Synthesis, characterization and thermal analysis of polyaniline/ZrO2 composites

Conducting polyaniline-zirconium dioxide (PANI/ZrO₂) composites were synthesized by ‘in situ’ deposition technique in the presence of hydrochloric acid (HCl) as dopant by adding the fine grade powder (average particle size of approximately 20 nm) of ZrO₂ into the polymerization reaction mixture of aniline. The composites obtained were characterized by infrared spectra (IR) and X-ray diffraction (XRD) and thermogravimetric analysis (TGA). TG curves and DTG curves of the composites suggest that the thermal degradation process of PANI/ZrO₂ composites proceeds in two-steps and the composites are more thermally stable than that of the pure PANI. The improvement in the thermal stability for the composites is attributed to the interaction between PANI and ZrO₂, which restricts the thermal motion of PANI chains and shields the degradation of PANI in the composites.     

Synthesis and electrical–magnetic properties of polyaniline composites

Composites of polyaniline (PANI) with both conducting and ferromagnetic feature were synthesized by an improved method proposed by the authors. The electrical and ferromagnetic properties of the composites were measured as a function of the concentration of KOH solution used during polymerization. The conductivity of the composites at room temperature decreases with the increase of the concentration of KOH; the maximum conductivity of 8.0 × 10⁻¹ S/cm can be obtained when 25 wt % of concentration of KOH was used. For a high concentration of KOH, ferromagnetic properties of the composites including a high saturated magnetization (∼ 10.0 emu/g) depending on the concentration of KOH solution and a lower coercive force (H_c ≈ 0) independent of the concentration of KOH solution were observed. It has been demonstrated that magnetic particles (Fe₃O₄) with nanometer size in the composites can be attributed to the ferromagnetic properties of the composites observed. For a lower concentration of KOH solution, on the other hand, the magnetic properties of the composites can be decomposed to Curie susceptibility χ_c depending on the temperature and Pauli susceptibility χ_P independent of the temperature. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2799–2805, 1998     

Thermal stability and electrochemical performance of Polyaniline/Pr6O11 composites

In order to describe the influence of Pr₆O₁₁ on thermal and electrochemical performance of polyaniline (PANI), PANI/Pr₆O₁₁ composites were synthesized by in situ polymerization in the presence of sulfosalicylic acid (as dopant). The composites obtained was characterized by scanning electron microscope, Fourier transform infrared spectra, and X‐ray diffraction. The thermal stability of the composites was investigated by thermogravimetry and derivative thermogravimetry. Finally, the comparative analysis on the electrochemical properties of PANI/Pr₆O₁₁ composites electrodes, such as cyclic voltammetry, electrochemical impedance spectroscopy, and constant current charge–discharge test, was conducted under similar conditions. Scanning electron microscope, infrared, and X‐ray diffraction results show that interaction exists between PANI and Pr₆O₁₁, and the composites are more crystalline than pure PANI. Thermogravimetry and derivative thermogravimetry analyses indicate that PANI/Pr₆O₁₁ composites and pure PANI have similar thermal stability. Moreover, the studies regarded to capacitive properties show that the electrochemical performance of the composites is improved greatly when Pr₆O₁₁ is added in small amount. However, with increasing the amount of Pr₆O₁₁, the electrochemical performance of the composites become worse, which indicates a large amount of Pr₆O₁₁ has a negative effect on the capacitance. These results suggest that PANI is still in the conductive form after inserting the Pr₆O₁₁, and the capacitance performance of PANI can be improved only by a low percentage of Pr₆O₁₁. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis,characterization, and thermal properties of piezoelectric polyimides

Three amorphous piezoelectric polyimides have been synthesized and characterized to analyze their utility for high‐temperature applications. The studied polyimides have been prepared from 4,4′‐oxydiphthalic anhydride and the diamines 2,4‐di(3‐aminophenoxy)benzonitrile (poly2‐4), 2,6‐bis(3‐aminophenoxy)benzonitrile (poly2‐6), and 1,3‐bis‐2‐cyano‐3‐(3‐aminophenoxy)phenoxybenzene (poly2CN). These polyimides differ in the position of the dipolar groups ? CN in the aromatic ring (poly2‐4 and poly2‐6) and in the number of these groups in the repetitive unit (poly2‐6 and poly2CN). The imidization degree has been studied by Fourier transform infrared (FTIR) and thermogravimetry‐mass spectrometry (TG‐MS) and thermal properties by differential scanning calorimetry (DSC) and thermogravimetry (TG). The piezoelectric behavior has been analyzed from remnant polarization measurements. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 722–730, 2009     

Spectral,thermal and magnetic studies of 2-chloro-5-nitrobenzoates of rare earth elements(iii)

The conditions of the formation of yttrium(III) and lanthanide(III) 2-chloro-5-nitrobenzoates were studied and their quantitative composition and solubilities in water at 298 K were determined. The compounds are dihydrates and their solubilities are of the order of 10^-3 mol dm^-3. The FTIR, FIR and X-ray spectra for the complexes were recorded. All complexes are crystalline compounds. Their thermal decomposition was studied only in the range 293-523 K since on heating above 523 K the complexes decompose explosively. Hydrated 2-chloro-5-nitrobenzoates of rare earth elements lose two crystallization water molecules in one step. The enthalpy of dehydration process was established and the magnetic moments of the complexes were determined in the range 77-300 K. The compounds obey the Curie-Weiss law. The 4f electrons do not participate in the formation of the Ln-O bonds. This revised version was published online in August 2006 with corrections to the Cover Date.     

L-精氨酸铜配合物的磁性、铁电与热重研究

为了合成和研究具有磁性和铁电双重性能的配合物,本文选用L-精氨酸(L-Arg)配体与硝酸铜制备了一个配合物,其组成为[Cu(L-Arg)2]2+(NO3-)2·3H2O(1),单晶X射线衍射分析表明,该配合物的晶体结构属于单斜晶系手性空间群C2。磁性和铁电性能测试表明该配合物具有弱的铁磁行为和铁电双重性能。热分析显示该配合物在77-150℃失去自由水,从243℃开始分解。     

氧桥联稀土钆双核配合物磁学性质的密度泛函理论研究

采用密度泛函理论结合对称性破损态方法,选用氧桥联稀土钆双核配合物为研究对象,通过与实验值比较,探讨了不同泛函与基组对计算磁耦合常数的影响.结果表明,在B3LYP/TZV水平下(Gd为SARC-TZV),相对论效应采用DHK2方法,计算结果与实验测量值-0.022 5cm~(-1)最接近.不同体系测试结果显示,可在该水平下预测新合成稀土钆双核配合物的磁学性质.Mulliken自旋密度分析可知磁中心Gd以自旋极化为主.键级分析表明,2个磁中心之间的磁耦合作用通过桥联氧原子的超交换作用实现.分子磁轨道分析显示2个磁中心间存在较强的轨道相互作用,其磁轨道主要是由钆原子的4f_z~3,4f_z~2_x轨道和桥联氧原子的2pz轨道组成.     

Synthesis and properties of silica/polystyrene/polyaniline conductive composite particles

In this study, silica/polystyrene/polyaniline (SiO₂/PS/PANI) conductive composite particles were synthesized by four sequential reactions. The nanosized SiO₂ particles were synthesized from tetraethoxysilane (TEOS) by a sol–gel process with water as the solvent medium, followed by a surface modification with triethoxyvinylsilane; then the surface modified SiO₂ particles were used as seeds to synthesize SiO₂/PS composite particles with soapless seeded emulsion polymerization. Finally, the SiO₂/PS particles were used as seeds to synthesize the SiO₂/PS/PANI conductive composite particles. The sol–gel process of SiO₂, the effect of surface modification, and several other factors that influenced polymerization of styrene in the soapless seeded emulsion polymerization will be discussed. Either potassium persulfate (KPS) or 2,2′‐azobis(isobutyramidine) dihydrochloride (AIBA) was used as the initiator to synthesize the uniform SiO₂/PS particles successfully, and the cross‐section morphology of the SiO₂/PS particles was found to be of a core–shell structure, with SiO₂ as the core, and PS as the shell. The SiO₂/PS particles were well dispersed in many organic solvents. In the following step to synthesize SiO₂/PS/PANI conductive composite particles, sodium dodecyl sulfate (SDS) played an important role, specifically, to absorb aniline onto the surfaces of the SiO₂/PS particles to carry out the polymerization of aniline over the entire surface of the particles. The conductivity of the SiO₂/PS/PANI composite particles approached that of semiconductive materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 342–354, 2005     

Synthesis,characterization, optical,thermal and electrical properties of polybenzimidazoles

The variation of dielectric constant and dielectric loss of two novel polybenzimidazole (PBI) were studied at constant temperature with variable frequency. The polymers have shown maximum dielectric constant at low applied frequency 50 Hz at 393 K due to the space charge polarization. The AC conductivity and activation energy of polymers were arrived from dielectric constant and dielectric loss values. PBIs were synthesized by the oxidative polycondensation of benzimidazole monomers, 2-(1H-benzo [d] imidazole-2-yl)-4-bromophenol (BIBP), and 2-(1H-benzo [d] imidazole-2-yl)-6-methoxyphenol (BIMP) in an aqueous alkaline medium using NaOCl as oxidant. The monomers and polymers were characterized by various spectroscopic techniques. Fluorescence spectra of monomers and polymers showed their λ _max emission in the region of 472–479 and 463–472 nm respectively. The electrical conductivities of iodine doped polybenzimidazoles were measured by four-point probe technique and it increases with increase in iodine vapour contact time. The electrical conductivity values were correlated with the charge density on imidazole nitrogen obtained from Huckel calculation method. Both the PBI are having reasonably good thermal stability and are shown by high carbines residues of around 40% at 500°C in thermogravimetric analysis.     

Synthesis,characterization, and thermal properties of ladderlike polyepoxysiloxanes

Starting from trichlorosilanes and using 1,4‐phenylenediamine as a template, we have synthesized some ladderlike poly(glycidyl‐co‐alkyl/aryl)siloxanes (polyepoxysiloxanes or polyepoxies for short). The structures of copolymers were confirmed through IR, ¹H NMR, elemental analyses, and gel permeation chromatography. Curing behaviors of these polyepoxies in the absence and presence of a curing agent have been studied with DSC. It was shown that these epoxies could be cured without any curing agent. Copolymers having aromatic groups showed higher curing reactivity than those having alkyl groups. The experimental results also demonstrate that the curing reaction occurred solely via epoxy functionality, not via the condensation reaction of the hydroxy groups located at the end of polymer main chains. The thermal stability of the cured polymers was examined by thermogravimetric analysis. The results confirm that polyepoxies with aromatic groups had better thermal stability than those with alkyl groups. It was also found that polyepoxies cured with a diamine have a higher thermal stability than those cured in the absence of a curing agent. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2215–2222, 2001     

Synthesis,characterization, luminescence and magnetic properties of composite of polyaniline with nickel bisacetylacetonate complex

The present study involves the synthesis of polyaniline (PANI) and its composite with nickel bis(acetylacetonate) complex (Ni(acac)₂) via chemical oxidative polymerization method. PANI-Ni(acac)₂ composite was characterized by energy dispersive X-rays (EDX), fourier transformer infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM) techniques. Luminescence study was performed by UV–visible and fluorescence techniques. Relative fluorescence quantum yield of composite is a few orders of magnitude higher than pure PANI. The high fluorescence quantum yield of composite is probably due to greater chances of exciton formation and subsequent radiative decay to the ground state. Differential scanning calorimetric analysis (DSC) revealed higher thermal stability of composite than pure PANI, thereby allowing its use in devices which run at higher temperatures. On increasing the applied magnetic field, magnetic moment increases in both Ni(acac)₂ complex and PANI-Ni(acac)₂ composite, unlike to that in pure PANI. Thus, the present study holds promise for thermal purposes, luminescence properties and magnetic applications of the polyaniline composite.     

A kinetic analysis of thermal decomposition of polyaniline/ZrO<Subscript>2</Subscript> composite

Synthesis, characterization and thermal analysis of polyaniline (PANI)/ZrO₂ composite and PANI was reported in our early work. In this present, the kinetic analysis of decomposition process for these two materials was performed under non-isothermal conditions. The activation energies were calculated through Friedman and Ozawa-Flynn-Wall methods, and the possible kinetic model functions have been estimated through the multiple linear regression method. The results show that the kinetic models for the decomposition process of PANI/ZrO₂ composite and PANI are all D₃, and the corresponding function is ƒ(α)=1.5(1−α)^2/3[1−(1-α)^1/3]−1. The correlated kinetic parameters are E _a=112.7±9.2 kJ mol⁻¹, lnA=13.9 and E _a=81.8±5.6 kJ mol⁻¹, lnA=8.8 for PANI/ZrO₂ composite and PANI, respectively.     

Syntheses, structures, and magnetic properties of new rare earth coordination polymers constructed by 1,3,5-benzenetriacetic acid

Three new coordination polymers with formula [Gd(bta)(H₂O)·1.39H₂O] _n (1), [Dy(bta)(H₂O)·1.35H₂O] _n (2) and [Y(bta)(H₂O)₂·0.5H₂O] _n (3) were synthesized by using corresponding rare earth nitrates and 1,3,5-benzenetriacetic acid (H₃bta) under hydrothermal/solvothermal reaction conditions, and characterized by single-crystal X-ray diffraction. In these complexes, the carboxylate groups of bta³⁻ adopt different coordination modes, namely one carboxylate group adopts μ₂-η¹:η¹-bridging and each of the other two carboxylate groups adopts μ₂-η²:η¹-bridging coordination modes in 1 and 2, and one carboxylate group adopts a μ₂-η²:η¹-bridging coordination mode and each of the other two carboxylate groups adopts a μ₂-η¹:η¹-bridging mode for the major component and one carboxylate group adopts a μ₂-η²:η¹-bridging coordination mode, one has a μ₂-η¹:η¹-bridging mode and the third has a monodentate mode for the minor component in 3. The magnetic properties of the complexes 1 and 2 were investigated in the temperature range of 1.8–300 K.     

Mechanical and thermal properties of epoxy/silicon carbide nanofiber composites

The silicon carbide (SiC) nanofibers (0.1, 0.25, and 0.5 phr), produced by self‐propagating high‐temperature synthesis (SHS), are used to reinforce the epoxy matrix cured with an anhydride hardener. Morphological studies reveal a better dispersion of SiC nanofibers and a good level of adhesion between nanofiber and the matrix in composites with lower (0.1 and 0.25 phr) nanofiber loading. The flexural studies show that a maximum increase in flexural properties is obtained for composites with 0.25 phr SiC nanofiber. The fracture toughness of epoxy is found to increase with the incorporation of SiC nanofibers, and 0.25 phr SiC nanofiber loading shows maximum fracture toughness value. The possible fracture mechanisms that exist in epoxy/SiC nanofiber composites have been investigated in detail. Thermogravimetric analysis reveals that SiC nanofibers are effective fillers to improve the thermal stability of epoxy matrix. Copyright © 2014 John Wiley & Sons, Ltd.     

Structure and magnetic properties of homobinuclear gadolinium (III) complex of isonicotinoyl hydrazone

The crystal structure of [Gd₂(μ-L)₃(H₂O)₂]1.5(NO₃)1.5 (OH)5H₂O (where L is union of N, N-Diisonicotinoyl-2-hydroxy-5-methyl-isophthalaldehyde dihydrazone) has been determined by X-ray diffraction method. The complex crystallizes in the monoclinic system, space group P2₁/c with a=1.6654(3), b=1.6904(3), c=2.8039(6) nm, β=91.30(3), final R factor is 6.3%. The structure consists of [Gd₂(μ-L)₃(H₂O)₂]³⁺ cation, one and a half nitrate and 1.5 hydroxyl anions and five water molecules. Within dinuclear cation, Gd(III)—Gd(III) is bridged by oxygen and nitrogen atoms of the three ligands, resulting in Gd? Gd distance of 0.36353(2) nm. Gd(III) exhibits a distorted 1333 stack coordination environment. Magnetic susceptibility measurements in the temperature range 300–4 K revealed the occurrence of weak antiferromagnetic exchange interaction between two Gd(III) ions with a J value of—0.22, and g of 1.93.     

Synthesis,characterization, and electrical properties of polypyrrole/multiwalled carbon nanotube composites

Size‐controllable polypyrrole (PPy)/multiwalled carbon nanotube (MWCNT) composites have been synthesized by in situ chemical oxidation polymerization directed by various concentrations of cationic surfactant cetyltrimethylammonium bromide (CTAB). Raman spectra, FTIR, SEM, and TEM were used to characterize their structure and morphology. These results showed that the composites are core (MWCNT)–shell (PPy) tubular structures with the thickness of the PPy layer in the range of 20–40 nm, depending on the concentration of CTAB. Raman and FTIR spectra of the composites are almost identical to those of PPy alone. The electrical conductivities of these composites are 1–2 orders of magnitude higher than those of PPy without MWCNTs. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6449–6457, 2006     

Synthesis,characterization and enhanced electrical properties of CTAB-directed polyaniline nanoparticles

Inverse microemulsion system of cetyltrimethylammonium bromide (CTAB) molecules is utilized for virtually monodispersed and controlled growth of HCl polyaniline (PANI) nanoparticles at room temperature (ca. 300 K). The templated electroconductive polymer reveals lamellar crystalline structure under X-ray diffraction signifying marked sub-chain alignment of the polymerized nanoparticles. The nanostructured polymer has spherically symmetric morphology in a size range of 2.0 nm to 6.0 nm under electron microscope examination. Gel permeation chromatography gives polydispersity index of 1.02 for nanostructured polymer in agreement with the size monodispersity transpired by electron microscopy. The d.c. electrical conductivity σ _dc of PANI at room temperature is 10.11 S/cm whereas the variation of conductivity with temperature in the range 227–303 K reveals that the conducting mechanism can be considered as three-dimensional variable-range-hopping (3D-VRH). UV-Vis spectrum indicates two broad absorption bands due to polaron formation that contributes to enhanced electrical conductivity of the polymer. The fundamental absorption edge in the polymer is formed by direct allowed transitions to the extent that the optical band gap value was found to be 2.35 eV. The crystalline nanostructure and homogeneous doping attained in the cationic template of amphiphile are argued as contributing factors to the enhanced conductivity of the polymer.     

Physicochemical interactions between polyaniline and graphene oxide: the reasons for the stability of their chemical structure and thermal properties

Several works are reported in the literature on the use of a conducting polymer such as polyaniline (PANI) and its combination with graphene oxide (GO). Graphene derivatives have an important contribution to improve the electrochemical performance of charge transfer and polarization of the polymer in energy storage cells. To understand the chemical phenomena in PANI–GO interaction, this article presents the relationships of the thermal, chemical, and morphostructural properties of this composite material. This synergistic effect between the materials is responsible for performance enhancing. Therefore, in this work, after PANI electrosynthesis on carbon fiber and further dipping of GO, Field Emission Gun, Raman spectroscopy, X-Ray Excited Electron Photon Spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction, Differential Scanning Calorimetry, and thermogravimetric techniques were used to characterize these materials. GO tends to stabilize the molecular structure of PANI in its protonation/deprotonation and redox processes. Through thermal analysis, it was possible to observe that GO increases the stability of PANI at higher temperatures, minimizing mass loss rates and changing the polymer's glass transition temperature. And when observing the structure of the material under the influence of temperature, the GO kept the structures practically unaltered (PANI crystallographic orientation) up to 150 °C. These facts highlight important material stability data to be considered in energy storage system applications.     

Synthesis and characterization of conductive polyaniline/TiO2 composite nanofibers

Fibrillar conductive polyaniline/TiO₂ (PANI/TiO₂) nanocomposites with different TiO₂ amount were synthesized with a template-free in situ polymerization method and characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR) and conductivity measurement. The morphology determination shows that the PANI/TiO₂ composite nanofibers are relatively uniform with the diameter and length in the range of 20–40 nm and 390–420 nm respectively. It also shows that the TiO₂ of the composite is rutile crystalline and PANI has some degree of crystallinity. The IR measurement indicates that there is a strong interaction between the PANI and TiO₂ nanoparticles, and it has a beneficial effect on the thermal stability of the composite nanofiber. The conductivity of PANI/TiO₂ composites changes with TiO₂ amount and reaches an optimum value of 2.86 S/cm at 11.1 wt% TiO₂. Translated from Journal of Northwest Normal University (Natural Science), 2006, 42(4): 67–70 (in Chinese)