Conducting polymer nanoparticles synthesized in an ionic liquid by chemical polymerisation

Ionic liquids are ideal media for the synthesis and application of conducting polymers as they can exhibit excellent oxidative and reductive stability, allowing access to potentials outside the smaller electrochemical window of molecular solvent/electrolyte systems. Here we report the first use of an ionic liquid for the chemical synthesis of poly(pyrrole), poly(thiophene) and poly(terthiophene) using a variety of oxidants. The polymers have been analysed by UV–vis spectroscopy, cyclic voltammetry and dynamic light scattering, which shows the particles to be <500 nm diameter. TEM analysis shows the individual poly(thiophene) particles to be <100 nm.     

Optical and electrical characterizations of ZnS nanoparticles embedded in conducting polymer

ZnS nanoparticles of average size (5 nm) have been prepared using thioglycerol. Inorganic–organic hybrid nanocomposites have been synthesized by dispersing nanosized ZnS in the conducting polyaniline matrix. The samples have been characterized by X-ray diffraction (XRD), transmission electron microscope (TEM) and scanning electron microscope (SEM) and UV–vis spectrophotometer. The wavelength of optical absorption peak of ZnS nanoparticle increases from 270 to 330 nm with the decrease of polyaniline concentration. Studies on direct current (DC) electrical conductivity as a function of temperature suggest that three-dimensional Mott’s hopping process occurs in ZnS–polyaniline nanocomposites. The correlated barrier hopping is confirmed from temperature dependent alternating current (AC) conductivity. The incorporation of ZnS nanoparticles enhances the barrier height.     

Conducting polymer functionalized multi-walled carbon nanotubes with noble metal nanoparticles: Synthesis,morphological characteristics and electrical properties

We report the synthesis of conducting polyaniline-functionalized multi-walled carbon nanotubes (MWCNTs-f-PANI) containing noble metal (Au and Ag) nanoparticles composites (MWCNTs-f-PANI-Au or Ag-NC). MWCNTs-f-PANI was initially synthesized by functionalizing acyl chloride terminated carbon nanotubes (MWCNTs-COCl) with 2,5-diaminobenzenesulphonic acid (DABSA) via amide bond formation, followed by surface initiated in situ chemical oxidative graft polymerization of aniline in the presence of the ammonium persulphate (APS) as an oxidizing agent. MWCNTs-f-PANI was then dispersed into an aqueous Au or Ag metal salt solution followed by the addition of sodium citrate, which acted as a reducing agent. The resulting composite contained a high level of well dispersed Au or Ag nanoparticles (MWCNTs-f-PANI/Au-NC or MWCNTs-f-PANI-Ag-NC). Morphological and structural characteristics, as well as electrical conducting properties of the hybrid nanocomposites were characterized using various techniques including high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UV–visible spectroscopy (UV–vis) and four-probe measurements. FT-IR spectra confirmed that PANI was covalently bonded to MWCNTs. TEM images revealed the presence of Au or Ag nanoparticles finely dispersed in the composites with a size of <15 nm. XRD analysis revealed the presence of strong interactions between the metal nanoparticles and MWCNTs-f-PANI, where the metal particles were present in a phase-pure crystalline state with face centered cubic (fcc) structure. The room temperature electrical conductivity of the MWNCTs-f-PANI/Au or Ag composites was 4.8–5.0 S/cm, respectively, which was much higher than that of CNTs-f-PANI (0.18 S/cm) or pure PANI (2.5 × 10^?3 S/cm). A plausible mechanism for the formation of nanocomposites is presented. We expect that the new synthesis strategy reported here will be applicable for the synthesis of other hybrid CNTs–polymer/metal nanocomposites with diverse functionalities. This new type of hybrid nanocomposite material may have numerous applications in nanotechnology, gas sensing, and catalysis.     

Conducting polymer composites of polypyrrole and polyindene

Polypyrrole-polyindene composites were prepared via electrochemical methods. Two different approaches were utilized. In the first, the electro-initiated polymerization of indene on a platinum electrode was achieved at 2.0 V versus Ag/Ag⁺ in acetonitrile. Then the polyindene-coated electrode was used for the electrochemical polymerization of pyrrole at 1.0 V versus Ag/Ag⁺. In the second case, electrochemical coating of platinum electrode with polypyrrole at 1.0 V versus Ag/Ag⁺ was carried out and indene was polymerized on the conducting polymer at 2.0 V versus Ag/ Ag⁺ in acetonitrile medium. The characterizations of these composites were done by FT-IR, scanning electron microscopy (SEM) and thermal gravimetric analysis (TGA). Electrical conductivities were evaluated by two-probe and four-probe methods.     

二氧化钛包覆微细金刚石的制备及表征

以聚乙烯吡咯烷酮（PVP）为偶联剂,钛酸四丁酯（TBOT）为TiO₂前驱体,氨水为催化剂,通过St?ber法制备核-壳结构的二氧化钛包覆微细金刚石（UFD@TiO₂）,研究溶液pH值、氨水及去离子水的加入量对UFD@TiO₂的影响。采用XRD、SEM及DSC-TG等手段对UFD@TiO₂进行表征,利用三点弯曲法测定添加UFD或UFD@TiO₂的陶瓷结合剂试样的抗折强度,通过SEM观察陶瓷结合剂试样断口的微观形貌。实验结果表明:当溶液pH值约为8,氨水体积分数为0.8%,去离子水体积分数为0.8%时,TBOT水解生成的TiO₂易在金刚石表面异质形核,可获得致密均匀的TiO₂膜层;UFD@TiO₂的起始氧化温度为650℃,比UFD的起始氧化温度583℃提高了67℃;UFD@TiO₂-陶瓷结合剂试样的抗折强度比UFD-陶瓷结合剂试样的抗折强度提高了20.9%。      

Semiconducting properties of thin films with embedded nanoparticles

We demonstrate here the possibility of designing semiconducting thin films with controlled electrochemical properties. The thin films are composed of (i) an insulating binder and (ii) a semiconductor nanopowder which enables the fine tuning of the semiconducting properties of the layers. Thus, p- and n-type silicon particles (obtained from a top-down technique), or metal-oxide ZnO, SnO2 and NiO nanoparticles (synthesized using a bottom-up protocol) are successfully integrated into spin-coated or screen-printed thin films and used as semiconducting materials. The flat band potential (Vfb) of the films is then easily tuned from 0 V to ?1.138 V.     

Developing hybrid polymer composites with embedded shape-memory alloy wires

Adaptive composites integrate actuating and sensing materials into a structural material (e.g., the integration of thin shapememory alloy [SMA] wires can function as actuating elements into fiber-reinforced polymer composites). SMA composites can open new perspectives on the development of engineering structures and devices with adaptive shape, stiffness, damping, and other properties. Materials design involving the constitutive modeling of SMA composite thermomechanical responses is a key topic in the development of the adaptive composites. As such, example simulation results obtained using a recently developed composite model are presented. For more information, contact P. Šittner, Institute of Physics, Academy of Sciences of the Czech Republic, Na Slovance 2, Prague 8, 182 21, Czech Republic; 4202 66052657; fax 4202 821227; e-mail sittner@fzu.cz.     

Formation of nanocomposites of platinum with nanotubular titanium dioxide

Metal oxide nanocomposites of platinized titania nanotube arrays (Pt-TNT) have been formed via electrochemical anodization-precipitation. Initially, the vertically aligned amorphous TiO₂ nanotube arrays (TNTs) were formed in accordance with potentiostatic electrochemical anodization of titanium with the use of 1 M H₂SO₄ + 0.3% HF electrolyte. Then, using the potentiostatic and pulse electrodeposition, precipitates of Pt on TNT were formed from 0.04 M solution of chloroplatinic acid (CPA). It has been shown with the use of SEM and Raman spectroscopy that, in order to prepare functional metal oxide Pt-TNT nanocomposites, pulse electrodeposition and subsequent annealing at 400°C are preferable, because they lead to TNTs that are homogeneously distributed along the surface and in bulk (with anatase structure) for platinized layers and conglomerates.     

超声波辐照对水合二氧化钛晶体结构和煅烧二氧化钛粒度的影响

介绍在硫酸氧钛水解过程初期引入超声波辐照,采用透射电子显微镜、X射线衍射仪和激光粒度测试技术对水解产物-水合二氧化钛及其在650℃的煅烧产物二氧化钛进行表征.结果表明:超声波辐照作用不仅促进了硫酸氧钛的水解过程而且使水解产物的晶格参数发生改变,特别是锐钛型四方晶胞的c轴从0.951 4 nm缩短到0.918 1 nm,同时,晶胞体积缩小,晶粒度减小.在煅烧以后,c轴伸长明显使原有的晶格畸变消失.与未受超声波辐照的水解产物不同,受过超声波作用的水合二氧化钛在煅烧之后其平均颗粒度减小的趋势达10%,从水合二氧化钛的0.712μm减小为0.639 μm.     

Magnetic properties of polymer matrix composites with embedded ferrite particles

Polymeric composite materials offer advantages for many applications because of a combination of properties, which includes high specific mechanical strength and elastic modulus and corrosion resistance. However, the non-magnetic nature of these materials impedes the use of non-destructive evaluation (NDE) techniques using magnetic sensors. In this work, glass fiber-reinforced epoxy magnetic composites were produced with the addition of 10 wt% of cobalt or barium ferrite particles. Circular plates with notches of 1, 5 and 10 mm in diameter were produced and characterized using magnetic flux leakage (MFL) technique. The effect of particle size on the magnetic properties of the composites was also investigated for the barium ferrite. The results indicated a good correlation between the measured magnetic signals and the presence of notches. Smaller average particle sizes hindered the identification of the smallest notch. However, it resulted in better signal-to-noise ratio for the intermediate and larger size notches.     

Hollow structure snap-fit design embedded with shape memory polymer sheet

Active disassembly uses innovative components within the product design to promote self disassembly as natural decomposition. The use of smart materials, more specifically shape memory alloys and shape memory polymers, has been extensively documented. However, the difficulty of reusing those components with smart materials is becoming a problem in disassembly processes during regular product repair and maintenance. In order to improve the reusability of the components, the authors design a hollow structure snap-fit embedded with shape memory polymer sheets. Theoretical simulation and prototype testing are presented in this paper to demonstrate the advantages of the new snap-fit design.     

Pressure leaching of converter vanadium slag with waste titanium dioxide

The process of pressure leaching the converter vanadium slag with waste titanium dioxide without roasting was studied. Mineralogy analysis indicates that the converter vanadium slag contains mainly three mineral phases: magnetite, titanium magnetite, and silicate phase. Vanadium is in combination with iron, titanium, manganese, aluminum, and silicon. The impacts of leaching temperature, leaching time, stirring speed, liquid-to-solid ratio, and initial leaching agent concentration were investigated on the waste titanium dioxide leaching process. The results indicate that under the optimal conditions, the vanadium and the iron leaching rates are 96.85 % and 93.50 %, respectively, and the content of titanium is 12.6 % in the residue. The main mineral phases for the residues under the optimal operation conditions are quartz, ilmenite, anatase, and silicate phase, and the residues can be reused as the extraction of titanium raw materials for titanium dioxide production technology by the sulfate method.     

Polypyrrole nanoparticles and dye absorption properties

Polypyrrole (PPy) nanoparticles were prepared by using microemulsion polymerization processes at 3 °C. Particle characterization was performed by using FTIR, elementary analysis, UV–vis spectra and scanning electron microscope (SEM). The size of the nanoparticles varied from about 50 to 100 to 100 to 200 nm with the change in concentration of surfactant from 0.8 to 0.44 M. Polypyrrole nanoparticles were dedoped by a 10% NaOH solution, followed by a redoping process using a nuclear fast red kernechtrot dye, which has a sulfonate group. Dedoping changed the optical absorption properties of the nanoparticles.     

Self-assembled polyaniline nanotubes and nanoribbons/titanium dioxide nanocomposites

Self-assembled polyaniline (PANI) nanotubes, accompanied with nanoribbons, were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous medium, in the presence of colloidal titanium dioxide (TiO₂) nanoparticles of 4.5 nm size, without added acid. The morphology, structure, and physicochemical properties of the PANI/TiO₂ nanocomposites, prepared at various initial aniline/TiO₂ mole ratios, were studied by scanning (SEM) and transmission (TEM) electron microscopies, FTIR, Raman and inductively coupled plasma optical emission (ICP-OES) spectroscopies, elemental analysis, X-ray powder diffraction (XRPD), conductivity measurements, and thermogravimetric analysis (TGA). The electrical conductivity of PANI/TiO₂ nanocomposites increases in the range 3.8 × 10^?4 to 1.1 × 10^?3 S cm^?1 by increasing aniline/TiO₂ mole ratio from 1 to 10. The morphology of PANI/TiO₂ nanocomposites significantly depends on the initial aniline/TiO₂ mole ratio. In the morphology of the nanocomposite synthesized using aniline/TiO₂ mole ratio 10, nanotubes accompanied with nanosheets prevail. The nanocomposite synthesized at aniline/TiO₂ mole ratio 5 consists of the network of nanotubes (an outer diameter 30–40 nm, an inner diameter 4–7 nm) and nanorods (diameter 50–90 nm), accompanied with nanoribbons (a thickness, width, and length in the range of 50–70 nm, 160–350 nm, and ～1–3 μm, respectively). The PANI/TiO₂ nanocomposite synthesized at aniline/TiO₂ mole ratio 2 contains polyhedral submicrometre particles accompanied with nanotubes, while the nanocomposite prepared at aniline/TiO₂ mole ratio 1 consists of agglomerated nanofibers, submicrometre and nanoparticles. The presence of emeraldine salt form of PANI, linear and branched PANI chains, and phenazine units in PANI/TiO₂ nanocomposites was proved by FTIR and Raman spectroscopies. The improved thermal stability of PANI matrix in all PANI/TiO₂ nanocomposites was observed.     

综合利用钛铁矿制备二氧化钛、钛酸锂和磷酸铁锂

以钛铁矿为原料,经机械活化-盐酸浸出得到水解钛渣和富铁浸出液;用H2O2将水解钛渣中的Ti配位溶出,得到配位浸出液,并以其为反应物制备纳米级片状的过氧钛化合物;该过氧钛化合物经洗涤、煅烧制备得到纳米级片状的TiO2,其纯度高达99.31%(质量分数)。将过氧钛化合物与Li2CO3混合,球磨后煅烧合成性能优良的锂离子电池负极材料Li4Ti5O12。以富铁浸出液为原料,经选择性沉淀制备含少量Al和Ti的FePO4.xH2O,并以其为前驱体制备了Al-Ti掺杂的LiFePO4。该LiFePO4在1C和2C倍率下的首次放电比容量分别达151.3和140.1(mA.h)/g,循环100次之后容量无衰减。该方法也可用于钛白粉副产品硫酸亚铁的回收利用,制备性能优异的LiFePO4。     

Electronic structure and momentum density distribution of titanium dioxide

LCAO calculations have been performed for the electronic and structural properties of the rutile TiO₂ under the periodic HF and DFT schemes. The methods have been applied to study Compton profiles and the structure factors. The experimental Compton profile based on Am²⁴¹ Compton spectrometer for polycrystalline TiO₂ has been compared with the calculations. The calculated Compton profile from HF-LCAO has been found to be in good agreement with the measurement compared to the ionic model and DFT-LCAO method. The published experimental X-ray structure factors support the FLAPW method more than the periodic HF-LCAO method. Signatures of charge transfer on compound formation are observed. Partial ionic as well as covalent character of bonding is observed on the basis of structure factor as well as momentum density analysis. The present work enables to examine the DFT and HF approaches in terms of structure factor and the Compton profile studies.     

复合钛白的制备技术现状与趋势

综述了近年来国内外制备复合钛白的简单机械混合法、强力机械研磨法、粒一粒包覆改性法、TiCl4水解法、TiOSO4水解法、氟化法、微波合成法和碳酸化法等八种方法的原理及工艺技术,评价了其工艺流程、产品成本、产业化前景和推广价值．对其发展进行了展望。