In situ preparation of monodispersed Ag/polyaniline/Fe3O4 nanoparticles via heterogeneous nucleation

Acrylic acid and styrene were polymerized onto monodispersed Fe₃O₄ nanoparticles using a grafting copolymerization method. Aniline molecules were then bonded onto the Fe₃O₄ nanoparticles by electrostatic self-assembly and further polymerized to obtain uniform polyaniline/Fe₃O₄ (PANI/Fe₃O₄) nanoparticles (approximately 35 nm). Finally, monodispersed Ag/PANI/Fe₃O₄ nanoparticles were prepared by an in situ reduction reaction between emeraldine PANI and silver nitrate. Fourier transform infrared and UV-visible spectrometers and a transmission electron microscope were used to characterize both the chemical structure and the morphology of the resulting nanoparticles.     

Paper-like graphene-Ag composite films with enhanced mechanical and electrical properties

In this paper, we have reported that paper-like graphene-Ag composite films could be prepared by a facile and novel chemical reduction method at a large scale. Using ascorbic acid as a reducing agent, graphene oxide films dipped in Ag⁺ aqueous solutions can be easily reduced along with the decoration of different sizes of Ag particles distributed uniformly. The results reveal that the obtained films exhibit improved mechanical properties with the enhancement of tensile strength and Young''s modulus by as high as 82% and 136%, respectively. The electrical properties of graphene-Ag composite films were studied as well, with the sheet resistance of which reaching lower than approximately 600 Ω/□. The graphene-Ag composite films can be expected to find interesting applications in the area of nanoelectronics, sensors, transparent electrodes, supercapacitors, and nanocomposites.     

Novel mesoporous MnO2 for high-rate electrochemical capacitive energy storage

MnO₂ with novel mesoporous structure has been firstly synthesized via a simple in situ reduction process by using different carbon materials as sacrificed template and reducing agent. The morphology and microstructure of as-synthesized mesoporous MnO₂ were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), nitrogen adsorption and desorption experiments. The results demonstrate that porous MnO₂ prepared using mesoporous carbon as template has very large specific surface area and uniform pore-size distribution. The electrochemical measurements showed that novel porous MnO₂ have higher capacity (221 F g⁻¹) with excellent rate and higher capacity retention as electrochemical capacitors (ECs) electrode materials, which may be attributed to the unique nanostrcture of porous MnO_2. These all imply that MnO₂ with novel mesoporous structure has been attractive for practical and large-scale applications in mobile equipment.     

Intercalated structure of polypropylene/in situ polymerization-modified talc composites via melt compounding

Talc was modified with methyl methacrylate (MMA) or butyl acrylate (BA) via in situ polymerization. The talc/isotactic polypropylene (PP) composites with nano-sized intercalated structure were formed by melt compounding of PP with the modified talc. The results showed that the talc layers were partially delaminated, aligned along the flow direction, and uniformly dispersed in the PP matrix. The thickness of the PMMA-modified talc layers in the PP matrix was in the range 80-240 nm, while the PBA-modified talc was even thinner. PMMA or PBA macromolecules attached on the surface of talc layers hindered the crystallization of the PP component. Moreover, the aligned pristine talc layers promoted the orientation of the PP crystals. However, the extent of PP crystal orientation decreased in the presence of PMMA or PBA-modified talc.     

The effect of synthesis procedure on the structure and properties of palladium/polycarbonate nanocomposites

In this paper, we compare two procedures for the synthesis of palladium (Pd)/polycarbonate (PC) nanocomposites as well as their morphological, optical, thermal and electrical properties. Pd nanoclusters were produced by the reduction of palladium chloride using a variation of Brust's method. Discrete Pd nanoclusters of ∼15 nm size were formed in the absence of PC in the reaction mixture (ex situ method) while agglomeration of Pd nanoclusters was noticed in the presence of PC in the reaction mixture (in situ method). Fourier transform infrared spectroscopy (FTIR) suggests nanoparticle-polymer interactions and polymer conformational changes in the in situ nanocomposite films. Even after having the same Pd content, the ex situ nanocomposites films were found to transmit more light than the in situ nanocomposites. The glass transition temperature (T_g), decreased by ∼16 °C for both the ex situ and in situ samples. Thermogravimetric analysis (TGA) indicated that the presence of Pd nanoclusters significantly improved the thermal stability of the nanocomposites, as evidenced by the enhanced onset of degradation by ∼20 °C and ∼40 °C for the in situ and ex situ nanocomposites, respectively. The electrical conductivity measurement shows a dramatic difference between these nanocomposites with a significantly higher value for the in situ nanocomposite (resistivity = 2.1 × 10⁵ Ωm) compared to the ex situ nanocomposite (resistivity = 7.2 × 10¹³ Ωm).     

Temperature dependence of surface composition and morphology in polymer blend film

Thin films of poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN) blend can phase separate upon heating to above its critical temperature. Temperature dependence of the surface composition and morphology in the blend thin film upon thermal treatment was studied using in situ X-ray photoelectron spectroscopy (XPS) and in situ atomic force microscopy (AFM). It was found that in addition to phase separation, the blend component preferentially diffused to and aggregated at the surface of the blend film, leading to the variation of surface composition with temperature. At 185 °C, above the critical temperature, the amounts of PMMA and SAN phases were comparable. At lower temperatures PMMA migrated to the surface, leading to a much higher PMMA surface content than in the bulk. The migration and preferential segregation of a blend component in thin films demonstrated here are responsible for the great difference between in situ and ex situ experimental (not real quenching or annealing) results of polymer blend films, and help explain the slow kinetics of surface phase separation at early stage for blend thin films reported in literature. This is significant for the control of surface properties of polymer materials.     

Electroreduction of oxygen on glassy carbon electrodes modified with in situ generated anthraquinone diazonium cations

The electrochemical reduction of oxygen on glassy carbon (GC) electrodes modified with in situ generated diazonium cations of anthraquinone (AQ) has been studied using the rotating disk electrode (RDE) technique. The electrografting of the GC electrodes was carried out in two different media: in acetonitrile and in an aqueous acidic solution (0.5 M HCl). 1- and 2-Aminoanthraquinone were used as starting compounds for the formation of the corresponding diazonium derivatives. The anthraquinone diazonium cations were generated by reaction of the aminoanthraquinones with tert-butyl nitrite and sodium nitrite in acetonitrile and in 0.5 M HCl, respectively. For comparison purposes, the previously synthesised and crystallised diazonium tetrafluoroborates of anthraquinone were used for the GC surface modification. Cyclic voltammetry was employed to determine the surface concentration of AQ in O₂ free 0.1 M KOH. The electrocatalytic behaviour towards O₂ reduction was similar for all the AQ-modified electrodes studied. The kinetic parameters of oxygen reduction were determined using a surface redox catalytic cycle model. The rate constant of the reaction between the semiquinone radical anion of AQ and molecular oxygen was virtually independent of the point of attachment of the quinone to the electrode surface.     

In situ generation of diazonium cations in organic electrolyte for electrochemical modification of electrode surface

The modification of glassy carbon electrode was achieved by electrochemical reduction of in situ generated diazonium cations in acetonitrile. The in situ generation of 4-nitrophenyl diazonium cations in acetonitrile was investigated by spectroscopic methods. UV-visible spectroscopy revealed slow kinetics for the reaction of 4-nitroaniline with tert-butylnitrite in acetonitrile to form the corresponding diazonium cation. As a result, a coupling reaction, which implies a consumption of the amine and loss of the already formed diazonium cations, was evidenced by ¹H NMR spectroscopy. This spectroscopic study allowed the optimization of the in situ diazonium cations generation prior to the modification step. The electrochemical modification of the carbon electrodes with 4-nitrophenyl, 4-bromophenyl and anthraquinone groups was characterized by cyclic voltammetry and the resulting grafted layer were characterized by electrochemical techniques. The cyclic voltammetric behaviour during the electrochemical grafting was very similar to the one observed for an isolated diazonium salt dissolved in acetonitrile. In the case of the anthraquinone-modified electrode, the use of acetonitrile, into which the corresponding amine is soluble but not in aqueous media, allowed for its grafting by the in situ approach. The barrier properties of these grafted layers are similar to those obtained from isolated diazonium salts. Finally, the chemical composition of the grafted layers was determined by X-ray photoelectron spectroscopy and surface coverage in the range 5-7 × 10⁻¹⁰ mol cm⁻² was estimated for films grown in our experimental conditions.     

Controllable electrochemical synthesis of La/ZnO hierarchical nanostructures and their optical and magnetic properties

Here we presented a facile electrochemical deposition route for the controllable preparation of La³⁺/ZnO hierarchical nanostructures, such as flower-like nanostructures consisted of nanorods, flower bundles, and hexagonal nanorods with nests at the top. These prepared La³⁺/ZnO deposits were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis spectrophotometer, and photoluminescence spectroscopy. The formation process of La³⁺-doped ZnO and the growth mechanisms of La³⁺/ZnO hierarchical nanostructures were discussed. The UV and PL spectra measurements show that the surface morphologies of La³⁺/ZnO deposits have an obvious effect on their optical properties and we can easily adjust their optical properties as well as La³⁺/ZnO nanostructures by changing electrochemical deposition parameters. In addition, the magnetic properties of La³⁺/ZnO deposits were also investigated.     

Preparation of electrospun nanofibers of carbon nanotube/polycaprolactone nanocomposite

Multiwalled carbon nanotube/polycaprolactone nanocomposites (MWNT/PCL) were prepared by in situ polymerization, whereby functionalized MWNTs (F-MWNTs) and unfunctionalized MWNTs (P-MWNTs) were used as reinforcing materials. The F-MWNTs were functionalized by Friedel-Crafts acylation, which introduced the aromatic amine (COC₆H₄-NH₂) groups on the side wall. The F-MWNTs were chemically bonded with the PCL chains in the F-MWNT/PCL, as indicated by the appearance of the amide II group in the FT-IR spectrum. The TGA thermograms showed that the F-MWNT/PCL had better thermal stability than PCL and P-MWNT/PCL. The PCL and the nanocomposite nanofibers were prepared by an electrospinning technique. The nanocomposites that contain more than 2 wt% of MWNTs were not able to be electrospun. The bead of the F-MWNT/PCL nanofiber was formed less than that of the P-MWNT/PCL. The nanocomposite nanofibers showed a relatively broader diameter than the pure PCL nanofibers. The MWNTs were embedded within the nanofibers and were well oriented along the axes of the electrospun nanofibers, as confirmed by transmission electron microscopy.     

Gelation and degradation characteristics of in situ photo-crosslinked poly(l-lactide-co-ethylene oxide-co-fumarate) hydrogels

The objective of this work was to determine the gelation kinetics, extent of swelling, sol fraction, and degradation kinetics of photo-crosslinked poly(l-lactide-co-ethylene oxide-co-fumarate) (PLEOF) hydrogels, with N-vinyl-2-pyrrolidone (NVP) crosslinker, as a function of composition as well as the time and intensity of UV radiation. The gelation process was monitored by in situ rheometry. The crosslinking was shown to be facilitated by increasing NVP concentration up to a certain value above which the hydrogel shear modulus did not increase with additional amount of NVP. Increasing the hydrophobicity of PLEOF macromer resulted in a decrease in the hydrogel swelling ratio and increase in sol fraction which was due to a reduction in the apparent reactivity of the PLEOF fumarate units. The degradation characteristics of PLEOF hydrogels depended on the ratio of PLA to PEG with PLEOF 30/70 (30% lactide) having the highest degradation rate.     

Improvement of mechanical properties for PP/PS blends by in situ compatibilization

The effect of the in situ compatibilization on the mechanical properties of PP/PS blends was investigated. The application of Friedel-Crafts alkylation reaction to the PP/PS-blend compatibilization was assessed. Styrene/AlCl₃ was used as catalyst system. The graft copolymer (PP-g-PS) formed at the interphase showed relatively high emulsifying strength. Scission reactions, occurring in parallel with grafting, were verified for PP and PS at high catalyst concentration, but no crosslinking reactions were detected. Tensile tests were performed on dog-bone specimens of the blends. Both elongation at break and toughness increased with catalyst concentration. At 0.7% AlCl₃, a maximum was reached, which amounted to five times the value of the property for the uncompatibilized blend. At higher catalyst concentrations these properties decreased along with the PP molecular weight due to chain-scission reactions. On the other hand, the tensile strength did not change with the catalyst concentration. The in situ compatibilized blends showed considerable improvement in mechanical properties, but were adversely affected by chain scissions at high catalyst contents.     

A correlation of electrochemical and spectroelectrochemical properties of poly(o-toluidine)

A comparative discussion of the electrochemical and spectroelectrochemical properties of poly(o-toluidine) POT, a methyl substituted derivative of polyaniline, PANI, is presented. POT exists in various oxidation states and shows an insulator to conductor transition when doped by electrooxidation. The transformation of the polymer film from its non-conducting leucoemeraldine to its conducting emeraldine state and further on to its again non-conducting pernigraniline form was observed with different techniques including cyclic voltammetry, in situ conductivity measurements and in situ UV-vis and Raman spectroelectrochemical methods. Results reveal that POT shows a good correlation between its electrochemical and spectroelectrochemical properties in its different oxidation states.     

Fabrication of tin-filled carbon nanofibres by microwave plasma vapour deposition and their in situ heating observation by environmental transmission electron microscopy

Sn-filled carbon nanofibres (CNFs) are fabricated by microwave plasma chemical deposition. Scanning electron microscopy observations revealed the existence of a Sn island under the CNFs. The structure of the CNFs is investigated, and the behaviour of Sn in the internal space of CNFs is revealed by performing in situ heating observations by environmental transmission electron microscopy (ETEM). ETEM observations reveal that they have low-crystallized carbon wall and Sn occupies not only the CNF’s internal space but also its carbon wall. The Sn inside the CNF is completely covered by the carbon wall. Further, the in situ heating observations reveal that Sn within the internal space and the carbon wall of the CNFs diffused to the outside during heating. Moreover, it is found that higher membered carbon rings and defects in the graphite layer act as diffusion routes between disordered carbon layers.     

Microstructure and optical properties of Ag/ITO/Ag multilayer films

Transflective and highly conductive Ag/ITO/Ag multilayer films were prepared by magnetron sputtering on glass substrates. The microstructure and optical properties of Ag/ITO/Ag multilayer films were systematically investigated by X-ray diffraction, scanning electron microscopy, and ultraviolet-visible spectroscopy. The optical properties of the multilayer films were significantly influenced by the thickness of the Ag surface layer from 3.0 to 12.6 nm. The multilayer film of Ag9.3nm/ITO142nm/Ag9.3nm shows the best comprehensive property. It could satisfy the requirement for transflective LCD.     

Ag/Bi2WO6 plasmonic composites with enhanced visible photocatalytic activity

Three-dimensional flower-like Bi₂WO₆ microspheres with the diameter of about 4 μm were prepared by a facile hydrothermal method using bismuth nitrate pentahydrate and sodium tungstate dihydrate as raw materials. A novel Ag-modified Bi₂WO₆ was synthesized through a simple and practical photoreduction process. The UV–vis diffuse reflectance spectra indicate that the Ag/Bi₂WO₆ samples have a significantly enhanced optical absorption in the visible light region than that of pure Bi₂WO₆ microspheres due to the surface plasmon resonance (SPR) of Ag nanoparticles on the surface of pure Bi₂WO₆. The photocatalytic activities of the as-prepared samples were evaluated by the decolorization of rhodamine B under simulated sun-light irradiation. The results reveal that the photocatalytic activities of the Ag/Bi₂WO₆ samples increase first and then decrease with increasing amount of loading Ag and the 1.0 wt% Ag-loaded Bi₂WO₆ sample exhibits the best photocatalytic activity compared with the other samples. The enhanced photocatalytic activity could be attributed to the synergistic effect of the strong SPR and the effective separation of photogenerated electrons and holes caused by Ag nanoparticles.     

核壳结构微纳橡胶粒子的可控合成及对PPO/PS共混体系的增韧

采用乳液聚合方法在粒径为100 nm的聚丁二烯(PB)胶乳上接枝聚合苯乙烯(St),合成了核壳比为70/30(PB/PS)的PB-g-PS接枝共聚物,将其与聚苯醚(PPO)、聚苯乙烯(PS)树脂熔融共混,制备出一系列橡胶含量、基体组成不同的PPO/PS/PB-g-PS共混物,并考察了共混物的相容性、力学性能及形态结构。结果发现:PPO与PS为完全相容体系,且PB-g-PS在PPO/PS基体中的均匀分散程度随体系中PPO引入量的增大而明显改善,共混物的冲击强度及屈服强度也随之逐渐增大,进而促使共混物发生脆-韧转变所需的橡胶含量逐渐降低;随着共混体系中橡胶含量的增加,共混物的冲击强度逐渐提高,而屈服强度却逐渐降低,共混物的韧性断裂特征越发显著。     

Short-wavelength light beam in situ monitoring growth of InGaN/GaN green LEDs by MOCVD

In this paper, five-period InGaN/GaN multiple quantum well green light-emitting diodes (LEDs) were grown by metal organic chemical vapor deposition with 405-nm light beam in situ monitoring system. Based on the signal of 405-nm in situ monitoring system, the related information of growth rate, indium composition and interfacial quality of each InGaN/GaN QW were obtained, and thus, the growth conditions and structural parameters were optimized to grow high-quality InGaN/GaN green LED structure. Finally, a green LED with a wavelength of 509 nm was fabricated under the optimal parameters, which was also proved by ex situ characterization such as high-resolution X-ray diffraction, photoluminescence, and electroluminescence. The results demonstrated that short-wavelength in situ monitoring system was a quick and non-destroyed tool to provide the growth information on InGaN/GaN, which would accelerate the research and development of GaN-based green LEDs.     

Investigation of the peel behavior of polyethylene/polybutene-1 peel films using in situ peel tests with environmental scanning electron microscopy

The micro-deformation processes of sealed low-density polyethylene/isotactic polybutene-1 (PE-LD/iPB-1) films with different contents of iPB-1 up to 20 m.-% (mass-percentage) were investigated in this study.The peel process was analyzed in detail using in situ peel test measurements with environmental scanning electron microscopy (ESEM). This method enables the direct correlation of recorded force-elongation data with observed structural phenomena. Thus, important parameters, e.g., the peel initiation value, could be determined directly from in situ measurements. The dependence of the peel properties on the iPB-1 content was analyzed and the correlation between micro-structure and performance of the peel process was clarified.Furthermore, the structural reason behind the dependence of the peel properties on the peel angle was identified. The crack propagation types interlaminar and translaminar were analyzed in detail with the ESEM. The translaminar crack propagation was further characterized using a tilted microscope stage with a mounted tensile tester.The direct contact of the electron beam with the non-conductive sample surface can cause beam damage. The beam damage, indicated by the absorbancy band at 965 cm⁻¹ in the infrared spectrum, was investigated in dependence on the total irradiation time.