Ripening and growth of zinc oxide nanorods from nanoparticles in 1,4 butanediol solvent

Zinc oxide nanorod formation in 1,4-butanediol was studied as a function of time and temperature using TEM and UV–Vis absorption spectra. Nanorod morphologies are formed by annealing of dilute nanodots, initially formed by sol–gel reaction in 1,4-butanediol. The nanorod morphology is unusual in the termination of the c-axis facets, with one end perpendicular to the a facets (flat) and the other faceted into a six-sided point. Ripening of nanodots proceeds via the Lifshitz–Slyozov–Wagner model of diffusion limited coarsening, and annealing at elevated temperature leads a transition to nanorod morphologies. Nanoparticle dissolution and shape development affect the axial ratio of the growing nanorods. Evidence of oriented attachment was not observed in the ripening study. The use of 1,4-butanediol allows for higher temperature reaction than in alcohols, without the use of pressure vessels.     

Influence of nanodispersed boehmite on polypropylene photooxidation

Nanocomposites containing pure or organically modified nanoboehmites of different sizes were prepared by melt compounding with polypropylene. The samples were UV light irradiated in artificial accelerated conditions representative of solar irradiation (λ > 300 nm) at 60 °C in air. The chemical modifications resulting from photooxidation were followed by IR and UV-visible spectroscopies. The presence of pristine nanoboehmites was shown to change the rate of oxidation of polypropylene by reducing the oxidation induction period due to the presence of residual processing antioxidant. The differences of the oxidation induction periods between the nanocomposites and the pristine polymer disappear after solvent extraction of the antioxidant. The inefficiency of traditional antioxidant in retarding the photooxidation of polypropylene containing nanodispersed boehmite is proved. Antioxidant migration to the boehmite surface induced by the preferential interaction with the polar filler is proposed as an explanation. The oxidative behaviour of the organically modified boehmites was shown to depend on the type of organic substituent. p-Toluenesulfonate reduces the adsorption of antioxidants while the presence of a long-chain alkyl benzensulfonate increased the oxidation rate by generation of radical initiators.     

Fabrication of TiN nanorods by electrospinning and their electrochemical properties

TiN nanorods were synthesized using electrospinning technique followed by thermolysis in different atmospheres. A dimethyl formamide-ethanol solution of poly-(vinyl pyrrolidone) and Ti (IV)-isopropoxide was used as the electrospinning precursor solution and as-spun nanofibers were calcined at 500 °C in air to generate TiO₂ nanofibers. Subsequently, a conversion from TiO₂ nanofibers to TiN nanorods was employed by the nitridation treatment at 600∼1400 °C in ammonia atmosphere. A typical characteristic of the final products was that the pristine nanofibers were cut into nanorods. The conversion from TiO₂ to TiN was realized when the nitridation temperature was above 800 °C. As-prepared nanorods were composed of TiN nano-crystallites and the average crystallite size gradually increased with the increase of the nitridation temperature. Electrochemical properties of TiN nanorods showed strong dependence on the nitridation temperature. The maximum value of the specific capacitance was obtained from the TiN nanorods prepared at 800 °C.     

Effect of polyether diamine on gas permeation properties of organic-inorganic hybrid membranes

The quantitative incorporation and high dispersion of platinum nanoparticles into MCM-41 has been carried out by the coordination between Pt(IV) ion and APTMS-anchored MCM-41. Before and after calcination of Pt/APTMS/MCM41 samples, the Pt content in samples was evaluated from home-made photoacoustic spectrometer (PAS). The PAS bands at 350 nm and 450 nm can be assigned to d–d transition bands of Pt complexes. By increasing the concentration of Pt solution, the PAS intensity of Pt/APTMS/MCM41 was increased proportionally up to 1.0×10⁻² M, and remained constant above 1.0×10⁻² M. It can be attributed to the saturation of Pt content within Pt/APTMS/MCM41. The Pt content in the saturated Pt/APTMS/MCM41 was 8.5 wt% (the theoretical value), 9.7 wt% (measured by EDX) and 9.2 wt% (measured by ESCA), respectively. This indicates that the content of Pt precursor within MCM-41 could be controlled by the concentration of Pt precursor solution. The PAS intensity of calcined Pt/APTMS/MCM41's in H₂ flow was increased up to 1.0×10⁻² M and remained nearly constant above 1.0×10⁻² M. Therefore, we suggest that the formation of Pt complexes with APTMS-anchored MCM-41 made it possible to incorporate quantitatively Pt nanoparticles in the range of 0.5–9.2 wt% within MCM-41 channels.     

Preparation of CuInS2 Thin Film Using Sulfides Nanoparticle Precursor Ink

A low cost spin coating route of fabricating CuInS₂ polycrystalline thin films by reactive sin-tering method was put forward. The ink for spin coating was optimized by pre-reducing the precursor powders in hydrogen, which turned the nanoparticle precursor powders from mixed sulfides into a mixture of CuInS₂ and Cu-In metal alloys. The results of scanning electron microscopy, energy dispersive spectroscopy, X-ray diffraction, and Raman spectra showed that this optimization could highly improve the performance of CuInS₂ polycrystalline thin films, including higher packing density, less impurity phases, and better quality. The en-ergy gap of optimized CuInS₂ thin film was determined to be about 1.45 eV by absorption spectroscopy measurement.     

Preparation and characterization of Cu (II) Schiff base complex functionalized boehmite nanoparticles and its application as an effective catalyst for oxidation of sulfides and thiols

The synthesis, characterization, and evaluation of a Schiff base Cu (II) complex functionalized boehmite nanoparticles (Cu-complex-boehmite) as a new catalyst for oxidation of sulfides and thiols in the presence of hydrogen peroxide with complete selectivity and high conversion under solvent-free and mild reaction conditions were reported. Characterization of the catalyst was performed with various physicochemical methods. This effective catalyst was evaluated in terms of activity and reusability. It indicated high catalytic activity, good recoverability and reusability, and supplied the corresponding products in high yields and short reaction times. In addition, it shows notable advantages such as simplicity of operation, heterogeneous nature, easy work up, and it could be used at least eight times with no significant loss of its activity.     

BiOI@La(OH)3纳米棒异质结制备及其增强可见光催化去除NO性能

一维La(OH)3纳米棒具有特殊的电子结构和多功能特性,特别是作为半导体光催化剂引起了人们极大的兴趣.但La(OH)3禁带宽度较大,且只能吸收紫外光,所以光催化效率较低,可见光利用能力较差,限制了La(OH)3的实际应用.因此,需要开发一种高效的改进方法来提高La(OH)3的可见光催化性能.本课题组发展了一种有效的改进La(OH)3方法,通过简易的方法将BiOI纳米颗粒沉积在La(OH)3纳米棒上,有效增强了对可见光的吸收能力和光生载流子的分离能力.本文采用X射线衍射(XRD)、透射电镜(TEM)、扫描电镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)、荧光光谱(PL)、光电子能谱(XPS)、电子自旋共振(ESR)、N2吸附和元素分析等手段研究了BiOI@La(OH)3纳米棒异质结的构建原理及增强可见光催化性能的原因.XRD和XPS结果表明,通过简易化学沉积法原位构建了BiOI@La(OH)3异质结,并且在异质结中没有杂相生成.由SEM图像可见,原始La(OH)3由分散的一维纳米棒组成,平均直径为30–50 nm.通过BiOI与La(OH)3表面的紧密接触成功构建异质结,但BiOI纳米颗粒未改变La(OH)3纳米棒的形貌.由TEM和HRTEM图像可见,La(OH)3纳米棒的平均长度为30–50 nm,并且在BiOI@La(OH)3异质结中可以清晰看出BiOI和La(OH)3之间紧密接触的界面和晶格间距.N2物理吸附结果显示,随着BiOI量的增加,BiOI@La(OH)3异质结的比表面积增加,但孔体积未现明显变化.UV-Vis DRS结果显示,引入BiOI后明显促进了La(OH)3对可见光的吸收能力和利用效率,从而有利于增强可见光催化活性.通过理论计算分别得到BiOI和La(OH)3的价带和导带位置,表明具有非常匹配的能带结构可以促进BiOI光生电子的有效转移.可见光催化去除NO测试结果表明,BiOI@La(OH)3异质结的光催化活性高达50.5%,明显优于BiOI和La(OH)3.ESR测试结果显示,BiOI@La(OH)3异质结可见光催化活性中起主要作用的活性物种是?OH.结合表征结果,BiOI@La(OH)3纳米棒异质结可见光催化性能增强的原因主要有三个:(1)BiOI@La(OH)3异质结增大的比表面积有利于反应物和产物在催化剂表面扩散,同时可提供更多活性位点参与光催化反应;(2)禁带宽度影响光催化效率,当BiOI与La(OH)3达到合适比例时,既可以促进可见光吸收,也可以使光生电子具有较强还原能力;(3)BiOI@La(OH)3异质结有利于光生载流子的分离,从而显著提高其光催化活性.     

H型(PS)2PEG(PS)2嵌段共聚物在旋涂过程中的结晶行为

采用原子力显微镜和X射线衍射等手段研究了H型(PS)₂PEG(PS)2嵌段共聚物在不同溶剂和不同浓度的溶液中旋涂所得薄膜的形貌, 并与聚乙二醇(PEG)均聚物进行了比较. 虽然(PS)₂PEG(PS)₂中PS的链长很短, 但对形貌有很大影响, PS链段的存在改变了聚合物在基底上的稳定性, 使用四氢呋喃为溶剂, 当溶液浓度较小时, 在旋涂过程中发生去润湿, 然后再发生结晶, 膜厚较大时去润湿被抑止, 所得形貌与PEG均聚物类似. 以甲苯为溶剂时, 由于PEG和PS与溶剂的相互作用不同, 共聚物在溶液中形成胶束, 从而改变了聚合物的结晶形貌.     

Structural and magnetic properties of self assembled Fe-doped Cu2O nanorods

Cuprous oxide (Cu₂O) nanorods doped with iron impurities have been synthesized by the polyol method using sodium dodecyl sulfate as the surfactant. The X-ray diffraction measurement reveals the pure phase of simple cubic Cu₂O and the electron microscopy displays its one dimensional morphology. Ferromagnetism was observed at room temperature in the magnetic measurements of the doped samples while undoped sample exhibits only diamagnetism. Room temperature Mössbauer spectra for the samples exhibited only doublets but no sextet, which corresponds to the presence of paramagnetic iron sites. As magnetic moment contribution of the doped ions was insignificant for the observed magnetism, ferromagnetic property in the doped samples could have been originated from the defects as cation vacancies. Existence of the defects was supported by the room temperature photoluminescence spectra of the doped samples in reference to the undoped sample.     

Effect of the linear siloxane chain in cyclic silsesquioxane (CSSQ) on the mechanical/electrical property of the thin films

Several kinds of cyclic silsesquioxane (CSSQ) precursors containing linear siloxane chain were prepared to improve both the mechanical properties of their thin films and the compatibility with heptakis (2,3,6-tri-O-methyl)-β-cyclodextrin (tCD) as a porogen. The precursors were synthesized using a hydrolysis/condensation reaction with 2,4,6,8-tetramethyl-2,4,6,8-tetra (trimethoxysilylethyl) cyclotetrasiloxane (cyclic monomer) and three kinds of linear siloxane monomers. As the linear siloxane chain length increases in the CSSQ precursors, the compatibility between the CSSQ precursor and tCD molecules improved due to the chain flexibility of the precursor. Moreover, the mechanical strength of the CSSQ precursor (4ST37) containing linear tetrasiloxane was the best among the prepared precursors. The enhancement of mechanical property might also be attributed to the content of Si-OH groups as well as the chain flexibility, which could help the crosslinking reaction of Si-OH groups in the film curing process.     

Effect of crystalline structure on the hardness and interfacial adherence of flame sprayed poly(ether-ether-ketone) coatings

Flame sprayed PEEK (poly-ether-ether-ketone) coatings, with an amorphous structure, were subjected to isothermal treatments with annealing temperatures from 180 to 300 °C and holding times from 1 to 30 min. The coating structures were studied by means of differential scanning calorimetry (DSC) and X-ray diffraction (XRD) analyses. All the annealed coatings exhibited semi-crystalline structures. Coexistence of thick and thin lamellae in the spherulites of annealed coatings can be deduced. The Knoop hardness and the interfacial adhesion of the coatings were examined. The annealed coatings exhibit higher hardness than the amorphous one. The formation of the thick lamellae is a determining factor for improving the coating hardness, which could restrict the motions and slippages of the polymer chains. However, the annealed coatings exhibit a weak adherence to the substrate. Some fissures or spherical porosities could be observed, in certain zones, on the coating/substrate interface. The formation of these fissures and porosities could be ascribed to the coating residual stress and the large volume contraction during the crystallization that occurred under the annealing conditions.     

Tribological properties of ormosil coatings

Transparent plastics are not scratch resistant. The damage leads to a loss of optical properties. Coatings prepared using either tetraethoxysilane or colloidal silica particles embedded in glymo is a way to avoid these disadvantages. Tribological experiments are carried out to better understand the surface modification due to a sliding friction. It is shown that the wear track is not directly related to usual mechanical properties such as Young's modulus and the hardness of the coating. The different stages leading to material loss are discussed in term of particle removal and debris circulation (accumulation or elimination) through the friction track. The mechanical properties of the film combined with the film to substrate adhesion are expected to play an important role as it can be deduced from results obtained as a function of the coating composition.     

Coaxial electrospinning core-shell fibers for self-healing scratch on coatings

Polystyrene (PS) fibers with core-shell structure were prepared by coaxial electrostatic spinning using liquid epoxy or curing agent as the core and PS solution as the shell. Scratch self-healing coatings were realized by using the healant-loaded core-shell fibers in the matrix.     

CTAB assisted hydrothermal synthesis, controlled conversion and CO oxidation properties of CeO2 nanoplates, nanotubes, and nanorods

In this work, CeO₂ nanoplates were synthesized by a hydrothermal reaction assisted by hexadecyltrimethylammonium bromide (CTAB) at 100-160 °C. The size of nanoplates was around 40 nm. Further experiment showed that the controlled conversion of nanoplates into nanotubes, and nanorods can be realized by changing the reaction time, temperature, and CTAB/Ce³⁺ ratio value. X-ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) nitrogen adsorption-desorption measurements were employed to characterize the samples. The CO oxidation properties of nanorods, nanoplates, and nanotubes were investigated. An enhanced catalytic activity has been found for CO oxidation by using CeO₂ nanoplates as compared with CeO₂ nanotubes and nanorods, and the crystal surfaces (100) of CeO₂ nanoplates were considered to play an important role in determining their catalytic oxidation properties.     

Influence of Poly (methyl metacrylate) Addition on Resistive Switching Performance of P3HT/P(VDF-TrFE) Blend Films

Organic semiconducting/ferroelectric blend films attracted much attention due to their elec-trical bistability and rectification properties and thereof the potential in resistive memory devices. Blend films were usually deposited from solution, during which phase separation oc-curred, resulting in discrete semiconducting phase whose electrical property was modulated by surrounding ferroelectric phase. However, phase separation resulted in rough surface and thus large leakage current. To further improve electrical properties of such blend films, poly(methyl metacrylate) (PMMA) was introduced as additive into P3HT/P(VDF-TrFE) semiconducting/ferroelectric blend films in this work. It indicated that small amount of PMMA addition could effectively enhance the electrical stability to both large electrical stress and electrical fatigue and further improve retention performance. Overmuch PMMA addition tended to result in the loss of resistive switching property. A model on the con-figuration of three components was also put forward to well understand our experimental observations.     

Preparation and evaluation of solid-phase microextraction fibres based on functionalized latex nanoparticle coatings for trace analysis of inorganic anions

The use of a functionalized latex nanoparticle coating as a new sorbent phase for solid-phase microextraction (SPME) was examined. By means of electrostatic absorption onto ionized silanol groups, a fused-silica rod was coated with polymeric nanoparticles functionalized with quaternary ammonium groups. Optimum conditions for the preparation of the coated fibre are presented. The fibre was used for the extraction of a mixture of seven anions from water samples which are analysed by coupling the SPME fibre to an ion chromatographic system via a special interface. The results obtained proved the suitability of this novel coating as a new SPME fibre. A linear calibration for the target analytes was achieved over the concentration range from 5 μg L⁻¹ to 5 mg L⁻¹ (r² > 0.988), while limits of detection for these ions were all below 3.7 μg L⁻¹ (S/N = 3). The reproducibility of a single fibre (n = 4) under similar conditions was between 7 and 12%, while the fibre to fibre reproducibility (n = 5) was between 8.9 and 14%.     

Novel organic/inorganic hybrid self-assembly aggregates of ferrocene-poly(styrene)-b-poly[3-(trimethyoxysilyl)propyl methacrylate]

Ferrocene-poly(styrene)-b-poly[3-(trimethyoxysilyl)propyl methacrylate] (Fc-PS₂₁₂-PTMSPMA₁₂) was synthesized via atom transfer radical polymerization (ATRP) and characterized. The self-assembly of the resultant polymer was investigated. The organic/inorganic hybrid nanoparticles from self-assembly aggregates of Fc-PS₂₁₂-PTMSPMA₁₂ including spheres, vesicles, and large compound vesicles (LCVs) were obtained and the morphologies were fixed by a gelation process.     

Effect of crystallite size on the thermal phase change and porous properties of boehmite

The effect of crystallite size on the thermal phase change and porous properties of boehmite was investigated using boehmites with crystallite sizes of 2.9 to 24.4 nm and boehmite gels prepared by precipitation and hydrothermal methods. The dehydroxylation temperature of boehmite increases, its phase transition temperature from gamma- to theta-Al(2)O(3) decreases and the theta- to alpha-Al(2)O(3) transition temperature increases as the crystallite size of the boehmite increases. Boehmite with a crystallite size of approximately 5 nm shows the highest specific surface area and greatest thermal stability. This boehmite contains pores of about 2-3 nm radius, suggested to be responsible for the superior porous properties and thermal stability.     

Synthesis and properties of iron oxide coated carbon nanotubes hybrid materials and their use in epoxy coatings

Multi‐walled carbon nanotubes (MWCNTs) were acidified with nitration mixture, and the Fe₂O₃‐MWCNTs (iron oxide coated multi‐walled carbon nanotubes) hybrid material via sol‐gel method then verified the results through scanning electron microscope, X‐ray diffraction, and thermal gravimetric analysis. We modified the hybrid material with silane coupling agent (KH560), Fe₂O₃‐MWCNTs/epoxy, MWCNTs/epoxy composites coating, and the pure epoxy coatings were respectively prepared. The properties of the composite coatings were tested through the electrochemical workstation (electrochemical impedance spectroscopy), shock experiments, and thermal gravimetric analysis. Finally, we used scanning electron microscope to observe the surface conditions of the coatings. The results show that Fe₂O₃‐MWCNTs have good dispersion in the epoxy resin, and the Fe₂O₃‐MWCNTs/epoxy composite coatings have enhanced mechanical properties and corrosion resistance. Copyright © 2015 John Wiley & Sons, Ltd.