied successfully to prepare highly branched polymers with a multiplicity of end reactive functionalities including Ti alkoxide, hydroxyl and vinyl functional groups.     

Interior-architectured ZnO nanostructure for enhanced electrical conductivity via stepwise fabrication process

Fabrication of ZnO nanostructure via direct patterning based on sol-gel process has advantages of low-cost, vacuum-free, and rapid process and producibility on flexible or non-uniform substrates. Recently, it has been applied in light-emitting devices and advanced nanopatterning. However, application as an electrically conducting layer processed at low temperature has been limited by its high resistivity due to interior structure. In this paper, we report interior-architecturing of sol-gel-based ZnO nanostructure for the enhanced electrical conductivity. Stepwise fabrication process combining the nanoimprint lithography (NIL) process with an additional growth process was newly applied. Changes in morphology, interior structure, and electrical characteristics of the fabricated ZnO nanolines were analyzed. It was shown that filling structural voids in ZnO nanolines with nanocrystalline ZnO contributed to reducing electrical resistivity. Both rigid and flexible substrates were adopted for the device implementation, and the robustness of ZnO nanostructure on flexible substrate was verified. Interior-architecturing of ZnO nanostructure lends itself well to the tunability of morphological, electrical, and optical characteristics of nanopatterned inorganic materials with the large-area, low-cost, and low-temperature producibility.     

Flame retardancy and thermal properties of poly(butylene succinate)/ nano-boehmite composites prepared via in situ polymerization

Poly(butylene succinate) (PBS) and its nanocomposites with nanoboehmite (nBhm) were synthesized via direct esterification between succinic acid and butylene glycol (BG). Boehmite (Bhm) nanoparticles, up to 2%, were added in the polycondensation step. Repeatability of runs was observed by the amount of the gathered water. Temperature trajectory was considered as an indication of the polycondensation start. Mixing torque was measured and its rapid increase, up to 0.6 Nm, was deliberated as the end of the process. Polycondensation time decreases with an increase in amount of nBhm due to the catalytic role of aluminum in Bhm. The chemical structure of PBS was proved through Fourier transform infrared spectroscopy and nuclear magnetic resonance spectroscopies. XRD spectrum and scanning electron microscope images show a good distribution of nanoparticles in the polymer matrix. Differential scanning calorimetric results determine that T_g increases with the nanoparticle content. Improved Avrami equation was fitted to study the kinetics of the crystallization of samples. As a result, spherulite crystal growth was determined based on the Avrami index. Thermal gravimetric analysis trends are the same, however, nanocomposites show more residual ash. Atomic force microscopy images show that nanocomposites have a rough surface. It was observed that the flame advancement decreases up to 60% and limiting oxygen index increases up to 8%.     

Effect of flake size on thermal properties of graphene oxide/poly(methyl methacrylate) composites prepared via in situ polymerization

The effect of graphene oxide (GO) flake size on thermal properties of GO/poly(methyl methacrylate) (GO/PMMA) composites prepared via in situ polymerization was investigated. Two styles of GO sheets were synthesized from different sizes of graphite powders by modified Hummers' method and GO/PMMA composites with GO of different sizes were prepared via in situ polymerization. Transmission electron microscopy verified that GO sheets produced from large graphite powders was obviously larger than that from small graphite powders. The similar number of layers and disorder degree of two types of GO sheets were proved by X‐ray diffraction and Raman, respectively. X‐ray diffraction and scanning electron microscopy results of GO/composites proved the homogenous dispersion of both two types of GO sheets in polymer matrix. Dynamic mechanical analysis and thermogravimetric analysis results showed that large GO sheets exhibit better improvement than small GO sheets in thermal properties of the composites. Compared with neat PMMA, the glass transition temperature and decomposition temperature of the composites with large GO sheets (0.20 wt %) were increased by 15.9 and 25.9 °C, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46290.     

Microstructures and photovoltaic performances of bismuth-ion doped Cu(In,Ga)Se2 films prepared via sputtering process

Bismuth-ion doped Cu(In,Ga)Se₂ (CIGS) solar cells were fabricated via sputtering technique. The influence of bismuth-ion doping on structural and photovoltaic characteristics of the fabricated CIGS films were explored in details. With doping of bismuth ions, the grain sizes of CIGS layers were enhanced appreciably due to liquid-phase sintering with the yielded intermediate compound. The secondary ion mass spectroscopy profile results indicated that the diffusion of bismuth ions into CIGS layers promoted dissemination of gallium species from the back contacts to the surface of CIGS layers. According to Hall measurement analysis, the carrier concentration in CIGS films was enhanced significantly with the doping of bismuth ions in the prepared films. The conversion efficiency of the bismuth-ion doped samples was increased approximately 10% in comparison with undoped samples due to the elevated gallium-ion diffusion and grain growth. Various photovoltaic parameters including saturated current and diode factors of the prepared doped CIGS solar cells were decreased owing to the inhibition of electron-hole recombination. This investigation demonstrated the improved photovoltaic performance and the structural characteristics of fabricated CIGS films after the doping of bismuth ions.     

Comprehensive dynamic failure mechanism of thermal barrier coatings based on a novel crack propagation and TGO growth coupling model

Comprehensive understanding of failure mechanism of thermal barrier coatings (TBCs) is essential to develop the next generation advanced TBCs with longer lifetime. In this study, a novel numerical model coupling crack propagation and thermally grown oxide (TGO) growth is developed. The residual stresses induced in the top coat (TC) and in the TGO are calculated during thermal cycling. The stresses in the TC are used to calculate strain energy release rates (SERRs) for in-plane cracking above the valley of undulation. The overall dynamic failure process, including successive crack propagation, coalescence and spalling, is examined using extended finite element method (XFEM). The results show that the tensile stress in the TC increases continuously with an increase in an undulation amplitude. The SERRs for TC cracks accumulate with cycling, resulting in the propagation of crack toward the TC/TGO interface. The TGO cracks nucleate at the peak of the TGO/bond coat (BC) interface and propagate toward the flank region of the TC/TGO interface. Both TC cracks and TGO cracks successively propagate and finally linkup leading to coating spallation. The propagation and coalescence behavior of cracks predicted by this model are in accordance with the experiment observations. Therefore, this study proposed coating optimization methods towards advanced TBCs with prolonged thermal cyclic lifetime.     

Synthesis and thermal behavior of poly(methyl methacrylate)/Maghnia bentonite nanocomposite prepared at room temperature via in situ polymerization initiated by a new Ni(II)α‐benzoinoxime complex

Poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate)/clay nanocomposite (PMMA/OBT) were successfully prepared in dioxan at room temperature via in situ radical polymerization initiated by a new Ni(II)α‐ Benzoinoxime complex as a single component in presence of 3% by weight of an organically modified bentonite (OBT) (originated from Maghnia, Algeria) and characterized by FTIR, ¹H‐NMR and viscometry. Mainly intercalated and partially exfoliated PMMA/OBT nanocomposite was elaborated and evidenced by X‐Ray diffraction (XRD) and transmission electron microscopy (TEM). The intrinsic viscosity of PMMA/OBT nanocomposite is much higher than the one of pure PMMA prepared under the same conditions. Differential scanning calorimetry (DSC) displayed an increase of 10°C in the glass transition temperature of the elaborated PMMA/OBT nanocomposite relative to the one of pure PMMA. Moreover, the TGA analysis confirms a significant improvement of the thermal stability of PMMA/OBT nanocomposite compared to virgin PMMA: the onset degradation temperature of the nanocomposite, carried out under nitrogen atmosphere, increased by more than 45°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011