Application of raman spectroscopy and sequential injection analysis for pH measurements with water dispersion of polyaniline nanoparticles

A novel method for pH measurements between pH 7.5 and 10.4 is reported in this paper. The method combines Raman spectroscopy and the automated sequential injection analysis system (SIA) and makes use of the acid-base properties of a commercially available water dispersion of polyaniline (PANI) nanoparticles with a mean particle size of 46 nm. The useful pH range of the PANI nanoparticles is broader than for conventional acid-base indicators, due to the 1:2 reaction stoichiometry of the proton-ligand complex of the nanoparticles. The pH measurements were conducted with the 633-nm laser excitation wavelength by calculating the difference between the Raman intensities of the primary and reference wavenumbers. In this study, the pH-sensitive CH=CH stretching band at 1422 cm-1 and C-H in-plane bending band of the quinoid form at 1163 cm-1 were chosen as the primary wavenumbers. The presented method is fast and allows pH to be measured with a precision of 0.2 pH unit. The advantage of the proposed method is that the hysteresis effect, which is usually observed for PANI films, can be overcome with the PANI nanoparticles, because a fresh nanoparticle solution is used in each measurement. It should be pointed out, that this work is a fundamental study showing the applicability of Raman spectroscopy in combination with the SIA technique for pH measurements in specific applications, where the conventional glass pH electrode cannot be used.     

Conducting polyaniline nanoparticles and their dispersion for waterborne corrosion protection coatings

A novel approach for preparing waterborne corrosion protection polyaniline (PANI)-containing coatings was developed. First, conducting polyaniline/partially phosphorylated poly(vinyl alcohol) (PANI/P-PVA) spherical nanoparticles with significant dispersibility in aqueous media were prepared by the chemical oxidative dispersion polymerization in presence of partially phosphorylated poly(vinyl alcohol) (P-PVA). The PANI/P-PVA-containing coatings with different PANI/P-PVA contents were then prepared, employing waterborne epoxy resin as the matrix. The corrosion protection property of PANI/P-PVA-containing coatings on mild steel was investigated by salt spray test and electrochemical impedance spectroscopy (EIS) technique in 3.0 wt % NaCl aqueous solution. The results indicated that the waterborne PANI/P-PVA-containing coatings (PANI/P-PVA content, 2.5 wt %) could offer high protection because the impedance values remained at higher than 1 × 10(7) Ω cm(2) after 30 days of salt spray tests. All the results were compared with these of the waterborne coatings containing PANI nanoparticles in the emeraldine salt form (PANI ES), and the protection mechanism was also proposed with the evidence of scanning electron microscope (SEM) and X-ray photoelectron spectrometry (XPS).     

Synthesis of hollow polyaniline nanoparticles with reactive template

γ-Fe₂O₃ nanoparticles were used as the reactive templates for the fabrication of the hollow polyaniline nanoparticles via the chemical oxidative polymerization of aniline in the presence of hydrochloric acid. The particle size of the doped hollow polyaniline nanoparticles in the emeraldine form was determined by the reactive template. It was found that the reacting temperature played an important role in the formation of the hollow nanoparticles because of the low redox potential of Fe(III) ion. However, the kind of the protonic acids used had no influence on the fabrication of the hollow nanostructure. The formation mechanism of the hollow polyaniline nanoparticles was also proposed.     

Electrocatalytic properties and electrochemical stability of polyaniline and polyaniline modified with platinum nanoparticles in formaldehyde medium

We report the electro-oxidation of formaldehyde on polyaniline films modified with Pt nanoparticles (PANI-Pt films) in an aqueous sulfuric acid solution. The electrodeposition of Pt particles on the PANI matrix was found to promote a mass loss of the film, with a similar effect occurring after cycling the PANI films in the acidic medium containing formaldehyde. However, despite the electrochemical instability of PANI-Pt films, on films containing larger amounts of incorporated Pt particles, the oxidation of formaldehyde produces adsorbed CO species (CO_ads) at a lower positive potential than on bulk Pt. Our findings also indicate that electro-oxidation of CO_ads on the PANI-Pt film surface depends not only on the thickness of PANI film but also on the amount of Pt particles incorporated into the PANI matrix.     

Optical depth measurements by shadow-band radiometers and their uncertainties

Shadow-band radiometers in general, and especially the Multi-Filter Rotating Shadow-band Radiometer (MFRSR), are widely used for atmospheric optical depth measurements. The major programs running MFRSR networks in the United States include the Department of Energy Atmospheric Radiation Measurement (ARM) Program, U.S. Department of Agriculture UV-B Monitoring and Research Program, National Oceanic and Atmospheric Administration Surface Radiation (SURFRAD) Network, and NASA Solar Irradiance Research Network (SIRN). We discuss a number of technical issues specific to shadow-band radiometers and their impact on the optical depth measurements. These problems include instrument tilt and misalignment, as well as some data processing artifacts. Techniques for data evaluation and automatic detection of some of these problems are described.     

Synthesis and electrical properties of polymer composites with polyaniline nanoparticles

Nano-sized polyaniline (PANI) particles dispersed in aqueous solution were prepared using both poly(vinyl alcohol) (PVA) and poly(styrene sulfonic acid) (PSSA) as polymeric stabilizers. Size of the spherical PANI particle synthesized using PVA with a HCl dopant (PANI-HCl/PVA) was about 150 nm in diameter, and that with PSSA (PANI-PSSA) was about 50 nm, with a uniform size distribution. Doping level of the PANI-PSSA measured by UV–visible spectrometer was higher than that of PANI-HCl/PVA. The PVA based composite films using both PANI-HCl (PANI-HCl/PVA) and PANI-PSSA (PANI-PSSA/PVA) were prepared by a casting method for different PANI content and their electrical conductivities were measured. A percolation threshold of PANI concentration for conductivity of composite was found only around 10 wt.% of PANI for the PANI-PSSA/PVA, and furthermore, the PANI-PSSA/PVA became more conductive above the threshold point than PANI-HCl/PVA.     

Optical studies of polyaniline nanostructures

An investigative infrared spectroscopic study is undertaken of nano polyaniline (PANI) samples differing in size and morphology in order to explore the sensitivity of spectral behavior on these factors. IR spectroscopy is used for studying the changes in the interaction between polymeric molecules as parts of nanodimensional structures. A time dependent interfacial oxidative polymerization of aniline monomer is conducted in order to obtain the desired nano PANI samples in doped form. The morphological changes in samples so obtained are characterized using scanning electron microscopy (SEM). The SEM images of samples obtained using the time dependent interfacial polymerization show preferential formation of 1D nano/micro structures with dimensions varying with reaction time intervals, which is also confirmed by transmission electron microscopy (TEM). X-ray diffraction study is undertaken to assess the crystalline nature of the samples. The IR spectra and the X-ray diffraction pattern of samples reflect these morphological variations. A comparative study of bulk polyaniline sample obtained using standard procedures is also undertaken. Significant variations in the conductivity of different polyaniline samples are also observed. The 10 min sample shows significantly enhanced conductivity as compared to the 20 min and 24 h. PANI samples having well defined nanofibers.     

Water-soluble polyaniline with strong photoluminescence in physiological pH environment

Polyaniline (PANI) can show strong photoluminescence (PL) and well dispersed ability in water after simple refluxing with H₂SO₄ (sulfonated polyaniline, SPANI). This kind of fluorescent SPANI exhibits pH sensitive PL properties, especially, the strongest PL intensity is obtained in physiological pH environment (pH 7–8). The pH sensitive PL properties of SPANI are mainly attributed to the structure transition under different pH conditions.     

Synthesis and dispersion of yttria-stabilized zirconia (YSZ) nanoparticles in supercritical water

Yttria-stabilized zirconia (YSZ) nanoparticles were synthesized in supercritical water (SCW) without the use of mineralizers that are conventionally used to ensure basic conditions during synthesis. Process parameters were varied and their effect on the synthesis yield and particle morphology and composition were investigated. Conditions for synthesizing a stoichiometric YSZ nanopowder were identified. Dry YSZ particles collected in the continuous SCW process were redispersed in water in order to study their aggregation characteristics (including the size of agglomerates and the degree of agglomeration) in aqueous dispersions. Surface modification by the addition of polyethylenimine (PEI) was shown to result in stable dispersions of particles with average diameters between 50 nm and 100 nm.     

Synthesis of acicular iron oxide nanoparticles and their dispersion in a polymer matrix

An alternative forced hydrolysis approach for the synthesis of -FeOOH of varying dimensions was achieved. The -FeOOH particles were converted into -Fe₂O₃ in a colloidal process, which eliminated the agglomeration of -Fe₂O₃ particles. The acicular -Fe₂O₃ nanoparticles could be readily dispersed into an organic solvent. Preliminary studies have demonstrated that the dispersion of the -Fe₂O₃ nanorods in a polymer matrix is feasible leading to an organic-inorganic nanocomposite.     

Large-scale preparation of polyaniline nanospheres anchored with thiol-stabilized gold nanoparticles

Reported herein is the preparation of a new nanostructured composite consisting of PANI(SH) (where PANI(SH) is poly(aniline-co-4-aminothio phenol)) and gold nanoparticles (AuNPs)) via "seed"-induced bulk polymerization. The PANI(SH)-AuNPs composite was designated as PANI(SH)-Au-NS(P). The composite was characterized in terms of its morphology and structural, thermal, and electrochemical properties. The field emission scanning electron microscopy (FESEM) image of PANI(SH)-Au-NS(P) revealed the presence of PANI(SH) nanospheres (sizes: approximately 150-250 nm) with finely distributed AuNPs (approximately 10 nm). The usefulness of PANI(SH)-Au-NS(P) as an electrocatalyst towards the oxidation of methanol was tested.     

Photoacoustic flow measurements with gold nanoparticles

The hypothesis that quantitative blood flow measurements are feasible with the time-intensity based method in photoacoustic imaging using gold nanoparticles as contrast agent is experimentally tested. The in vitro results show good linearity between the measurements and the theory, thus suggesting the potential of relative photoacoustic flow measurements with gold nanoparticles.     

Radical-initiator-Induced solid-state polymerization of butadiyne nanocrystals in water and their dispersion stabilization

Butadiyne nanocrystals in water are usually polymerized by UV or gamma-ray irradiation to give polydiacetylene (PDA) nanocrystals. In this study, we confirmed that solid-state polymerization of 1,6-di(N-carbazolyl)-2,4-hexadiyne (DCHD) and 5,7-dodecadiyn-1,12-diyl bis[N-(butoxycarbonyl-methyl)carbamate] (4BCMU) could be stimulated by water-soluble radical initiators. The radical initiators used were potassium peroxodisulfate, three kinds of azo-type compounds and a redox initiator. In all cases, the solid-state polymerization was confirmed by color change into blue indicating that PDA modified by the radical residues at the end was formed. However, nanocrystal cohesion occurred especially when the concentration of the initiators was high or the dispersion was kept for a long time. In order to improve the dispersion stability, two kinds of surfactants, i.e., sodium dodecyl sulfate (SDS) or dodecyltrimethylammonium chloride (DTMAC), were added to the DCHD nanocrystal aqueous dispersion. As a result, when anionic SDS was added, the solid-state polymerization of nanocrystals proceeded without coagulation and quantitative conversion was confirmed for all initiators. Cationic DTMAC has no effect on dispersion stabilization. PDA nanocrystal surfaces in water are negatively charged in nature and electric interaction of nanocrystals with the cations results in decrease of surface charge and aggregation of nanocrystals.     

Optical roughness measurements with fringe projection

The characterization of roughness of engineering surfaces over an area is an important task for different applications as well as for manufacturing processes. The surface roughness is in particular an important factor in determining the performance of a workpiece. We demonstrate that the fringe projection technique allows very fast three-dimensional surface inspections. The inspection time for an entire measurement is reduced to less than 5 s with standard hardware. Based on a zoom stereo microscope setup, we demonstrate a modular measuring instrument. The magnification-dependent vertical resolution can be as high as 0.1 microm. The special properties for roughness measurements are demonstrated, especially the comparability with a tactile sensor and with other optical sensors, which is discussed in connection with amplitude parameters.     

Optical dispersion of radiation-grafted fluoro-polymer

Controlling the index of refraction of polymers plays an important role in their advanced nonlinear optical and electro-optical applications as well as in nanophotonics and biophotonic technologies. A radiation-induced grafting of acrylic acid (AAc) onto poly(tetrafluoroethylene-co-perfluorovinyl ether) (PFA) copolymer films was carried out to synthesize graft copolymer films using gamma-irradiation by the mutual method. The resulted films were characterized by Fourier transform infrared spectroscopy. The grafting process is associated with cross-linking through which a considerable change in the material refractive index is achieved. The linear refractive index, optical dispersion, and the quantum parameters of grafted poly(tetrafluoroethylene-co-perfluorovinyl ether) (PFA-g-PAAc) polymeric film are determined in a wide spectral range of 0.2-3 microm. The wavelength for zero material dispersion is evaluated. The oscillator, dispersion, and lattice energies, respectively, are calculated revealing the optical properties of the studied trunk polymeric substrate and the grafted ones. The origin of the optical properties has been discussed.     

Colloidal dispersion and rheology study of nanoparticles

The effects of dispersant ammonium poly(methacrylic acid) (PMAA-NH₄) and poly(acrylic acid) (PAA) on nano-Al₂O₃ particle dispersion have been investigated. Under the same dispersion viscosity, Al₂O₃ of 38 nm size requires 20 times more PAA dispersant than Al₂O₃ of 0.2 μm size but with only 9 times specific surface area increase. For the same carboxylic acid group to Al₂O₃ mole ratio, the PAA dispersant adsorbs more readily onto nano-Al₂O₃ particles than the PMAA-NH₄ dispersant and has better dispersion efficiency. Rheology measurements confirm the better dispersion and higher dispersion efficiency when PAA is used. Maximum solids loading has been predicted for each suspension based on the rheological data; this predication capability can serve as the important guidance for future dispersion designs.     

Synthesis of ultra-fine conducting polyaniline micro/nanotubes using fiber template and their NH3 gas sensitivity

We have recently fabricated ultra-fine conducting polyaniline (PANI) tubes with high gas sensitivity. This route includes two steps. Firstly, aniline polymerizes on the surface of a suitable fiber template prepared by electrospun nitrocellulose (NC). Then, the NC fiber template is dissolved and the ultra-fine PANI tubes are obtained. The structure of the conducting PANI tubes is characterized by IR spectrum and wide-angle X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results indicate that the PANI shows the shape of ultra-fine tubes with average inner diameter of 250-350 nm. The wall thickness of the ultra-fine PANI tubes increases with increasing the content of oxidant. The conductivity of the doped PANI tubes is about 6.9 x 10(-2) S. The results of gas sensitivity of the ultra-fine PANI tubes indicate that the PANI tubes can act as "electronic nose" to detect toxic NH3 gas below 20 ppm.     

Multi-holed clay nanotubes and their modification with a polyaniline nanolayer

A facile in situ mechanical–chemical polymerization method for synthesis of polyaniline/halloysite nanocomposites was developed. Electron micrographs of the composites showed novel multi-holed clay nanotubes modified with a porous polyaniline nanolayer. After removing clay tube cores, polyaniline nanotubes can be obtained. Moreover, novel multi-holed clay nanotubes were obtained after removing polymer shells.     

Optical vector network analyzer for single-scan measurements of loss, group delay, and polarization mode dispersion

We present a method for measuring the complete linear response, including amplitude, phase, and polarization, of a fiber-optic component or assembly that requires only a single scan of a tunable laser source. The method employs polarization-diverse swept-wavelength interferometry to measure the matrix transfer function of a device under test. We outline the theory of operation to establish how the transfer function is obtained. We demonstrate the enhanced accuracy, precision, and dynamic range of the technique through measurements of several components.     

Optical imaging-guided cancer therapy with fluorescent nanoparticles

The diagnosis and treatment of cancer have been greatly improved with the recent developments in nanotechnology. One of the promising nanoscale tools for cancer diagnosis is fluorescent nanoparticles (NPs), such as organic dye-doped NPs, quantum dots and upconversion NPs that enable highly sensitive optical imaging of cancer at cellular and animal level. Furthermore, the emerging development of novel multi-functional NPs, which can be conjugated with several functional molecules simultaneously including targeting moieties, therapeutic agents and imaging probes, provides new potentials for clinical therapies and diagnostics and undoubtedly will play a critical role in cancer therapy. In this article, we review the types and characteristics of fluorescent NPs, in vitro and in vivo imaging of cancer using fluorescent NPs and multi-functional NPs for imaging-guided cancer therapy.