Synthesis and thermal study of octahedral silver nano-plates in polyvinyl alcohol (PVA)

Octahedral silver nano-plates were synthesized from aqueous solution of silver nitrate and polyvinyl alcohol. The colloid formed is dried on glass plates by simple dip-coating method to inhibit the growth of the particles, and to analyze the samples. Samples were characterized by X-ray diffractometer, transmission electron microscope (TEM), thermo-gravimetric analysis (TGA), and differential scanning calorimetry (DSC) techniques. The UV–Vis absorption spectra of these silver nano-plates revealed a high intense plasmon absorption peak near 425 nm. In addition three emission peaks were observed when the excitation was fixed at 222 nm.     

Assessing the degradation profiles of a thermoresponsive polyvinyl alcohol (PVA)-based hydrogel for biomedical applications

Primary challenges associated with the design and success of polymeric biomedical devices are generally related to the control of the biomaterial in terms of degradability characteristics, sufficient processability characteristics, and required mechanical strength that may be altered during sterilization or manufacturing procedures. Polyvinyl alcohol-based thermoresponsive biomaterials provide a distinct advantage for biomedical applications as their physiochemical properties can be easily modified according to their desired use. In this work, we evaluated the thermal degradation characteristics of a polyvinyl alcohol (PVA)/polyethylene glycol (PEG)/polyvinylpyrrolidone (PVP) hydrogel that undergoes a steam sterilization autoclave cycle at 121°C to induce fluid-like behavior. FTIR was used to characterize the evolution of the area of the carbonyl region between 1800 and 1525 cm⁻¹. The carbonyl area increased at temperatures beyond 121°C which were used to accelerate the onset of degradation during both thermal oxidation and pyrolysis. The change in the carbonyl region was shown to correlate with respect to both temperature and time of exposure. The carbonyl region increased significantly in the presence of oxygen at temperatures above 150°C. Despite showing signs of thermal degradation at temperatures exceeding 150°C, our biomaterial was shown to be stable at 121°C during thermal degradation testing. Furthermore, bulk property analysis showed the hydrogel's mechanical and swelling properties were preserved even after being subject to multiple autoclave cycles beyond what would be experienced during a sterilization or clinical procedure.     

Novel antibacterial hybrid materials based on polyvinyl alcohol and mercaptopropyltriethoxysilane with embedded silver nanoparticles (PVA/AgNps/MPTES)

Hybrid materials based on polyvinyl alcohol (PVA) and mercaptopropyltriethoxysilane (MPTES) with embedded silver nanoparticles (AgNps) have been synthesized via a sol–gel method. Silver nanoparticles were obtained via thermal reduction in the presence of PVA as a stabilizer and reducing agent. The formation of silver nanoparticles within the PVA/MPTES matrix was proven by FTIR, XRD, and TEM analysis. The antibacterial activity of PVA/AgNps/MPTES materials was determined against strains belonging to Gram-positive and Gram-negative bacteria by disk diffusion and growth curve methods. The hybrid materials showed high antibacterial activity, which depends on the concentration of the silver nanoparticles.     

A thermal degradation mechanism of polyvinyl alcohol/silica nanocomposites

The thermal degradation mechanism of a novel polyvinyl alcohol/silica (PVA/SiO₂) nanocomposite prepared with self-assembly and solution-compounding techniques is presented. Due to the presence of SiO₂ nanoparticles, the thermal degradation of the nanocomposite, compared to that of pure PVA, occurs at higher temperatures, requires more reaction activation energy (E), and possesses higher reaction order (n). The PVA/SiO₂ nanocomposite, similar to the pure PVA, thermally degrades as a two-step-degradation in the temperature ranges of 300-450 °C and 450-550 °C, respectively. However, the introduction of SiO₂ nanoparticles leads to a remarkable change in the degradation mechanism. The degradation products identified by Fourier transform infrared/thermogravimetric analysis (FTIR/TGA) and pyrolysis-gas chromatography/mass spectrometric analysis (Py-GC/MS) suggests that the first degradation step of the nanocomposite mainly involves the elimination reactions of H₂O and residual acetate groups as well as quite a few chain-scission reactions. The second degradation step is dominated by chain-scission reactions and cyclization reactions, and continual elimination of residual acetate groups is also found in this step.     

NIR-SERS studies of DNA and DNA bases attached on polyvinyl alcohol (PVA) protected silver grass-like nanostructures

In this work, polyvinyl alcohol (PVA) protected silver grass-like nanostructure (PVA–Ag–GNS) with near infrared surface-enhanced Raman scattering (NIR-SERS) activity was prepared and employed to detect DNA and DNA bases. The PVA–Ag–GNS demonstrated high NIR-SERS activity and good optical reproducibility in the detection of adsorbates such as the case of crystal violet, DNA and DNA bases. By using of the tested molecule of thymine, the PVA–Ag–GNS shows a high enhancement factor (EF) of ∼10⁸. For NIR-SERS detection of DNA molecules, Raman signals from the DNA bases of guanine (630 cm⁻¹) and adenine (720 cm⁻¹) are greatly enhanced. For DNA molecules NIR-SERS detection, Raman signals from the DNA bases of guanine (630 cm⁻¹), adenine (720 cm⁻¹) and cytosine (1010 cm⁻¹) are greatly enhanced. The experimental results show that the NIR-SERS spectrum of DNA is dominated by guanine mode, which is followed by adenine and cytosine modes, respectively. Meanwhile, the NIR-SERS signal intensities of the DNA bases increase in the order of thymine (T) < cytosine (C) < adenine (A) < guanine (G). One can conclude that the adsorption strength of the DNA bases in DNA molecule with the silver surface is in the order T < C < A < G, which is different from that of the four DNA bases in individual molecule adsorbed on silver surface (T < A < G < C). On the other hand, the geometry optimization and calculated wavenumber of the complexes of adenine–Ag, guanine–Ag, cytosine–Ag and thymine–Ag for the ground states are performed with DFT, B3LYP functional and the LanL2DZ basis set. The calculated wavenumbers match well with the experimental results. According to our experiment and calculations, DNA base molecules adsorbed on silver surface via the intra-annular nitrogen atom which is adsorbed on the silver nanoparticle and formed metal–molecule complexes by the available lone pair.     

FT-IR/UATR and FT-IR transmission quantitative analysis of PBT/PC blends

Polymer blends are produced to achieve properties that pure polymers are unable to. The qualitative analysis of these blends is not always satisfactory to point out failures in the final product and, therefore, the determination of their content might be required. The aim of this study is to develop quantitative methodologies using Fourier transform infrared spectroscopy (FT-IR), reflection mode with the universal attenuated total reflectance accessory (UATR) and transmission techniques, for the determination of the content of each polymer present in the polymer blend poly (butylene terephthalate) (PBT) and polycarbonate (PC). FT-IR/UATR presented better results using the relative band (A₁₇₇₂/A₁₇₁₆). FT-IR/UATR presented error of 2.30%, which is a little higher than the accuracy limit of the spectrometer (≤2%), but still adequate for industrial applications.     

Influence of gamma-radiation on the behavior of humic acids from peat and tropical soil

HA samples obtained from sedimentary soil and peat in aqueous media were irradiated with -rays, in the dose range from 10 to 100 kGy, with the aim to study the chemical differences in the material before and after irradiation. The materials were analyzed by elemental analysis, UV/Vis spectroscopy (E₄/E₆ ratio), functional groups content, gel permeation chromatography (GPC) and IR spectroscopy. Gas chromatography was utilized to analyze the generated gases. Humic acids from peat and from soil are quite different. After irradiation an increasing in the average molecular weight was observed which depends on the material characteristics. There was observed also a release of CO₂ upon irradiation. By infrared spectroscopy, with the help of computer simulations, the characteristic bands of ester C=O and C–O stretchings reinforces the contribution of carboxylic groups in the condensation process.     

Peroxide induced crosslinking and degradation of polyvinyl chloride

Peroxide induced crosslinking and degradation of polyvinyl chloride (PVC) were experimentally investigated using an on-line electron spin resonance (ESR) spectroscopy technique. The reaction variables included temperature, peroxide type and concentration. A single line ESR spectrum was observed with its peak-to-peak width decreasing during the reaction. The mechanism involved in the reaction was elucidated based on the radical information. The radical concentration versus reaction time profile exhibited two distinct regions: the chemically initiated reaction continued by the thermal initiation. The addition of peroxide induced and significantly enhanced the thermal initiated crosslinking and degradation. The radical concentration data coupled with the extent of dehydrochlorination gave an estimate of the rate constant of polyene propagation. A significant decrease of the rate constant was observed during the reaction. The gel content and swelling ratio were also measured to provide additional information to the reaction process. The initial gelation rate increased with the increase of temperature and/or peroxide concentration. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 851–860, 1998     

Electrically induced gel-sol transition of polyvinyl alcohol/polyacrylamide semi-interpenetrated hydrogels

Polyvinyl alcohol/polyacrylamide semi-interpenetrated hydrogels were prepared via freeze-thaw process. When a 20 V of DC was applied across the gels, the gels with lower polyacrylamide content underwent a contraction or partly turned into solution, while for the gels with higher polyacrylamide concentration, a complete gel-sol transition was observed in a short time.     

Interactions between rotenone and humic acids by means of FT-IR and fluorescence spectroscopies

The aim of this work was to ascertain, on a comparative basis, the compositional, structural and functional differences occurring between three humic acids (HAs), HA S1 (isolated from a Mediterranean brown soil), HA S2 (isolated from a Bavarian brown soil), and HA SR (a Suwannee River standard aquatic HA, purchased from IHSS), and to investigate the influence of their intrinsic properties on the types of binding mechanisms toward the pesticide rotenone. Original HAs and their corresponding HA–rotenone products, obtained by two different interaction protocols, were analyzed for elemental and functional group composition, and spectroscopic techniques, such as Fourier-transform infrared (FT IR) with Fourier self-deconvolution (FSD) and fluorescence both in the single-scan and in three-dimensional modes. The HA S1 sample appeared to be characterized by a greater aromaticity degree and lower polarity with respect to the HA S2, featured by a mixed aromatic/aliphatic character, whereas mainly aliphatic and acidic resulted the HA SR. The data obtained suggested that the low water-soluble, non-polar pesticide rotenone resulted preferentially adsorbed onto HAs by hydrophobic interaction, that was the prevailing mechanism in the order HA S1 > HA S2 >>> HA SR, whereas hydrogen bonds resulted predominant in the opposite order.     

Swelling characteristics and application of gamma-radiation on irradiated SBR-carboxymethylcellulose (CMC) blends

Blends of styrene butadiene rubber (SBR) with varying loading degree from 60 wt% to 100 wt% of carboxymethylcellulose (CMC) have been prepared. Gamma radiation vulcanization of prepared blends was carried out with doses varying between 50 kGy and 250 kGy. Mechanical properties, namely, tensile strength (Ts), elongation at break (E_b) and hardness were followed up as a function of loading degree of CMC and gamma irradiation dose. Moreover, physical properties, specifically swelling number (SN) and gel fraction % (GF%) were undertaken. Results obtained showed an improvement in mechanical as well as in physical properties with increasing either CMC content or dose of irradiation. Thermal properties namely thermo gravimetric analysis (TGA) was carried out.     

Phase behavior and properties of polyvinyl alcohol/gelatin blends with novel pH‐dependence

A novel change of phase behavior and properties of polyvinyl alcohol (PVA)/gelatin blends as a function of pH was reported. The PVA/gelatin blends were found to be completely miscible in acidic condition (pH < 4), partially miscible in basic condition (pH > 8), and immiscible in neutral condition (pH was ca. 6). As a result, the membranes cast from acidic condition showed the highest tensile strength and the lowest alcohol vapor permeation (AVP) rate; those obtained from neutral condition showed the lowest tensile strength and highest AVP rate; the properties of membranes cast from basic condition lay in between. The interaction between PVA and gelatin was investigated via Fourier transform infrared spectrum (FTIR), differential scanning calorimetry (DSC), and Zetasizer measurement. The novel pH‐dependence of the blends was ascribed to the protonation of amino groups of gelatin in acidic condition, which resulted in a strong electrostatic attraction between ? NH of gelatin and ? OH of PVA. The partial miscibility in basic condition was due to the ionization of carboxyl groups of gelatin, which caused a stretching of gelatin via electrostatic repulsive force and a breakage of the H‐bonding among the molecular chains, leading to a limited interaction between PVA and gelatin and forming a partially miscible blend. In neutral conditions, there were almost no charges (very limited protonation and ionization) at the weak polyampholyte gelatin, and the strong H‐bonding among gelatin molecules themselves or PVA molecules themselves caused the phase separation between gelatin and PVA. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 239–247, 2009     

Radiation degradation of blends polypropylene/poly(ethylene-co-vinyl acetate)

Physicochemical and mechanical characteristics of irradiated electron beam polypropylene/ethylene-vinyl acetate (PP/EVA) blends and individual components were investigated. Although oxidation of alkyl radicals in the blends proceeds slower than in PP, the total oxidation effect monitored by content of oxygen-containing groups shows opposite tendency. Blending with EVA does not affect degree of PP crystallinity. The enthalpy of melting and crystallization of the blends reveal phase separation between dispersed copolymer and PP matrix. In all studied blends, degradation prevails over tendency of EVA to cross-linking.     

Photo-oxidative degradation of polyvinyl alcohol and measurement of thermally stimulated current

An investigation was made of the correlation between changes in the chemical structure of polyvinyl alcohol during photo-oxidation and a thermally stimulated current. Photo-oxidation was initiated by dehydration and greatly accelerated as a result of chain scission, which resulted from the formation of carbonyl groups of ester, aldehyde, ketone and carboxylic acid types. Two main peaks of thermally stimulated current were observed at 220 and 250 K in photo-oxidized polyvinyl alcohol. It became clear that these two peaks, resulting from depolarization of dipoles, correspond to an increase in the content of carbonyl groups and a decrease in the content of hydroxyl group, respectively.     

The degradation in solid state of polyvinyl alcohol by gamma-irradiation

The viscosity of polyvinyl alcohol (PVA) (Powder form) falls after irradiation. Gel does not occur after a dosage of above 1000 kGy. The G-values for scission under various conditions were measured. Irradiation of PVA brings about an increase in the intensity of a number of bands in the UV spectrum. It is shown that formation of unsaturated bonds and carbonyl groups occur under irradiation. The other one of radiolysis products is organic acid. After irradiation, the hydrolysis degree is unchanged.     

Capillary zone electrophoretic (CZE) study of uranium(VI) complexation with humic acids

The interaction of UO₂ ²⁺ with various humic acids (HA's) has been studied by capillary zone electrophoresis (CZE). The experiments were done in 10 mM acetate buffer with pH 3.3 and 4.0, to avoid hydrolysis of uranium. It was found that in slightly acidic media and low HA concentration (<3 mM), two complexes with uranium(VI) are formed by fast kinetics and uranyl migrates as cationic species. Electrophoretic mobilities are decreasing with the increasing HA/uranium ratio and a low soluble neutral compound is also formed. In addition, it was found that at HA concentrations higher than 3 mM negatively charged species are formed. Similar results were obtained for HA's of different origin (soil, peat, coal derived, IHSS standards). Conditional stability constants of the complexes UO₂ ²⁺-HA for Fluka I HA, were estimated to be log ₁ = 4.18±0.06 and log ₂ = 7.28±0.18.     

Structure and compatibility of poly(vinyl alcohol)-silk fibroin (PVA/SA) blend films

The structure and compatibility of poly(vinyl alcohol)-silk fibroin (PVA/SF) blend films were analyzed by differential scanning calorimetry (DSC), thermomechanical (TMA) and thermogravimetric (TGA) analysis, x-ray diffractometry, and scanning (SEM) and transmission (TEM) electron microscopy. DSC curves of PVA/SF blend films showed a major endothermic peak at 220°C, along with a peak at 280°C. These endotherms were assigned to the thermal decomposition of the ordered PVA elements and to the thermal degradation of silk fibroin, respectively. The PVA/SF blends behaved in a manner intermediate to the pure components, as suggested by both contraction expansion and sample weight retention properties recorded by TMA and TGA measurements. The IR absorption spectra of the blends were identified as purely a composite of the absorption bands characteristic of both PVA and SF pure polymers. The X-ray diffraction patterns of PVA/SF blends showed overlapping spacing due to PVA and SF. A dispersed phase formed by spherical particles of 3–7 μm diameter was observed by SEM and TEM. All these findings suggest that PVA and SF are incompatible. © 1994 John Wiley & Sons, Inc.     

Structural and electrical properties of polyvinyl alcohol (PVA):Methyl cellulose (MC) based solid polymer blend electrolytes inserted with sodium iodide (NaI) salt

This paper studies the structural and electrical properties of solid polymer blend electrolytes based on polyvinyl alcohol (PVA) and methylcellulose (MC) incorporated with sodium iodide (NaI). The polymer electrolyte films were assembled through a solution casting technique. The host matrix, which is doped with different NaI salt concentrations between 10 and 50 wt%, utilizes the most amorphous blend compositions (60 wt% Polyvinyl alcohol and 40 wt% methylcellulose). The structural behaviour of the electrolyte films was examined utilizing X-ray diffraction (XRD) and Fourier transformation infrared (FTIR) techniques. The semi crystalline nature of PVA:MC with inserted NaI was derived from the X-ray diffraction studies, while the XRD analysis suggests that the highest ion conductive sample displays the minimum crystalline nature. The interaction between polymer blends and inserted salt was conceived from the FTIR investigation. Shifting of peaks and variation in the intensity of FTIR bands was detected. To investigate the structural properties and calculate the degree of crystallinity of the films, the (XRD) technique was employed, while electrical impedance spectroscopy (EIS) was utilized for studying the conductivity of the samples. In order to comprehend all of the electrical properties of the ion-conducting systems, the EIS outcome of each electrolyte was matched with Equivalent Electrical Circuits (EEC) s. Ion transport parameters including mobility, carrier density and diffusion are well assessed for the samples and the dielectric properties were compared with the conductivity measurement. At lower frequencies, the dielectric constant was elevated and dielectric loss was detected. Loss tangent and electric modulus plots were used to study the relaxation nature of the samples. The highest ambient temperature conductivity of PVA loaded 50 wt% of NaI was determined to be 1.53 × 10⁻⁵ S/cm. The loss tangent relaxation peak shifts towards high-frequency side which indicates the decrease of relaxation time and faster ion dynamics.