Characterization of conductive composite films based on TEMPO-oxidized cellulose nanofibers and polypyrrole

Abstract  

In this article, conductive composite films based on TEMPO-oxidized cellulose nanofibers (TOCN) and polypyrrole (PPy) were synthesized in situ by a Chemical Polymerization Induced Adsorption Process of pyrrole on the surface of TOCN in aqueous medium. Resulting composite films were investigated by X-ray photoelectron spectroscopy, scanning, and transmission electron microscopy, N₂ gas adsorption analysis, thermogravimetric analysis, mechanical tests, and conductivity measurements in the ambient air. Our results showed a stable, flexible, and highly electrically conductive composite film in which PPy nanoparticles coated the surface of the TOCN network. In addition, the advantage in using the famous material, TOCN, is clearly due to the presence of carboxylate (COOH/COO⁻Na⁺) and hydroxyl (OH) moieties on the surface of TOCN. These reactive moieties could enhance the adsorption process of positively charged PPy backbone during polymerization. TEM observations demonstrated the formation of a PPy coat along the surface of the cellulose nanofibers having a diameter of about 90 nm which is relatively higher compared to the initial diameter of pure TOCN (~9 nm). Despite the physical and chemical treatment of TOCN during polymerization, the micrometric length of the cellulosic nanomaterial was maintained. In addition, the incorporation of polyvinyl alcohol as an additive in the TOCN/PPy composite seems to enhance the flexibility of composite films (bent up to 180°) without losing the high electrical conductivity. Finally, because of the high conductivity and good mechanical properties of the TOCN/PPy composite films obtained in this work, they can be used as a promising material in applications of sensors, flexible electrodes, and other fields requiring electrically conductive flexible films.     

Synthesis of polypyrrole film by pulse galvanostatic method and its application as supercapacitor electrode materials

Polypyrrole (PPy) film-coated stainless steel electrodes were prepared from aqueous solution containing 0.5 M p-toluene sulphonic acid and 0.1 M pyrrole using pulse galvanostatic method (PGM) and galvanostatic method (GM). The morphology was characterized by scanning electron microscopy. The electrochemical properties of PPy films were investigated with cyclic voltammetry, charge–discharge tests, and ac impedance spectroscopy. The results showed that the PGM-PPy films exhibited higher specific capacitance, better high-rate discharge ability and lower resistance, and were more promising for applications in supercapacitor than GM-PPy films. The specific capacitance (SC) of PGM-PPy films was 403 F g⁻¹ in 1 M H₂SO₄ electrolyte and 281 F g⁻¹ in 1 M NaNO₃ electrolyte.     

Synthesis, characterization and conductivity studies of polypyrrole-fly ash composites

In situ polymerization of pyrrole was carried out in the presence of fly ash (FA) to synthesize polypyrrole-fly ash composites (PPy/FA) by chemical oxidation method. The PPy/FA composites have been synthesized with various compositions (10, 20, 30, 40 and 50 wt%) of fly ash in pyrrole. The surface morphology of these composites was studied with scanning electron micrograph (SEM). The polypyrrole-fly ash composites were also characterized by employing X-ray diffractometry (XRD) and infrared spectroscopy (IR). The a.c. conductivity behaviour has been investigated in the frequency range 10²–10⁶ Hz. The d.c. conductivity was studied in the temperature range from 40–200°C. The dimensions of fly ash in the matrix have a greater influence on the observed conductivity values. The results obtained for these composites are of greater scientific and technological interest.     

Ferromagnetic conductive polypyrrole doped with water-soluble ferrocene derivative

In this paper, we report synthesis and characterization of polypyrrole (PPy) doped with a new water-soluble ferrocene derivative of p-ferrocenyl benzene sulfonic acid (BSAFc). The ferromagnetic conductive PPy powder was obtained by chemical polymerization. XPS and FT-IR were used to clarify the structure of PPy powder and confirm the existence of ferrocene group in the PPy powder. A complete understanding of the electronic structure of iron in PPy powder was achieved by Mössbauer spectrum measured at room temperature, which indicates that ⁵⁷Fe in the PPy powder is in the low-spin electronic structure of trivalence. The PPy powder exhibited an electrical conductivity of about 10⁰ S/cm at room temperature, a coercive force of 20 Oe and saturation magnetization of 1.76 emu/g at low temperature of 1.8 K. Thermogravimetric analysis (TGA) showed that the PPy powder had the same thermostability as normal PPy. The electro-active PPy freestanding film was also synthesized by doping with the new water-soluble ferrocene derivative via electrochemical polymerization, which is significant for developing the application of the PPy film in secondary battery, membrane electrode and so on.     

Non-destructive Thermal Diagnostics of Porous Materials

Developed mathematical models of apparent thermal conductivity of porous materials are applied to non-destructive methods of thermal diagnostics. The non-destructive thermal diagnostics of porous materials can be used to estimate the size of pores and cracks in the range 10⁻⁹ to 10⁻³ m. A fractal model of porous structure and dependences of thermal conductivity/diffusivity on (experimental) gas pressure are used as a basis for structure parameter calculations. The measuring element (sensor) in this method is the mean free path of gas molecules in pores and cracks (Knudsen number) that is very sensitive to changes in gas pressure. Possible applications of the developed methods include non-destructive thermal diagnostics (NDTD) of nano- and micro-crack sizes; opening, closing and size changes of the cracks at high temperatures in a wide temperature range; evaluation of interfacial and contact heat barrier resistance for coatings; remote laser thermal diagnostics of the cracks; as well as obtaining data on strength, thermal shock behavior, failure and fatigue behavior of coatings and other structures. Examples of several applications of the NDTD method are presented. Invited paper presented at the Fifteenth Symposium on Themophysical Properties, June 22–27, 2003, Boulder, Colorado, U.S.A.     

Design and characteristics of HTSC SQUID magnetometer with a sensitivity of 10−13 THz−1/2

The results are presented of the experimental studies on forming weak links in yttrium ceramics by scribing and high-voltage discharge. The energy resolution of SQUIDs and the magnetic field sensitivity of magnetometers produced according to these methods were 6×10⁻²⁸ J/Hz and 10⁻²⁸ J/Hz, 5×10⁻¹³ T/Hz^1/2 and 2·5×10⁻¹³ T/Hz^1/2, respectively. Different designs of HTSC interferometers sensitive to the external magnetic field variation are described. The factors affecting the sensitivity of r.f. HTSC SQUID-magnetometers are considered.     

Effects of hydrogen on the mechanical properties of a 2 1/4Cr–1Mo steel

This paper explores the effects of hydrogen on the mechanical properties of a 2 1/4Cr–1Mo steel. The results for both microstructural conditions, as received and aged, indicated a loss of ductility after hydrogen charging treatment, but the yield strength and ultimate tensile strength remained unaltered. The fractograph analysis revealed that the fracture mode was modified by the hydrogen. The steel in the as-received condition showed craters and fisheyes on the fracture surface. The aged steel showed a brittle appearance associated with cleavage facets and small portion of areas with dimples. The hydrogen diffusivity and solubility were investigated using electrochemical permeation technique. It was observed that the hydrogen diffusivity decreased from 2.3 ± 0.4 × 10⁻¹⁰ m² s⁻¹ in the as-received condition to 5.7 ± 0.1 × 10⁻¹¹ m² s⁻¹ in the aged condition. The hydrogen solubility showed an increase for the aged condition in comparison to the as received sample. Both phenomena can be attributed to carbide evolution during aging, resulting in an increase of the carbide/matrix interfacial area.     

Hybrid organic–inorganic materials based on polypyrrole and 1,3-dithiole-2-thione-4,5-dithiolate (DMIT) containing dianions

The synthesis of hybrid materials by electropolymerization of pyrrole and inorganic complexes based on the DMIT ligand (1,3-dithiole-2-thione-4,5-dithiolate), e.g. [NEt₄]₂[M(DMIT) _n ] (M = Ni, Pd or Pd, n = 2; M = Sn, n = 3], in acetonitrile solution is reported. Spectroscopic data showed that DMIT-containing anions, [M(DMIT) _n ]²⁻, were inserted into the polypyrrole framework without chemical modification during the electropolymerization process. Cyclic voltammetry showed that materials obtained were electroactive, undergoing redox processes related to both the conducting polymer and the counteranions. The electrochemical results also suggest that, in the case of the transition metal containing films, the counteranions are not trapped in the PPy matrix but undergo anion exchange during the redox cycle of PPy. However, an opposite behaviour was observed with the film with [M(DMIT) _n ]²⁻. The films exhibit good thermal stabilities and have conductivity values expected for semiconductors. This study of these hybrid materials highlights the importance of targeting specific materials for specific applications.

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Montmorillonite/polypyrrole nanocomposites. The effect of organic modification of clay on the chemical and electrical properties

Montmorillonite/polypyrrole (MMT/PPy) nanocomposites, with 15% mass loading of PPy, were prepared by the in situ polymerization of pyrrole in the presence of montmorillonite (MMT) or organo-modified montmorillonite (oMMT) in aqueous solutions containing an oxidant and an anionic surfactant. The morphology of MMT/PPy nanocomposites distinctly differs from that of the untreated MMT as shown by SEM. X-ray photoelectron spectroscopy showed that the MMT/PPy nanocomposite has an MMT-rich surface, whereas the oMMT/PPy nanocomposite surface has a rather organic nature. Due to the organic modification of MMT by the alkylammonium chloride, polymerization of pyrrole at the surface of oMMT is much more efficient in producing a conductive adlayer resulting in an enhancement of conductivity of the oMMT/PPy nanocomposites (1.1 S cm^− 1) compared to MMT/PPy (3.1 × 10^− 2 S cm^− 1). The difference in the behaviour of oMMT/PPy and MMT/PPy is interpreted in terms of surface energy minimization by the alkylammonium ions present at the surface of organo-modified MMT. Indeed, the dispersive contribution to the surface energy (γ_s^d), as determined by inverse gas chromatography at 150 °C, was estimated to be 34.0 mJ/m² for oMMT, much lower than the value of 216 mJ/m² determined for MMT.     

MWNTs/PANI composite materials prepared by in-situ chemical oxidative polymerization for supercapacitor electrode

Multi-walled carbon nanotubes (MWNTs)/polyaniline (PANI) composite materials were prepared by in-situ chemical oxidative polymerization of an aniline solution containing well-dispersed MWNTs. The supercapacitive behaviors of these composite materials were investigated with cyclic voltammetry (CV), charge–discharge tests, and ac impedance spectroscopy, respectively. The composites based on the charge-transfer complex between well-dispersed MWNTs and PANI matrixes show much higher specific capacitance, better thermal stability, lower resistance, and were more promising for applications in supercapacitors than a pure PANI electrode. The highest specific capacitance value of 224 Fg⁻¹ was obtained for the MWNTs/PANI composite materials containing MWNTs of 0.8 wt%. The improvement mechanisms of the capacitance of the composite materials were also discussed in detail.     

Thermal Conductivity and Interfacial Thermal Resistance: Measurements of Thermally Oxidized SiO2 Films on a Silicon Wafer Using a Thermo-Reflectance Technique

This article describes the development of a method to measure the normal-to-plane thermal conductivity of a very thin electrically insulating film on a substrate. In this method, a metal film, which is deposited on the thin insulating films, is Joule heated periodically, and the ac-temperature response at the center of the metal film surface is measured by a thermo-reflectance technique. The one-dimensional thermal conduction equation of the metal/film/substrate system was solved analytically, and a simple approximate equation was derived. The thermal conductivities of the thermally oxidized SiO₂ films obtained in this study agreed with those of VAMAS TWA23 within ± 4%. In this study, an attempt was made to estimate the interfacial thermal resistance between the thermally oxidized SiO₂ film and the silicon wafer. The difference between the apparent thermal resistances of the thermally oxidized SiO₂ film with the gold film deposited by two different methods was examined. It was concluded that rf-sputtering produces a significant thermal resistance ((20 ± 4.5) × 10⁻⁹ m²·K·W⁻¹) between the gold film and the thermally oxidized SiO₂ film, but evaporation provides no significant interfacial thermal resistance (less than ± 4.5 × 10⁻⁹ m²·K·W⁻¹). The apparent interfacial thermal resistances between the thermally oxidized SiO₂ film and the silicon wafer were found to scatter significantly (± 9 × 10⁻⁹ m²·K·W⁻¹) around a very small thermal resistance (less than ± 4.5 × 10⁻⁹ m²·K·W⁻¹).     

The deformation and fracture behaviour of glass-filled ABS

The tensile and fracture characteristics of pigmented ABS containing 30 wt % rubber reinforced with 30 wt % glass fibre have been examined over a range of strain-rates extending from approximately 10⁻⁴ to 10⁻¹ sec⁻¹ within the temperature range 293 to 353 K. The glass fibre-reinforced composite had significantly increased fracture strength compared with the base polymer but possessed decreased ductility. The marked yield point which is characteristic of the ABS base polymer was absent from the reinforced material. Two different regions were found to exist on the fracture surfaces of composite specimens. One region possessed the characteristics of a weak interfacial bond while the other showed evidence of strong, interfacial bonding. In both regions extensive fibre pull-out was observed. The variation in fracture strength and morphology with strain-rate and temperature of testing is explained in terms of the properties of an interfacial region adjacent to the fibres which possesses viscoelastic properties different from those of the bulk polymer. The effect of adiabatic heating at the crack tip is also taken into account in the high temperature—high strain rate regime.     

Polyaniline and polypyrrole modified conductive nanocomposites of polyfuran and polythiophene with montmorillonite clay

Nanocomposites of polyfuran (PF) and polythiophene (PTP) with montmorillonite clay (MMT) were prepared and modified by loading of polyaniline (PANI) and polypyrrole (PPY) moieties via polymerization of aniline (ANI) and pyrrole (PY) in aqueous dispersions of PF-MMT and PTP-MMT nanocomposites. Formation of PANI and PPY and their subsequent incorporation in the PF-MMT and PTP-MMT composites was confirmed by FTIR absorption studies. X-ray diffraction (XRD) patterns of PANI and PPY modified PF-MMT and PTP-MMT composites showed that PF-MMT and PTP-MMT intercalates were still present in the modified composites. Scanning electron microscopic analysis revealed distinctive morphological patterns of the various composite particles. The dc conductivity values of PANI and PPY modified PF-MMT and PTP-MMT composites were in the order of 10⁻² S/cm in either system – a value much improved compared to the same for both of the unmodified PF-MMT (10⁻⁷ S/cm) and PTP-MMT (10⁻⁵ S/cm) nanocomposites respectively.     

Physicomechanical and thermophysical properties of SiC-based ceramics

Fine-grain SiC-based ceramics have been produced via infiltration of molten silicon into preforms fabricated from SiC and graphite powders, with a phenol-formaldehyde resin as a binder. The materials thus prepared have a density of 2.70–3.15 g/cm³, dynamic modulus of elasticity from 200 to 400 GPa, compressive strength from 800 to 1900 MPa, bending strength from 150 to 315 MPa, thermal expansion coefficient (KTE) of 4.1 × 10⁻⁶ K⁻¹, and thermal conductivity of 140–150 W/(m K). Their properties are compared to those of known silicon carbide materials fabricated by other processes. The results indicate that the density and physicomechanical properties of the silicon carbide ceramics depend little on the fabrication process and are determined primarily by the SiC content. Increasing the SiC content from 20 to 99.5 wt % increases the density of the ceramics from 2.2 to 3.15 g/cm³ and leads to an exponential rise in their physicomechanical parameters: an increase in modulus of elasticity from 95 to 430 GPa, in compressive strength from 120 to 4200 MPa, and in bending strength from 70 to 410 MPa. The thermal conductivity of the ceramics depends very little on the fabrication process, falling in the range 100–150 W/(m K) over the entire range of SiC concentrations. Their KTE decreases slightly, from 4.3 × 10⁻⁶ to 2.4 × 10⁻⁶ K⁻¹, as the SiC content increases to 99–100 wt %.     

Growth and characterization of HfO2 high-k gate dielectric films by laser molecular beam epitaxy (LMBE)

The HfO₂ gate dielectric films were fabricated by the laser molecular beam epitaxy (LMBE) technique. High-resolution transmission electron microscopy (HRTEM) observation showed that under optimized condition, there is no detectable SiO₂ interfacial layer in the as-deposited film and a SiO₂ interfacial layer of about 0.4 nm was formed at the Si interface due to the post deposition annealing. Capacitance–voltage (C–V) measurement of the film revealed that the equivalent oxide thickness was about 1.3 nm. Such a film showed very low leakage current density of 1.5 × 10⁻² A cm⁻² at 1 V gate bias from the current–voltage (I–V) analysis. The conduction mechanisms as a function of temperature T and electric field E were also systematically studied.     

Elevated temperature sliding wear behavior of WCP-reinforced ferrous matrix composites

WC_P-reinforced ferrous matrix composites were processed by direct addition of WC_P (100–150 μm) and the melt of the matrix alloy to a rotating mold at 1000 rpm. Dry sliding wear behaviors of the composites containing about 80 vol.% of WC_P and high-speed steel counterpart were investigated at room temperature and 400 °C against a rotating die steel ring. And wear experiments were performed under loads of 50, 100, and 150 N and a fixed sliding velocity of 30 m/s. Results show that at room temperature, both materials exhibited a marked increase in wear rate with load applied. Wear rates of the composites and high-speed steel under loads of 50, 100, and 150 N at room temperature achieved 1.61 × 10⁻⁶, 2.14 × 10⁻⁶, 3.56 × 10⁻⁶, and 3.11 × 10⁻⁶, 23.08 × 10⁻⁶, 57.39 × 10⁻⁶ g/m, respectively. At a testing temperature of 400 °C, the composites exhibited a marked increase in wear rates and high-speed steel exhibited mild wear (characterized by extremely low wear rates) over the range of loads considered in these experiments. Wear rates of both the composites and high-speed steel at 400 °C achieved 2.42 × 10⁻⁶, 5.19 × 10⁻⁶, 6.64 × 10⁻⁶, and 4.1 × 10⁻⁶, 8.92 × 10⁻⁶, 26.02 × 10⁻⁶ g/m, respectively, under different loads. Finally, the wear-mechanism was discussed in this article.     

The effects of strain rate,density, and temperature on the mechanical properties of polymethylene diisocyanate (PMDI)-based rigid polyurethane foams during compression

Compressive experiments on three types of rigid polyurethane foams were conducted by employing modified split Hopkinson pressure bars (SHPBs). The foam materials, which were based on polymethylene diisocyanate (PMDI), varied only in density (0.31 × 10³, 0.41 × 10³, and 0.55 × 10³ kg/m³) and were compressed at strain rates as high as 3 × 10³ s⁻¹. Dynamic experiments were also performed on these three foam materials at temperatures ranging from 219 to 347 K, while maintaining a fixed high strain rate of ~3 × 10³ s⁻¹. In addition, an MTS materials testing frame was used to characterize the low-strain-rate compressive response of these three foam materials at room temperature (295 K). Our study determined the effects of density, strain rate, and temperature on the compressive response of the foam materials, resulting in a compressive stress–strain curve for each material.     

Fabrication and thermal conductivity of near-net-shaped diamond/copper composites by pressureless infiltration

Near-net-shaped diamond/copper composites with a relative density of over 99% and thermal conductivity of over 350 Wm⁻¹ K⁻¹ are successfully fabricated by powder press-pressureless infiltration processing. The effects of infiltration temperature, infiltration time, interfacial thickness, and type of protective atmosphere on the thermal conductivity of the diamond/copper composites were investigated. The results showed that the diamond-copper composites with complicated shape exhibited better thermal properties, which can be widely used in electronic packaging field. It was found that the properties of diamond-copper composites infiltrated in high vacuum atmosphere were better than that of composites infiltrated in other atmospheres. The thickness of interface showed great effects on the properties of composites. The carbide interfaces were attributed to the decrease of interfacial thermal resistance and enhancement of wetting properties between the diamonds and copper.     

Kinetic studies of water uptake and loss in glass-ionomer cements

The water sorption and desorption behaviour of three commercial glass-ionomer cements used in clinical dentistry have been studied in detail. Cured specimens of each material were found to show slight but variable water uptake in high humidity conditions, but steady loss in desiccating ones. This water loss was found to follow Fick’s law for the first 4–5 h. Diffusion coefficients at 22 °C were: Chemflex 1.34 × 10⁻⁶ cm² s⁻¹, Fuji IX 5.87 × 10⁻⁷ cm² s⁻¹, Aquacem 3.08 × 10⁻⁶ cm² s⁻¹. At 7 °C they were: Chemflex 8.90 × 10⁻⁷ cm² s⁻¹, Fuji IX 5.04 × 10⁻⁷ cm² s⁻¹, Aquacem 2.88 × 10⁻⁶ cm² s⁻¹. Activation energies for water loss were determined from the Arrhenius equation and were found to be Chemflex 161.8 J mol⁻¹, Fuji IX 101.3 J mol⁻¹, Aquacem 47.1 J mol⁻¹. Such low values show that water transport requires less energy in these cements than in resin-modified glass-ionomers. Fick’s law plots were found not to pass through the origin. This implies that, in each case, there is a small water loss that does not involve diffusion. This was concluded to be water at the surface of the specimens, and was termed “superficial water”. As such, it represents a fraction of the previously identified unbound (loose) water. Superficial water levels were: Chemflex 0.56%, Fuji IX 0.23%, Aquacem 0.87%. Equilibrium mass loss values were shown to be unaffected by temperature, and allowed ratios of bound:unbound water to be determined for all three cements. These showed wide variation, ranging from 1:5.26 for Chemflex to 1:1.25 for Fuji IX.     

Enhancing the thermoelectric performance by defect structures induced in p-type polypyrrole-polyaniline nanocomposite for room-temperature thermoelectric applications

Organic thermoelectric materials mainly conducting polymers are green materials that can convert heat energy into electrical energy and vice versa at room temperature. In the present work, we investigated the thermoelectric properties of polymer nanocomposite of polypyrrole (PPy) and polyaniline (PANI) (PPy/PANI) by varying the pyrrole: aniline monomer ratios (60:40, 50:50, and 40:60). The PPy/PANI composite is prepared by in-situ chemical polymerization of PPy on PANI dispersion. It has been observed that the combination of two conducting polymers has enhanced the electrical and thermal properties in the PPy/PANI composite due to the strong π–π stacking and H-bonding interaction between the conjugated structure of PPy and conjugated structure of PANI. The maximum electrical conductivity of 14.7 S m^?1 was obtained for composite with high pyrrole content, whereas the maximum Seebeck coefficient of 29.5 μV K^?1 was obtained for composite with high aniline content at 366 K. Consequently, the PPy/PANI composite with pyrrole to aniline monomer ratio of 60:40 exhibits the optimal electrical conductivity, Seebeck coefficient, and high power factor. As a result, the maximum power factor of 2.24 nWm^?1 K^?2 was obtained for the PPy/PANI composite at 60:40 pyrrole to aniline monomer ratio, which is 29 times and 65.8 times higher than PPy (0.077 nWm^?1 K^?2) and PANI (0.034 nWm^?1 K^?2), respectively.