Carbonized Leather Waste with Deposited Polypyrrole Nanotubes: Conductivity and Dye Adsorption.

This paper reports the conversion of a waste to a conducting material, exploiting the ability to adsorb pollutant organic dyes. Leather waste was carbonized at 800 °C in an inert nitrogen atmosphere. The resulting biochar was used for in-situ deposition of polypyrrole nanotubes produced by the oxidative polymerization of pyrrole in the presence of methyl orange. The composites of carbonized leather with deposited polypyrrole nanotubes of various composition were compared with similar composites based on globular polypyrrole. Their molecular structure was characterized by infrared and Raman spectra. Both conducting components formed a bicontinuous structure. The resistivity was newly determined by a four-point van der Pauw method and monitored as a function of pressure applied up to 10 MPa. The typical conductivity of composites was of the order of 0.1 to 1 S cm-1 and it was always higher for polypyrrole nanotubes than for globular polypyrrole. The method also allows for the assessment of mechanical features, such as powder fluffiness. The conductivity decreased by 1-2 orders of magnitude after treatment with ammonia but still maintained a level acceptable for applications operating under non-acidic conditions. The composites were tested for dye adsorption, specifically cationic methylene blue and anionic methyl orange, using UV-vis spectroscopy. The composites were designed for future use as functional adsorbents controlled by the electrical potential or organic electrode materials.

Flexible, ultrathin and light films from one-dimensional nanostructures of polypyrrole and cellulose nanofibers for high performance electromagnetic interference shielding.

Combining highly conducting one-dimensional nanostructures of polypyrrole with cellulose nanofibers (CNF) into flexible films with tailored electrical conductivity and mechanical properties presents a promising route towards the development of eco-friendly electromagnetic interference shielding devices. Herein, conducting films with a thickness of 140 µm were synthesized from polypyrrole nanotubes (PPy-NT) and CNF using two approaches, i.e., a new one-pot synthesis consisting of in situ polymerization of pyrrole in the presence of structure guiding agent and CNF, and a two-step synthesis, in which CNF and PPy-NT were physically blended. Films based on one-pot synthesis (PPy-NT/CNFin) exhibited higher conductivity than those processed by physical blending, which was further enhanced up to 14.51 S cm-1 after redoping using HCl post-treatment. PPy-NT/CNFin containing the lowest PPy-NT loading (40 wt%), thus the lowest conductivity (5.1 S cm-1), displayed the highest shielding effectiveness of -23.6 dB (>90 % attenuation), thanks to the good balance between its mechanical properties and electrical conductivity.

Carbonized Leather Waste: A Review and Conductivity Outlook.

The carbonization of collagen-based leather waste to nitrogen-containing carbon is reviewed with respect to the preparation, characterization of carbonized products, and applications proposed in the literature. The resulting nitrogen-containing carbons with fibrous morphology have been used as adsorbents in water pollution treatment, in electrocatalysis, and especially in electrodes of energy-storage devices, such as supercapacitors and batteries. Although electrical conductivity has been implicitly exploited in many cases, the quantitative determination of this parameter has been addressed in the literature only marginally. In this report, attention has been newly paid to the determination of conductivity and its dependence on carbonization temperature. The resulting powders cannot be compressed into pellets for routine conductivity determination. A new method has been used to follow the resistivity of powders as a function of pressure up to 10 MPa. The conductivity at this pressure increased from 9.4 × 10-8 S cm-1 for carbonization at 500 °C to 5.3 S cm-1 at 1000 °C. The conductivity of the last sample was comparable with conducting polymers such as polypyrrole. The carbonized leather thus has the potential to be used in applications requiring electrical conduction.

Conducting and Magnetic Hybrid Polypyrrole/Nickel Composites and Their Application in Magnetorheology.

Hybrid organic/inorganic conducting and magnetic composites of core-shell type have been prepared by in-situ coating of nickel microparticles with polypyrrole. Three series of syntheses have been made. In the first, pyrrole was oxidised with ammonium peroxydisulfate in water in the presence of various amounts of nickel and the composites contained up to 83 wt% of this metal. The second series used 0.1 M sulfuric acid as a reaction medium. Finally, the composites with polypyrrole nanotubes were prepared in water in the presence of structure-guiding methyl orange dye. The nanotubes have always been accompanied by the globular morphology. FTIR and Raman spectroscopies confirmed the formation of polypyrrole. The resistivity of composite powders of the order of tens to hundreds Ω cm was monitored as a function of pressure up to 10 MPa. The resistivity of composites slightly increased with increasing content of nickel. This apparent paradox is explained by the coating of nickel particles with polypyrrole, which prevents their contact and subsequent generation of metallic conducting pathways. Electrical properties were practically independent of the way of composite preparation or nickel content and were controlled by the polypyrrole phase. On the contrary, magnetic properties were determined exclusively by nickel content. The composites were used as a solid phase to prepare a magnetorheological fluid. The test showed better performance when compared with a different nickel system reported earlier.

The Effect of Glass Fiber Storage Time on the Mechanical Response of Polymer Composite.

The growing demand for polymer composites and their widespread use is inevitably accompanied by the need to know their degradation behavior over a sufficiently long period of time. This study focuses on commercial glass fiber rovings, which were stored in the indoor environment for up to 11 years. Fibers with different storage times, from fresh up to the oldest, were used to produce unidirectional fiber-reinforced polyester composites that were characterized to determine their shear and flexural properties dependent on fiber storage time. A significant decrease in shear strength was observed throughout the aging of the fibers, down to a decrease of 33% for the oldest fibers. An important finding, however, was that the significant decrease in shear strength was only partially reflected in the flexural strength, which corresponded to a decrease of 18% for the oldest fibers at consistent flexural modulus.

Pressure-Sensitive Conducting and Antibacterial Materials Obtained by in Situ Dispersion Coating of Macroporous Melamine Sponges with Polypyrrole.

Melamine sponges were coated with polypyrrole during the in situ polymerization of pyrrole. The precipitation polymerization was compared with the dispersion mode, that is, with the preparation in the presence of poly(N-vinylpyrrolidone) and nanosilica as colloidal stabilizers. The coating of sponges during the dispersion polymerization leads to the elimination of the undesired polypyrrole precipitate, improved conductivity, and increased specific surface area. The sponges were tested with respect to their conductivity and as pressure-sensitive conducting materials with antibacterial performance.

Simplified Testing of the Bond Strength of Adhesives Used for Bonded Anchors.

The analysis presented in this paper is focused on problems of bond strength as an overall bond quality parameter of industrial adhesives for structural anchoring. In the first part, the problem of bond strength as the most important parameter influencing the final anchor resistance to tension load is described. Further in the text, a new methodology of simplified testing of the strength parameters of adhesives is described. Special test specimens made from steel are repeatedly used in this methodology. Additionally, results of these tests on some new recipes for adhesive are presented. Especially, epoxy resins with special fillers, such as carbon fibres, carbon nanotubes or graphene, were tested. The use of these adhesives in temperatures close to zero degrees Celsius was also tested.

One-Dimensional Nanostructures of Polypyrrole for Shielding of Electromagnetic Interference in the Microwave Region.

Polypyrrole one-dimensional nanostructures (nanotubes, nanobelts and nanofibers) were prepared using three various dyes (Methyl Orange, Methylene Blue and Eriochrome Black T). Their high electrical conductivity (from 17.1 to 60.9 S cm-1), good thermal stability (in the range from 25 to 150 °C) and resistivity against ageing (half-time of electrical conductivity around 80 days and better) were used in preparation of lightweight and flexible composites with silicone for electromagnetic interference shielding in the C-band region (5.85-8.2 GHz). The nanostructures' morphology and chemical structure were characterized by scanning electron microscopy, Brunauer-Emmett-Teller specific surface measurement and attenuated total reflection Fourier-transform infrared spectroscopy. DC electrical conductivity was measured using the Van der Pauw method. Complex permittivity and AC electrical conductivity of respective silicone composites were calculated from the measured scattering parameters. The relationships between structure, electrical properties and shielding efficiency were studied. It was found that 2 mm-thick silicone composites of polypyrrole nanotubes and nanobelts shield almost 80% of incident radiation in the C-band at very low loading of conductive filler in the silicone (5% w/w). Resulting lightweight and flexible polypyrrole composites exhibit promising properties for shielding of electromagnetic interference in sensitive biological and electronic systems.

Conducting polyaniline prepared in the solutions of formic acid: Does functionalization with carboxyl groups occur?

Polyaniline is a conducting polymer with an application potential in the field of biomedical engineering. By employing FTIR spectroscopy and conductivity measurements, it has been shown that the oxidation at stoichiometric peroxydisulfate-to-aniline mole ratio 1.25 in the solutions of formic acid in the range 0-10 M provides samples of a moderate conductivity of the orders 0.01-0.1 S cm-1. They consist of polyaniline and aniline oligomers as typical of the aniline oxidation in weak acids. The detailed investigation of the infrared spectra indicates a partial ring-carboxylation of polyaniline at high acid concentrations. The extent of structural defects is higher for a series prepared at over-stoichiometric peroxydisulfate-to-aniline mole ratio 2.5, which provided only non-conducting samples. The reference sample series represented by poly(aniline-co-o-aminobenzoic acid) was also prepared and is used in the discussion of the infrared spectra.

Role of p-Benzoquinone in the Synthesis of a Conducting Polymer, Polyaniline.

Polyaniline (PANI) and 2,5-dianilino-p-benzoquinone both are formed by oxidation of aniline in an acidic aqueous environment. The aim of this study is to understand the impact of addition of p-benzoquinone on the structure of PANI prepared by the oxidation of aniline hydrochloride with ammonium peroxydisulfate and to elucidate the formation of low-molecular-weight byproducts. An increasing yield and size-exclusion chromatography, Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy, and nuclear magnetic resonance analyses of the products show that p-benzoquinone does not act as a terminating agent in the synthesis of PANI and the content of 2,5-dianilino-p-benzoquinone increases with the increasing molar concentration of p-benzoquinone in the reaction mixture, [BzQ]. Regarding the structure of PANI, Raman and UV-visible spectra show that the doping level and the charge delocalization both decrease with the increase of [BzQ], and the FTIR spectra of the PANI bases indicate an increased concentration of benzenoid units at higher [BzQ]. We explain these observations by an increasing concentration of structural defects in PANI chains and propose a 2,5-dianilino-p-benzoquinone-like structure of these defects present as pendant groups. The bands typical of 2,5-dianilino-p-benzoquinone-like moiety are observed even in the vibrational spectra of the sample prepared without addition of p-benzoquinone. This confirms in situ oxidation of aniline to p-benzoquinone within the course of the oxidation of aniline hydrochloride to PANI.

Electrically Conductive, Transparent Polymeric Nanocomposites Modified by 2D Ti3C2Tx (MXene).

The electrically conductive, transparent, and flexible self-standing thin nanocomposite films based on copolyamide matrix (coPA:Vestamelt X1010) modified with 2D Ti3C2Tx (MXene) nanosheets were prepared by casting and their electrical, mechanical and optical properties and then, were investigated. The percolation threshold of the MXene filler within the coPA matrix was found to be 0.05 vol. %, and the highest determined electrical conductivity was 1.4 × 10-2 S·cm-1 for the composite filled with 5 wt. % (1.8 vol. %) of MXene. The electrical conductivity of the as-prepared MXene was 9.1 S·cm-1, and the electrical conductivity of the MAX phase (the precursor for MXene preparation) was 172 S·cm-1. The transparency of the prepared composite films exceeded 75%, even for samples containing 5 wt. % of MXene, as confirmed by UV spectroscopy. The dynamic mechanical analysis confirmed the improved mechanical properties, such as the storage modulus, which improved with the increasing MXene content. Moreover, all the composite films were very flexible and did not break under repeated twisting. The combination of the relatively high electrical conductivity of the composites filled with low filler content, an appropriate transparency, and good mechanical properties make these materials promising for applications in flexible electronics.

Polypyrrole Nanotubes and Their Carbonized Analogs: Synthesis, Characterization, Gas Sensing Properties.

Polypyrrole (PPy) in globular form and as nanotubes were prepared by the oxidation of pyrrole with iron(III) chloride in the absence and presence of methyl orange, respectively. They were subsequently converted to nitrogen-containing carbons at 650 °C in an inert atmosphere. The course of carbonization was followed by thermogravimetric analysis and the accompanying changes in molecular structure by Fourier Transform Infrared and Raman spectroscopies. Both the original and carbonized materials have been tested in sensing of polar and non-polar organic vapors. The resistivity of sensing element using globular PPy was too high and only nanotubular PPy could be used. The sensitivity of the PPy nanotubes to ethanol vapors was nearly on the same level as that of their carbonized analogs (i.e., ~18% and 24%, respectively). Surprisingly, there was a high sensitivity of PPy nanotubes to the n-heptane vapors (~110%), while that of their carbonized analog remained at ~20%. The recovery process was significantly faster for carbonized PPy nanotubes (in order of seconds) compared with 10 s of seconds for original nanotubes, respectively, due to higher specific surface area after carbonization.

Solid-state reduction of silver nitrate with polyaniline base leading to conducting materials.

The polyaniline (PANI) base was ball-milled with silver nitrate in the solid state. Samples were prepared at various mole ratios of silver nitrate to PANI constitutional units ranging from 0 to 1.5 for three processing times, 0, 5, and 10 min. The emeraldine form of PANI was oxidized to pernigraniline, and the silver nitrate was reduced to metallic silver. Nitric acid is a byproduct, which may protonate the residual emeraldine and pernigraniline. The changes occurring in the structure of PANI are discussed on the basis of Fourier transform IR and Raman spectroscopies. Raman spectra revealed the formation of pernigraniline salt. The reaction between the two nonconducting components, emeraldine base and silver nitrate, produced a mixture of two conducting components, emeraldine or pernigraniline nitrate and metallic silver. The accompanying conductivity changes were determined. The increase in the conductivity of the original base, 10(-9) S cm(-1), up to 10(-2) S cm(-1) was found to depend on the mole ratio of silver nitrate to PANI base and on the processing time of the components in the ball mill.

Coating of zinc ferrite particles with a conducting polymer, polyaniline.

Particles of zinc ferrite, ZnOFe2O3, were coated with polyaniline (PANI) phosphate during the in situ polymerization of aniline in an aqueous solution of phosphoric acid. The PANI-ferrite composites were characterized by FTIR spectroscopy. X-ray photoelectron spectroscopy was used to determine the degree of coating with a conducting polymer. Even a low content of PANI, 1.4 wt%, resulted in the 45% coating of the particles' surface. On the other hand, even at high PANI content, the coating of ferrite surface did not exceeded 90%. This is explained by the clustering of hydrophobic aniline oligomers at the hydrophilic ferrite surface and the consequent irregular PANI coating. The conductivity increased from 2 x 10(-9) to 6.5 S cm(-1) with increasing fraction of PANI phosphate in the composite. The percolation threshold was located at 3-4 vol% of the conducting component. In the absence of any acid, a conducting product, 1.4 x 10(-2) Scm(-1), was also obtained. As the concentration of phosphoric acid increased to 3 M, the conductivity of the composites reached 1.8 S cm(-1) at 10-14 wt% of PANI. The ferrite alone can act as an oxidant for aniline; a product having a conductivity 0.11 S cm(-1) was obtained after a one-month immersion of ferrite in an acidic solution of aniline.

Poly(phenylenediamine) Dispersions.

The formation and properties of poly(phenylenediamine) colloidal dispersions were investigated. Oxidative dispersion polymerization of 1,3-phenylenediamine dihydrochloride stabilized with poly(N-vinylpyrrolidone) was taken as a reference experiment. Conductivity, temperature, and acidity of the reaction mixture were recorded during the polymerization. Oxidations of all three phenylenediamine bases, of corresponding dihydrochlorides, and of dihydrochlorides in excess acid are compared. The effect of the nature of steric stabilizer on the course of polymerization was found to be marginal. Dispersion polymerization was observed to proceed faster than the precipitation one. Dynamic light scattering was used to assess particle sizes in poly(phenylenediamine) dispersions. The results are discussed in relation to an analogous polymerization of aniline leading to polyaniline dispersions. Copyright 2001 Academic Press.