Polymer Blending as a Novel Approach for Tuning the SPR Peaks of Silver Nanoparticles.

In the present work, a novel method is exhibited for tuning the surface plasmon resonance (SPR) peaks of silver nanoparticles based on chitosan-Poly(vinyl alcohol) blend polymer nanocomposites. Silver nanoparticles were synthesized by in situ method through the chitosan host polymer. The absence of crystalline peaks of PVA in the blend system indicated the occurrence of miscibility between CS and PVA polymers. The UV⁻vis spectra of CS:AgNt samples shows SPR bands with weak intensity. Obvious tuning in SPR peaks of silver nanoparticles occurred when different amounts of PVA polymer incorporated to the CS:AgNt system. The appearance of distinguishable crystalline peaks of Ag° nanoparticles at 2θ = 38.6° and 2θ = 44.2° in the blend system reveals the role of polymer blending in the enhancement of SPR peaks of silver nanoparticles. Silver nanoparticles synthesized in this work with enhanced SPR peaks are important in various applications and areas such as optoelectronic devices. The TEM images show dispersed silver nanoparticles. The dielectric constant of PVA is higher than that of chitosan. The result of dielectric constant study validates the Mie model which reveals the fact that the dielectric constant of the surrounding material has a great effect on the SPR peak intensity of nanoparticles.

Effect of PVA Blending on Structural and Ion Transport Properties of CS:AgNt-Based Polymer Electrolyte Membrane.

In this work, the role of poly(vinyl alcohol) (PVA) blending on structural and electrical properties of chitosan:silver nitrate systems is studied. The X-ray diffraction (XRD) results show that the crystalline phase of chitosan (CS) is greatly scarified by silver nitrate (AgNt) salt. The crystalline domain of CS:AgNt is more broadened at 10 wt % of PVA. The spike and semicircular arcs can be separated in impedance plots. At high temperatures, the spike regions remained. The direct current (DC) conductivity was calculated from the bulk resistance obtained from the impedance plots. The dielectric constant and DC conductivity versus PVA content exhibited similar behavior. The maximum DC conductivity at ambient temperature was 1.1 × 10-6 S/cm for 10 wt % of PVA. The DC ionic conductivity increased to 9.95 × 10-5 S/cm at 80 °C. Above 10 wt % of PVA, the drop in DC conductivity and dielectric constant were observed due to the increase in viscosity. Shifting of relaxation peaks towards the lower frequency revealed the increase of resistivity of the samples. The linear increase of DC conductivity versus 1000/T indicated that ion transport followed the Arrhenius model. The incomplete semicircular arc in Argand plots indicated the non-Debye type of relaxation process. The Argand plots were used to distinguish between conductivity relaxation and viscoelastic relaxation. Three regions were distinguished in the alternating current (AC) spectra of the blend electrolyte samples. The plateau region in AC spectra was used to estimate the DC conductivity. The estimated DC conductivity from the AC spectra was close to those calculated from the impedance plots.

From Insulating PMMA Polymer to Conjugated Double Bond Behavior: Green Chemistry as a Novel Approach to Fabricate Small Band Gap Polymers.

Dye-doped polymer films of Poly(methyl methacrylate) PMMA have been prepared with the use of the conventional solution cast technique. Natural dye has been extracted from environmentally friendly material of green tea (GT) leaves. Obvious Fourier transform infrared (FTIR) spectra for the GT extract were observed, showing absorption bands at 3401 cm-1, 1628 cm-1, and 1029 cm-1, corresponding to O⁻H/N⁻H, C=O, and C⁻O groups, respectively. The shift and decrease in the intensity of the FTIR bands in the doped PMMA sample have been investigated to confirm the complex formation between the GT dye and PMMA polymer. Different types of electronic transition could be seen in the absorption spectra of the dye-doped samples. For the PMMA sample incorporated with 28 mL of GT dye, distinguishable intense peak around 670 nm appeared, which opens new frontiers in the green chemistry field that are particularly suitable for laser technology and optoelectronic applications. The main result of this study showed that the doping of the PMMA polymer with green tea dye exhibited a strong absorption peak around 670 nm in the visible range. The absorption edge was found to be shifted towards the lower photon energy for the doped samples. Optical dielectric loss and Tauc's model were used to estimate the optical band gaps of the samples and to specify the transition types between the valence band (VB) and conduction band (CB), respectively. A small band gap of around 2.6 eV for the dye-doped PMMA films was observed. From the scientific and engineering viewpoints, this topic has been found to be very important and relevant. The amorphous nature of the doped samples was found and ascribed to the increase of Urbach energy. The Urbach energy has been correlated to the analysis of X-ray diffraction (XRD) to display the structure-properties relationships.

Effect of High Salt Concentration (HSC) on Structural, Morphological, and Electrical Characteristics of Chitosan Based Solid Polymer Electrolytes.

Chitosan (CS) films doped with sodium triflate (NaTf) were prepared by the solution cast technique. The structural and morphological behaviors of the samples were examined by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The XRD patterns were deconvoluted to estimate the degree of crystallinity of the samples. The SEM micrograph showed the crystalline structure of the sample contained 50 wt % of NaTf salt. The disappearance of broad peaks of chitosan at 2θ ≈ 21° and 2θ ≈ 32° confirmed the occurrence of ion association at 50 wt % of NaTf salt. In impedance plots, a low frequency spike region and a high frequency semicircle, were distinguishable for low salt concentrations. The highest ambient temperature direct current (DC) electrical conductivity obtained for CS:NaTf was found to be 2.41 × 10-4 S/cm for the sample containing 40 wt % of NaTf salt. The role of lattice energy of salts on DC ionic conductivity was also discussed. The temperature dependence of DC conductivity was found to follow the well-known Arrhenius relationship. From the alternating current (AC) conductivity spectra, three distinct regions were recognized for the samples with NaTf salt concentration ranging from 10 wt % to 30 wt %. The plateau region of AC spectra was used to estimate the DC conductivity.

Synthesis of Polymer Nanocomposites Based on [Methyl Cellulose](1-x):(CuS)x (0.02 M ≤ x ≤ 0.08 M) with Desired Optical Band Gaps.

In this paper, the sample preparation of polymer nanocomposites based on methyl cellulose (MC) with small optical bandgaps has been discussed. Copper monosulfide (CuS) nanoparticles have been synthesized from the sodium sulphide (Na2S) and copper chloride (CuCl2) salts. Distinguishable localized surface resonance plasmon (LSRP) absorption peaks for CuS nanoparticles within the 680⁻1090 nm scanned wavelength range were observed for the samples. An absorption edge (Ed) was found to be widely shifted to a lower photon energy region. A linear relationship between the refractive index of the samples and the CuS fraction was utilized to describe the distribution of the particle. The optical bandgap of MC was reduced from 6.2 to 2.3 eV upon the incorporation of 0.08 M of CuS nanoparticles. The optical dielectric loss, as an alternative method, was used successfully to estimate the optical bandgap. Moreover, the electronic transition type was identified by using Tauc's extrapolation method. The plots of the optical dielectric constant and energy bandgap as a function of the CuS concentration were utilized to examine the validity of the Penn model. For the nanocomposite samples, the Urbach energy was found to be increased, which can be evidence for a large possible number of bands-to-tail and tail-to-tail transitions. However, from the X-ray diffraction (XRD) analysis, it was also found that the synthesized CuS nanoparticles disrupted the crystallinity phase of the MC polymer. Finally, fourier transform infrared (FTIR) spectroscopy for the samples was also performed. Significant decreases of transmittance intensity as well as band shifting in the FTIR spectra were observed for the doped samples.

Role of Ion Dissociation on DC Conductivity and Silver Nanoparticle Formation in PVA:AgNt Based Polymer Electrolytes: Deep Insights to Ion Transport Mechanism.

In this study, the role of ion dissociation on formation of silver nanoparticle and DC conductivityin PVA:AgNO3 based solid polymer electrolyte has been discussed in detail. Samples of silver ion conducting solid polymer electrolyte were prepared by using solution cast technique. Absorption spectroscopy in the ultraviolet⁻visible (UV⁻Vis) spectral region was used to investigate the formation of silver nanoparticles. Broad and sharp peaks due to plasmonic silver nanoparticles subjected to ion dissociation have been observed. The influence of dielectric constant on the intensity of surface plasmonic resonance (SPR) peaks attributed to silver nanoparticles was discussed. From impedance plots, the diameter of high frequency semicircle was found to be decreased with increasing salt concentration. The DC conductivity in relation to the dielectric constant was also explained. From the AC conductivity spectra, the dc conductivity was estimated to be close to that calculated from the bulk resistance. The temperature dependence of the DC conductivity was studied and found to follow Arrhenius equation within two distinguished regions. The AC conductivity at different temperatures has been studied to comprehend the ion conduction mechanism. The AC conductivity against frequency was found to obey the universal power law of Jonscher. Three distinct regions were recognized from the spectra of AC conductivity. The frequency exponent (S) was calculated for the dispersive region of the measured AC conductivity spectra. Various models were discussed to explain the behavior of S value with temperature. The behavior of S value with temperature was then used to interpret the DC conductivity pattern against 1000/T. Finally, from the comparison of calculated activation energy (Ea) and maximum barrier height (Wm), deep insights into ion conduction mechanism could be grasped.