STUDIES ON THE ELECTRICAL CONDUCTIVITY OF FREE-STANDING FILMS OF POLYANILINE

An insulate to metal transition was investigated based on the measurements of the dependence of the conductivity, activation energy on the protonation state of polyaniline (PANI). An isotropy in conductivity for stretched salt form of PANI was observed.For salt film of PANI, the Ⅰ-Ⅴ curve obeys Ohm's law, which shows a typical metal behavior, however, for base film or film with low protonation state, it can be explained by Space Charge Limited Current (SCLC). It is also found that the Ⅰ-Ⅴ curve of base film of PANI is independent of the work function of electrodes and the polymerization temperature.

Conductive Polyaniline/Cellulose/Graphite Composite Films with High Thermal Stability and Antibacterial Activity

Functional composite films were successfully prepared from cellulose, graphite(GP), and polyaniline(PANI) using a combination of physical and chemical processes. Cellulosewasdissolved in N-methylmorpholine-N-oxide monohydrate(NMMO) and regenerated in water to form the matrix. GP was dispersed in the NMMO solvent prior to the dissolution of the cellulose, and PANI was deposited on the surfaces of the cellulose/GP films by in situ chemical polymerization. The structures of the PANI/cellusose/GP composite films were investigated using X-ray diffraction analysis, Fourier transform infrared spectroscopy, scanning electron microscopy(SEM), and SEM/energy-dispersive X-ray spectroscopy. The mechanical strengths, thermal stabilities, conductivities, and antibacterial activities of the films were studied in detail. The results showed that GP formed a multilayered structure in the cellulose matrix and that the PANI nanoparticles were tightly wrapped on the film surface. The film thickness increased from 40 mm to 100 mm after the addition of GP and PANI. The tensile strength of the composite films was 80~107 MPa, with the elongation at break being 3%~10%. The final residual weight of the composite films was as high as 65%, and the conductivity of the composite films reached 14.36 S/m. The cellulose matrix ensured that the films were flexible and exhibited desirable mechanical properties, while the GP filler significantly improved the thermal stability of the films. The PANI coating acted as a protective layer during burning and provided good electrical conductivity and antibacterial activity against Escherichia coli; both of these characteristics were slightly enhanced by the incorporation of GP. These PANI/cellulose/GP composite films should be suitable for use in electronics, antistatic packing, and numerous other applications.

Preparation and Properties of Polyaniline Composite Films

Polyaniline (PAn) was synthesized by chemical oxidation polymerization. The conductive polymer doped by camphor sulfonic acid (CSA) and a matrix polymer, polyamide66, polyamide1010 or polyamide11, were dissolved in m-cresol and the blend solution was cast in a glass and dried for preparing polyaniline composite films. Conductivity was from 10 -6 to 10 0 Ω -1 ·cm -1 with different weight fraction of PAn-CSA. The crystallization of the films was studied by means of differential scanning calorimeter (DSC). The treatment of the composite films in different pH value solution would result in decrease of conductivity, especially in an alkaline solution.

Thermal conductivity of PVDF/PANI-nanofiber composite membrane aligned in an electric field

Poly(vinylidene fluoride)(PVDF) is a semi-crystalline thermoplastic polymer with excellent thermal stability,electrochemical stability and corrosion resistance, which has been widely studied and applied in industrial nonmetallic heat exchanger and piezoelectric-film sensor. In this study, polyaniline(PANI) nanofibers were synthesized using dodecylbenzene sulfonic acid as the surfactant. The obtained PANI nanofibers were blended in PVDF matrix to enhance thermal conductivity and tensile strength of composite materials. Electric field was applied for the orientation of membrane structure during membrane formation. Scanning electron microscope(SEM) images exhibited that the PANI nanofibers were well-dispersed in the composite membranes. The structure of composite membranes was more orderly after alignment. X-ray diffraction(XRD) and differential scanning calorimetry(DSC) indicated that the content of PANI nanofibers contributed to the transformation of PVDF from α-phase to β-phase. Both the tensile strength and thermal conductivity of composite membranes were significantly improved. This tendency was further enhanced by the application of electric field. The maximum tensile strength was obtained when the content of PANI nanofibers was 3 wt%, which was 46.44% higher than that of pure PVDF membrane. The maximum thermal conductivity of composite membranes after alignment was 84.5% greater than that of pure PVDF membrane when the content of PANI nanofibers was 50 wt%. The composite membrane is a promising new potential material in heat transfer field and the mechanism explored in this study would be informative for further development of similar thermal conductive polymeric materials.

Accurate determination of anisotropic thermal conductivity for ultrathin composite film

Highly anisotropic thermal conductive materials are of significance in thermal management applications. However,accurate determination of ultrathin composite thermal properties is a daunting task due to the tiny thermal conductance,severely hindering the further exploration of novel efficient thermal management materials, especially for size-confined environments. In this work, by utilizing a hybrid measuring method, we demonstrate an accurate determination of thermal properties for montmorillonite/reduced graphene oxide(MMT/r GO) composite film with a thickness range from 0.2 μm to2 μm. The in-plane thermal conductivity measurement is realized by one-dimensional(1D) steady-state heat conduction approach while the cross-plane one is achieved via a modified 3ω method. As-measured thermal conductivity results are cross-checked with different methods and known materials, revealing the high measurement accuracy. A high anisotropic ratio of 60.5, independent of composite thickness, is observed in our measurements, further ensuring the negligible measurement error. Notably, our work develops an effective approach to the determination of ultrathin composite thermal conductivity, which may promote the development of ultrathin composites for potential thermal-related applications.

Polyaniline-graphite composite film glucose oxidase electrode

A novel polyaniline-graphite composite film glucose oxidase （PGCF GOD） electrode was developed. The PGCF was synthesized by cyclic voitammetry method in 0.5 mol/L H2SO4 solution containing 1 g/L graphite powder and 0.2 mol/L aniline. The PGCF GOD electrode was prepared by doping GOD into the composite film. The morphology of the PGCF and the response property of the PGCF GOD electrode were investigated by scanning electron microscopy and electrochemical measurement, respectively. The results show that the PGCF has a porous and netty structure and the PGCF GOD electrode has excellent response property such as high sensitivity and short response time. Influences of pH value, temperature, glucose concentration and potential on the response current of the electrode were also discussed. The sensor has a maximum steady-state current density of 357.17μA/cm2 and an apparent Michaelis-Menten constant of 16.57 mmol/L. The maximum current response of the enzyme electrode occurs under the condition ofpH 5.5, 0.8 V and 65℃.

Temperature characterization of dielectric permittivity and AC conductivity of nano copper oxide-doped polyaniline composite

The polyaniline/copper oxide(PANI/CuO)nanocomposite was prepared by mixing solutions of polyaniline and copper oxide nanoparticles in dimethyl sulfoxide(DMSO).The synthesized polymer nanocomposites were characterized by X-ray powder diffraction(XRD),scanning electron microscope(SEM)and UV-visible spectroscopy.The characteristic peaks in XRD and UV-visible spectra confirmed the presence of CuO in the polymer structure.SEM images indicated morphological changes in the composite matrix as compared to the pristine PANI.The DC conductivity measurements were performed using two-probe method for various temperatures.AC conductivity and dielectric response of the composites were investigated in the frequency range of 10^(2)-10^(6)Hz using LCR meter.Dielectric permittivity
ε′(w)and dielectric loss factor
ε″(w)were investigated.It was observed thatε′(w)and
ε″(w)decrease with increase in frequency at all temperatures.At a particular frequency it is observed that bothε′(w)andε″(w)increase with increase in temperature.It was also observed that AC conductivity increased with increase in frequency and temperature.

Structural and electrical properties of HCl–polyaniline–Ag composites synthesized by polymerization using Ag-coated (NH_4)_2S_2O_8 powder

Ag nanoparticles were sputter-deposited on ammonium persulfate((NH_4)_2S_2O_8) powder to obtain(NH_4)_2S_2O_8-Ag powder, which was used to synthesize the HCl-doped polyaniline-Ag(HCl-PANI-Ag) composite via a polymerization procedure. The Ag nanoparticles were dispersed in the HCl-PANI matrix, and their sizes mainly ranged from 3 to 6 nm. The Ag nanoparticles did not affect the structure of emeraldine salt in the composite, and they increased the ordered crystalline regions in the HCl-PANI matrix. The HCl-PANI-Ag composite had a conductivity of(6.8 ± 0.1) S/cm, which is about four times larger than that of the HCl-PANI. The charge transport mechanism in the composite is explained by the three-dimensional Mott variable-range hopping(3D-Mott-VRH).

Electrical resistance response of polyaniline films to water,ethanol,and nitric acid solution

This paper reports on electrical resistance vs. aging time for the response of polyaniline films under exposure to water, ethanol and nitric acid （HNO3） solution. Camphor sulfonic acid-doped polyaniline films were prepared by a ＂doping-dedoping-redoping＂ method, the morphology and microstructures of the films were characterized by a scanning electron microscope and an x-ray diffractometer, the electrical resistance was measured by a four-probe method. It was found that a lower amount of water molecules infiltrating the film can decrease the film＇s resistance possibly due to an enhancement of charge carrier transfer between polyaniline chains, whereas excessive water molecules can swell inter-chain distances and result in a quick increase of resistance. The resistance of the film under exposure to ethanol increases and becomes much larger than the original value. However, HNO3 solution can decrease the film＇s resistance sharply possibly owing to doping effect of protonic acid. These results can help to understand the conduction mechanism in polyaniline films, and also indicate that the films have potential application in chemical sensors.

STABILITY AND ELECTROCHEMICAL PROPERTIES OF FULL-CONJUGATED SELF-ASSEMBLED FILMS BASED ON POLYANILINE AND ITS ACID-SUBSTITUTED DERIVATES

The stability of full-conjugated self-assembled （SA） multilayer films based on partially doped polyaniline （PANI） as a polycation and poly（o-aminobenzoic acid） （PCAN）, poly（aniline-2-sulfonic acid） （PSAN） as polyanions is investigated in alkali aqueous solutions. The self-assembled PANI-PCAN films keep their stability within 24 h in 1 mol/L NaOH solution,-the PANI-PSAN films, however, maintain the stability for 20 min in the same condition because the solubility of PSAN in alkali solutions is much higher than that of PCAN. The electrochemical properties of the SA films are determined, and the film-CdS composites formed in situ are also reported.

Electroanalytical studies on electrically conductive polyaniline： Nylon-6,6 composite film

Electrically conductive composite films ofpolyaniline and nylon-6.6 are prepared by diffusing aniline followed by oxidative polymerization of aniline into nylon-6.6 matrix. In order to determine the diffusion coefficient for the chloride ion diffusion into the composite matrix electrochemically, galvanostatic pulse method is used and the diffusion coefficient is estimated to be -6.48× 10^-17 cm^2s^-1. The results are discussed in view of them being potential replacement materials for battery. electrodes and sensors devices.

Janus(BNNS/ANF)-(AgNWs/ANF)thermal conductivity composite films with superior electromagnetic interference shielding and Joule heating performances

Highly thermal conductivity materials with excellent electromagnetic interference shielding and Joule heating performances are ideal for thermal management in the next generation of communication industry,artificial intelligence and wearable electronics.In this work,silver nanowires(AgNWs)are prepared using silver nitrate as the silver source and ethylene glycol as the solvent and reducing agent,and boron nitride(BN)is performed to prepare BN nanosheets(BNNS)with the help of isopropyl alcohol and ultrasonication-assisted peeling method,which are compounded with aramid nanofibers(ANF)prepared by chemical dissociation,respectively,and the(BNNS/ANF)-(AgNWs/ANF)thermal conductivity and electromagnetic interference shielding composite films with Janus structures are prepared by the"vacuum-assisted filtration and hot-pressing"method.Janus(BNNS/ANF)-(AgNWs/ANF)composite films exhibit"one side insulating,one side conducting"performance,the surface resistivity of the BNNS/ANF surface is 4.7×10^(13) Ω,while the conductivity of the AgNWs/ANF surface is 5,275 S/cm.And Janus(BNNS/ANF)-(AgNWs/ANF)composite film with thickness of 95 pm has a high in-plane thermal conductivity coefficient of 8.12 W/(m·K)and superior electromagnetic interference shielding effectiveness of 70 dB.The obtained composite film also has excellent tensile strength of 122.9 MPa and tensile modulus and 2.7 GPa.It also has good temperature-voltage response characteristics(high Joule heating temperature at low supply voltage(5 V,215.0℃),fast response time(10 s)),excellent electrical stability and reliability(stable and constant real-time relative resistance under up to 300 cycles and 1,500 s of tensile-bending fatigue work tests).

Study on Electrical Property of Polyaniline Composite Film

Polyaniline was synthesized by chemically oxidative poly-merization.By means of infrared spectroscopy,the dif-ference between its intrinsic state structure and its dopedstate structure was determined for researching the rela-tionship between macromolecular structure and conduc-tive property before and after doping.The morphologyof solution-processed polyblends with the electricallyconductive polyaniline-camphor sulfonic acid complex(PAn-CSA)was investigated by using scanning electronmicroscopy.The conductive percolation threshold of thecomposite films is about 2.8%.

STUDIES ON ENHANCED CONDUCTIVITY OF STRETCHED CONDUCTING POLYMERS

A physical model of series of the conductivity on chain and the interchain conductivitybetween chains is proposed to explain enhanced conductivity of stretched conducting polymers.This model suggests that the enhanced conductivity for stretched conducting polymers might bedue to increasing of the interchain conductivity between chains along the elongation direction afterdrawing processes if the conductivity on chain is assumed much larger than that of the interchainconductivity between chains. According to this model, it is expected that the temperaturedependence of conductivity measured by four-probe method for stretched conducting polymers iscontrolled by a variation of the interchain conductivity between chains with temperature, whichcan be used to explain that a metallic temperature dependence of conductivity for stretchedconducting polymers is not observed although the conductivity along the elongation direction isenhanced by two or three orders of magnitude.

FREE STANDING FILM OF POLYANILINE

A free standing film of polyaniline as large as 18 cm×18cm×0.002 cm can be obtained by evaporation of a solution of the chemically synthesized base in NMP. Its structure was examined by the elemental analysis, IR, U.V.-visible spectra, XPS, DSC, SEM and X-ray scattering and its conducting behavior as well as electrochemical properties were studied. Results show that the composition, structure of main chain, physical properties of the free standing film of polyanilme is similar to that of the powder. However, some differences in its electronic structure, conductivity at room temperature and potential of redox couple between the flee standing film and powder are observed, which may be due to cross-linking of the film of polyaniline.

Conductivity of Poly(methyl methacrylate)/Polystyrene/Carbon Black and Poly(ethyl methacrylate)/Polystyrene/Carbon Black Ternary Composite Films

Poly(methyl methacrylate)(PMMA)/polystyrene(PS)/carbon black(CB)and poly(ethyl methacrylate)(PEMA)/PS/CB ternary composite films were obtained using solution casting technique to investigate double percolation effect.In both PMMA/PS/CB and PEMA/PS/CB ternary composite films,the CB particles prefer to locate into PS phase based on the results of calculating wetting coefficient,which is also confirmed by SEM images.The conductivity of the films was investigated,and the percolation threshold(￠c)of both ternary composite films with different polymer blend ratios was determined by fitting the McLachlan GEM equation.Conductivity of PMMA/PS/CB ternary composite films showed a typical double percolation effect.However,due to the double emulsion structure of PEMA/PS polymer blends,the PEMA/PS/CB ternary composite films(PEMA/PS=50/50)showed a higher￠c,even CB only located in PS phase,which conflicts with the double percolation effect.A schematic diagram combined with SEM images was proposed to explain this phenomenon.

Thermally conductive polyvinyl alcohol composite films via introducing hetero-structured MXene@silver fillers

Ag nanoparticles were in-situ grown on the surface of MXene nanosheets to prepare thermally conductive hetero-structured MXene@Ag fillers.With polyvinyl alcohol(PVA)as the polymer matrix,thermally conductive MXene@Ag/PVA composite films were fabricated by the processes of solution blending,pouring,evaporative self-assembly.With the same mass fraction,MXene@Ag-III(MXene/Ag,2:1,w/w)presents more significant improvement in thermal conductivity coefficient(λ)than MXene@Ag,single MXene,Ag,simply blending MXene/Ag.MXene@Ag-III/PVA composite films show dual functions of excellent thermal conductivity and electromagnetic interference(EMI)shielding.When the mass fraction of MXene@Ag-III is 60 wt.%,the in-planeλ(λ_(∥)),through-planeλ(λ_(⊥)),EMI shielding effectiveness(EMI SE)are 3.72 and 0.41 W/(m∙K),32 dB,which are increased by 3.1,1.3,105.7 times than those of pure PVA film(0.91 and 0.18 W/(m∙K),0.3 dB),respectively.The 60 wt.%MXene@Ag-III/PVA composite film also has satisfying mechanical and thermal properties,with Young’s modulus,glass transition temperature,heat resistance index of 3.8 GPa,58.5 and 175.3℃,respectively.

First principles insights into oxide/polymer composites: SrTiO_(3) /polyaniline/graphene

A detailed computational investigation,based on density functional theory,of the interaction of polyani-line(PANI)and graphene nanoribbons(GNRs)with SrTiO_(3) is presented.The adsorption of PANI in var-ious oxidation states and co-adsorption with GNRs is found to be thermodynamically favourable.Ad-sorbed PANI introduces N and C 2p states into the SrTiO_(3) bandgap,while co-adsorption of PANI and GNRs leads to a bridging of the gap and semi-metallic behaviour,thus rendering the electrical properties highly sensitive to the loading of the GNRs/PANI in the composites.Modelling the lattice dynamics of the composites predicts a 68-88%reduction in the lattice thermal conductivity due to reduced phonon group velocities.Taken together,these findings provide insight into the growing number of experimental studies highlighting the enhanced thermoelectric performance of oxide-polymer composites and indicate co-adsorption with graphene as a facile direction for future research.

Thermally Conductive Polyimide/Boron Nitride Composite Films with Improved Interfacial Compatibility Based on Modified Fillers by Polyimide Brushes

Polyimide-based composite films with high thermal conductivity,good mechanical property and electrical insulating performance are urgently needed in the electronics and microelectronics fields.As one of the key technical challenges to be solved,interfacial compatibility between filler and matrix plays an important role for composite film.Herein,boron nitride was modified by grafting polyimide brushes via a twostep method,and a series of thermally conductive polyimide/boron nitride composite films were prepared.Both characterization and performance results proved that the interfacial interaction and compatibility was greatly enhanced,resulting in a significant reduction in defects and interfacial thermal resistance.The interphase width of transition zone between two phases was also efficiently enlarged due to polyimide brushes grafted on filler surface.As a result,composite films based on polyimide-grafted boron nitride exhibited significantly improved properties compared with those based on pristine filler.Tensile strength can reach up to 80 MPa even if the filler content is as high as 50 wt%.The out-of-plane and in-plane thermal conductivity of composite film increased to 0.841 and 0.850 W·m^(-1)·K^(-1),respectively.In addition,thermal and dielectric properties of composite films were also enhanced to some extent.The above results indicate that surface modification by chemically grafting polymer brushes is an effective method to improve two-phase interfacial compatibility so as to prepare composite film with enhanced properties.