EPR and electrical conductivity in microporous polyaniline

We have studied a series of microporous polyaniline (PANI) samples, each of the structure with micro-channels and micro-caves inside (a diameter of 1.5–2.5 μm), formed as a non-periodic network of microrods. Microporous polyaniline is a paramagnetic material and strong EPR signals with the g-factor in the range of 2.0030–2.0032 and the line width ΔB between 1.80 and 6.50 Gs have been measured for samples of various electrical conductivity. The EPR line asymmetry is high (almost 1.5) in the case of PANI samples of the highest electrical conductivity (0.35 S/cm).We found that lithium cations present in the reaction medium can stabilise values of the EPR line asymmetry parameter and g-factor observed for PANI samples prepared in such conditions. Lithium cations are able to influence the intermolecular hydrogen bonding which is essential for the interchain coupling leading to an increase in the EPR line asymmetry and a higher electrical conductivity. Thus, the properties of PANI samples are modified by lithium cations.     

The role of interface structure in oxidation reactions

The dynamics of the scale–metal interface exhibits an asymmetry in behavior in oxidation and other scaling reactions depending on whether the mechanism is one of cation or anion-diffusion. For the cation case, the growth step is at the free surface and line defects at the metal–scale interface serve to annihilate vacancies in the scaling mechanism. For the anion case, the growth step is at the scale–metal interface. Disconnections and dislocations provide the growth sites for the reaction and both their topological and elastic properties influence the mechanism. Scaling reactions to form nickel oxide and molybdenum disulfide are considered as examples. Conditions favoring scale fracture are discussed. The results are related to the reactive element effect and to the significance of the Pilling–Bedworth ratio.     

Optical and electrical transport properties of polyaniline–silver nanocomposite

Polyaniline–silver nanocomposite has been synthesized successfully by the chemical oxidative polymerization of aniline with ammonium peroxydisulphate as an initiator in presence of negatively charged silver nanoparticles. Silver nanoparticles are prepared by standard citrate reduction method. TEM, SEM, XRD, FTIR, TGA, DSC, optical absorption and photoluminescence studies are done for the morphological, structural, thermal and optical characterization of the polyaniline nanocomposite. From the TEM and SEM image, it is observed that nanoparticles are well dispersed in the polyaniline matrix. XRD pattern shows that polyaniline is amorphous, but peaks present in XRD pattern in polymer nanocomposites are for silver nanoparticles. TGA and DSC results show that polyaniline silver nanocomposite is more crystalline and more thermally stable. A surface plasmon absorption band is obtained from the optical absorption at 380 nm, which indicates that silver nanoparticles are present in the polyaniline matrix. The optical band gap of nanocomposite decreases with increasing content of silver nanoparticles. An enhancement in photoluminescence has been observed in polyaniline–silver nanocomposite than that in pure polyaniline. The electrical conductivity of polyaniline–silver nanocomposite increases with increase in silver nanoparticle content than that of pure polyaniline. This is a simple way by which optical and electrical properties of polyaniline may be enhanced by doping with suitable nanoparticles.     

Preparation and electrical–magnetic properties of polyaniline doped with ionic ferrocenesulfonic acid

Conducting polyaniline with electrical conductivity of 2.34 × 10⁻¹ S cm⁻¹ was obtained using ferrocenesulfonic acid as dopant. After the ferrocenesulfonic acid was oxidized with FeCl₃, though the electrical conductivity of the doped polyaniline decreased by 1–2 orders of magnitude, the magnetic susceptibility (χ) increased with the increase of the oxidation degree of ferrocenesulfonic acid. EPR spectra showed not only a signal with a g value of around 2, but also a so-called half-field signal with a g value of about 4 even at room temperature. Coexistence of ferromagnetic intrachain interactions and antiferromagnetic interchain interactions in the materials has been suggested.     

Nanostructured polyaniline synthesized using interface polymerization and its redox activity in a wide pH range

Purely nanostructured polyaniline with the conductivity of 7.2 S cm^?1 was synthesized via the quick addition of the oxidant of the solid ammonium peroxydisulfate into a cooled solution containing aniline and hydrochloric acid without any templates. The morphology of polyaniline is constructed of interwoven fibers with an average diameter of about 50 nm with lengths varying from 250 nm to 370 nm. In general, the conventional polyaniline completely lost its electric activity including conductivity and redox activity at pH 6; however, the polyaniline reported here shows two pairs of redox peaks on its cyclic voltammogram in 1.0 M NaCl solution with pH 7.0, which is similar to that of the conventional polyaniline in the more acidic solutions; and it still holds the redox activity until pH 9.0. The pH dependence of conductivity of polyaniline is also improved compared to that of the conventional polyaniline. The ESR measurements show that the deprotonated polyaniline still holds rather high unpaired spin densities. The ¹H NMR spectra of polyaniline synthesized using interface polymerization are different those of the conventional polyaniline. The electrochemical behavior and spectra of polyaniline synthesized via the quick addition of an oxidant solution into a solution of aniline were reported and discussed.     

Al-Zn-Mg-Cu合金组织和电导率及抗应力腐蚀性能研究

研究了三种Al-Zn-Mg-Cu合金在回归再时效状态下的组织、电导率与抗应力腐蚀性能的关系.结果表明,电导率≥35.46%IACS的合金均表现出良好的抗应力腐蚀性能与较高的拉伸强度,晶界组织为粗大分立的η相,晶内为均匀弥散的GP区和η'相;而电导率≤34.63%IACS的合金虽然拉伸强度较高,但抗应力腐蚀性能较低,晶界组织为尺寸较小的链状η相.分析表明,相对常规T73等过时效状态的高电导率(38%～42%IACS),回归再时效状态弥散的晶内组织导致了较低的电导率和高抗拉强度,但粗大分立的晶界析出相仍然使其获得了优良的抗应力腐蚀性能,从而使合金表现出电导率适中(35.46%～36.82%IACS)、抗应力腐蚀性能良好和拉伸强度高的特点.     

Composites of polyaniline and cellulose acetate: preparation,characterization, thermo-oxidative degradation and stability in terms of DC electrical conductivity retention

The composite films of polyaniline and cellulose acetate have been prepared by using two slightly different techniques. Thus-prepared polyaniline:celluloseacetate (PANI:CA) composite films were characterized by FTIR and SEM. The thermo-oxidative degradation was studied by thermogravimetric analysis (TGA) while the stability in terms of retention of DC electrical properties was studied in an oxidative environment by two slightly different techniques.     

Effect of temperature and moisture on electrical conductivity in polyaniline/polyurethane (PANI/PU) blends

Miscible blend of conductive polyaniline/polyurethane (PANI/PU) showed preferable electrical property at low percolation threshold compared to immiscible blend of PANI/polystyrene-isoprene-copolymer (PANI/SIS) and carbon black/PU composite (CB/PU). The time dependence of the electrical conductivity was investigated with these samples aged under different humidity and temperatures. The electrical conductivity of PANI/PU (11.5/88.5, v/v) decreased with aging time and the morphology changed with time in the coexistence of high moisture and high temperature. After the aging treatment, the film of the miscible blend was re-dissolved and re-cast. The morphology and electrical conductivity were found to recover to the same state as the original film. In addition, the recovery mechanism of the morphology and the conductivity was also proposed here.     

13C CPMAS NMR,XRD, d.c. and a.c. electrical conductivity of aromatic acids doped polyaniline

Aromatic acids, para-toluene sulfonic acid (PTSA) and sulfosalicylic acid (SSA), doped polyanilines at different dopant levels and prepared by chemical and electrochemical methods are characterized by the high-resolution solid-state ¹³C CPMAS NMR technique. X-ray diffraction (XRD) patterns of highly protonated samples show a peak around 24 °. There is increase in crystallinity as the dopant concentration is increased. Temperature dependence of d.c. electrical conductivity measurements suggests that conduction takes place in an inhomogeneous medium consisting of ‘metallic’ polymer particles embedded in an insulating matrix. A.c. electrical conductivity measured on some of these samples shows that σ_ac ∝ ω^s in the frequency range 10 Hz to 100 kHz, and s is found to decrease as the dopant concentration and the temperature are increased. For higher dopant concentration samples, σ_ac is found to be temperature independent in the frequency range 10 Hz–100 kHz. The real part of the dielectric constant showed a steep increase at low frequencies. The results of a.c. transport are discussed in terms of hopping of charges among defect states.     

Effects of electrical current on transport processes in resistance spot welding

Abstract

The effects of alternating current (ac) and direct current (dc) on cooling rate, solute distribution and nugget shape after solidification, which are responsible for microstructure of the fusion zone, during resistance spot welding, are realistically and extensively investigated. The computer program developed by Wang and Wei is used to predict transport variables in workpieces and electrodes during heating, melting, cooling and freezing periods. The model accounts for electromagnetic force, heat generations at the electrode/workpiece interface and faying surface between workpieces, and dynamic electrical resistance including bulk resistance and contact resistances at the faying surface and electrode/workpiece interfaces, which are functions of hardness, temperature, electrode force and surface condition. The computed results show that in contrast to dc, using ac readily produces the nugget in an ellipse shape. Deficit and excess of solute content occur in a thin layer around the boundary and interior of the nugget respectively.     

Blends of polyimide and dodecylbenzene sulfonic acid-doped polyaniline: Effects of polyimide structure on electrical conductivity and its thermal degradation

This paper describes the effects of polyimide (PI) structure on electrical conductivity of blends of dodecylbenzene sulfonic acid-doped polyaniline (PANI-DBSA) and PI, as well as its thermal degradation behavior. Four types of PIs with different molecular architecture were synthesized and subsequently solution blended with PANI-DBSA. Of the four types of PIs, 4-4′-diaminodiphenyl sulfone (DADPS)-based PI provides the highest conductivity to the blends. It is attributed to the rigid nature of DADPS, which may induce more extended conformation of PANI chains, and hence result in a more ordered structure. The conductivity of the blends has significant higher thermal stability than that of PANI-DBSA. The thermal stability is, however, independent on the polyimide structure. TGA studies show that the PI matrix may have hindered the thermo-oxidative degradation and evaporation of the dopants and thus slowed down the process of thermal degradation of the conductivity.     

In situ self-organization of carbon black–polyaniline composites from nanospheres to nanorods: Synthesis, morphology, structure and electrical conductivity

Nanostructured composites of polyaniline (PANI) with carbon black (CB) were synthesized by an in situ self-organization process. The synthesis is based on the polymerization of aniline in a micellar solution of p-toluenesulfonic acid (TSA) with different weight percentages of CB using ammonium peroxydisulfate (APS) as the oxidizing agent. Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR), UV–vis spectroscopy, and the four-probe meter were used to study the morphological, structural, thermal, and electrical properties of CB–PANI nanocomposites. The results demonstrate that the morphology, thermal stability, and electrical conductivity of the nanocomposites were significantly influenced by the content of CB. SEM results reveal that there was a transition in morphology from composite nanospheres to one-dimensional (1D) composite long nanorods with an increase of CB content. XRD and UV–vis spectra results revealed that there was an increase in the crystallinity and a shift of quinoid transition bands towards lower wavelengths as the amount of CB in the composite increased. The mechanism for the formation of nanostructured composites was explained on the basis of the self-organization of micelles. CB–PANI nanocomposites with a maximum electrical conductivity of 1.38 S/cm were obtained; this is at least three orders of magnitude higher than that of pristine PANI.     

The study of electrical and magnetic properties of LiPF6 doped polyaniline

The results of temperature dependent dc conductivity, EPR magnetic susceptibility, and X-ray photoelectron spectroscopy experiments (XPS) are reported for polyaniline (PAN) doped with lithium hexafluorophosphate (LiPF₆), PAN-LiPF₆. DC conductivity (σ_dc) and its temperature dependence of PAN-LiPF₆ samples vary with the average molecular weight (Mw) of polyaniline used and the composition of doping solution. The EPR linewidth and Pauli susceptibility (χ^P) depend on the Mw of PAN used. The σ_dc and the χ^P of the intermediate Mw PAN-LiPF₆ samples are higher than those of the low Mw PAN samples, indicating more highly conducting state of the intermediate Mw PAN samples. Based on the results of XPS and EPR experiments, some portions of quinoid rings in emeraldine base form of PAN are transformed into benzenoid rings through LiPF₆ doping process, indicating the formation of polarons. However, the existence of some portions of quinoid rings in PAN-LiPF₆ samples after doping suggests an inhomogeneous doping or a pseudo doping.     

Viscoelastic and conductivity properties of thermoreversible polyaniline–DNNSA gel in m-cresol

The rheological behavior of polyaniline (PANI)–dinonylnaphthalene sulfonic acid (DNNSA) in m-cresol is studied for different weight percent (w/v) of PANI–DNNSA_0.5. From rheological viewpoint the sample behaves like viscous fluid at low concentration (2 wt%) and gel at the concentration ≥8 wt%. The 4 wt% PANI–DNNSA_0.5 in m-cresol is at typical viscoelastic percolation region which is sol in the absence of shear but show invariant storage modulus with frequency at 30 °C. SEM picture indicates fibrillar network structure in the gel and the doped polyaniline remain as nanofiber at ≤2 wt% concentrations. The complete doping of PANI in all the systems is confirmed from UV–vis spectra. The dc conductivity of the gel increases with increasing the concentration of PANI–DNNSA_0.5 in m-cresol showing a jump at ～4% concentration (percolation threshold). ac-Conductivity increases with increase in PANI–DNNSA_0.5 concentration studied here for each frequency. At lower frequency (<10⁵ Hz) ac-conductivity increase slowly with frequency but at higher frequency (>10⁵ Hz) the increase is large having a curve like behavior. The gel state shows an increase of module by ～5 orders and also an increase of ～3 orders in ac-conductivity at the same frequency. The impedance spectroscopy results suggest the formation of combined resistance and capacitance (R–C) circuits in the gel and the increase of PANI–DNNSA_0.5 in the gel increases the capacitive feature more dominantly though the path becomes less resistive. The process also signifies the preparation of DNNSA doped PANI nanofiber in the gel medium.     

The manufacture and properties of polyaniline nano-films prepared through vapor-phase polymerization

We succeeded in the chemical preparation of nano-level thick polyaniline (PANI) emeraldine salt films on plastic substrate by an in situ vapor-phase deposition (VDP) polymerization method under ambient conditions, using a self-assembly method which is unprecedented. Homogeneous conductive PANI thin films were uniformly fabricated at nano-level thickness (20–100 nm), but their morphologies could grow as polycrystalline grains of a highly ordered structure, depending on the deposition conditions. The grain size was also controlled between 30 and 100 μm depending on the deposition time/temperature. The surface resistance of PANI films was enhanced up to 10⁴ Ω/square with crystallization and light transmittance was increased up to 90% in the case of a film less than 30 nm thick. A typical spectrum for the oxidized PANI, the emeraldine salts form, showing π–π^* transition and a polaron lattice were observed by UV–visible/IR and infrared /Raman spectroscopy.     

Synthesis,characterization and electrical conductivity of polyesters,polyamides and doped polymers

The synthesis and characterization of polyamides and polyesters containing azomethyne linkages are reported here. The electrical conductivity of the polymers is measured and the results explained with simple Pariser-Parr-Pople calculations. The polymers are doped with Ag and the electrical conductivity of each polymer is found to register a significant increase. Attempts are made to explain this increase.     

Cu/TiBN电接触材料的导电性及抗电弧侵蚀机理

采用渗硼烧结法合成了一种新型TiBN粉体材料,它兼有陶瓷性和金属性,电阻率为2.6×10-3Ω·cm。以TiBN和TiN为增强相,采用粉末冶金法制备了Cu/TiBN和Cu/TiN电接触材料,系统的研究了不同含量TiBN和TiN的电接触材料的微观结构和物理性能。结果表明,与TiN相比,TiBN增强相能明显改善Cu基电接触材料的导电性能、抗氧化性能、硬度和抗电弧侵蚀性能。当含量为5wt.%时,Cu/TiBN电接触材料的抗电弧侵蚀能力最好,重量损失仅为1.5mg。电弧侵蚀时,在Cu/TiBN表面生成TixOy、B2O3和N2等产物,这些产物能明显改善Cu/TiBN电接触材料的抗电弧侵蚀能力。新开发的Cu/TiBN电接触材料具有优异的物理性能和抗电弧侵蚀性能,在电接触行业中拥有广阔的应用前景。