Effect of gamma irradiation on the structural and optical properties of PVA/CdS nanocomposite films prepared by ex-situ technique

ABSTRACT

For a comprehensive understanding of the PVA/CdS nanocomposite properties, it is essential to select the suitable method for their preparation as well as elucidate the interfacial interactions, which still need support. CdS nanoparticles have been prepared by thermolysis method under the flow of nitrogen. Rietveld refinement of x-ray data shows that all the CdS samples have both cubic and hexagonal structures. Then PVA/CdS films were prepared by ex-situ technique. Samples from PVA/CdS nanocomposite have been irradiated with gamma doses in the range 10–120?kGy. The implanting of CdS NPs into PVA matrix was confirmed by XRD hand in hand with UV–vis and FTIR spectroscopic techniques. UV/VIS absorption spectra confirm the formation of hybridized film CdS/PVA nanocomposite with a refractive index in the range of 1.32–1.48 (at 500?nm). UV/VIS measurements were also used in calculating different optical parameters such as refractive index, extinction coefficient and optical band gap energy. Additionally, Tauc’s relation was used to determine the type of electronic transition. It is found that the gamma irradiation in the dose range 30-90?kGy led to a more compact structure of PVA/CdS nanocomposite and causes proper dispersion of CdS nanoparticles in the PVA matrix. This led to the formation of coordination reaction between OH of PVA and CdS nanoparticles, resulted in an increase in refractive index and the amorphous phase. Also, the gamma irradiation reduces the optical energy gap from 4.53 to 2.19?eV, and accompanied with an increase in the Urbach energy from 2.28 to 4.46?eV, at that dose range which could be attributed to the increase in structural disorder of the irradiated PVA/CdS nanocomposites due to crosslinking. Further, the color intensity ΔE, which is the color difference between the non-irradiated sample and the irradiated ones, was increased, from 0 to 10.8, with increasing the gamma dose, convoyed by an increase in the red and yellow color components.     

Effect of electron beam irradiation on the structural,thermal and optical properties of poly(vinyl alcohol) thin film

Poly(vinyl alcohol) (PVA) polymer was prepared using the casting technique. The obtained PVA thin films have been irradiated with electron beam doses ranging from 20 to 300 kGy. The resultant effect of electron beam irradiation on the structural properties of PVA has been investigated using X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR), while the thermal properties have been investigated using thermo-gravimetric analysis and differential thermal analysis (DTA). The onset temperature of decomposition T ₀ and activation energy of thermal decomposition E _a were calculated, results indicate that the PVA thin film decomposes in one main weight loss stage. Also, the electron beam irradiation in dose range 95–210 kGy led to a more compact structure of the PVA polymer, which resulted in an improvement in its thermal stability with an increase in the activation energy of thermal decomposition. The variation of transition temperatures with electron beam dose has been determined using DTA. The PVA thermograms were characterized by the appearance of an endothermic peak due to melting. In addition, the transmission of the PVA samples and any color changes were studied. The color intensity Δ E was greatly increased with increasing electron beam dose, and was accompanied by a significant increase in the blue color component.     

Polyacetylene nanoparticles-based preparation of polyaniline nanofibers

Abstract  

A conjugated polymer polyacetylene (PA) nanoparticles-based preparative strategy toward doped polyaniline (PANI) nanofibers has been demonstrated for the first time, carried out by chemical oxidative polymerization of aniline under rapid stirring using ammonium persulfate as the oxidant in acidic aqueous media in the presence of dodecylsulfate (SDS)-stabilized PA nanoparticles. It is found that only PANI nanoparticulates are formed when the synthesis is performed in the absence of PA nanoparticles. The optical properties and the electronic conductivity of the resulting doped nanofibers and the corresponding dedoped products were studied and the influence of the amount of PA nanoparticles used on the morphologies of PANI nanostructures was also investigated. A possible mechanism is proposed to explain the formation of the PANI nanofibers.     

与掺杂浓度相关的ZnS∶Mn纳米粒子的发光性质

采用溶胶法制备了Mn掺杂的ZnS纳米粒子,探讨了掺杂离子浓度对ZnS∶Mn纳米粒子的晶体结构和发光性质的影响。通过X射线衍射（XRD）对样品的结构进行了表征,结果表明：所制备的ZnS∶Mn纳米粒子为立方闪锌矿结构,其在Mn离子的掺杂浓度达到6%时不发生分相,但随着掺杂浓度的增加,纳米粒子的平均粒径会减小。光致发光光谱和荧光光谱的结果表明：通过改变掺杂离子的浓度可实现对ZnS∶Mn纳米粒子590 nm附近荧光发射波长的调节。此外,研究了温度对纳米粒子形貌和发光性质的影响。高分辨透射电子显微镜（HRTEM）观察发现,经过50℃陈化1 h后的ZnS∶Mn样品的平均粒径增大约为20 nm,且加热陈化有利于ZnS∶Mn纳米粒子中Mn2＋在590 nm处产生荧光。     

Preparation and property of polyvinyl alcohol-based film embedded with gold nanoparticles

Gold nanoparticles were prepared by a simple heat-treated method using polyvinyl alcohol (PVA) as reducing and stabilizing agent in this article. UV/Vis spectroscopy was used to monitor the preparation. The formation of a sharp band at ~530 nm in the UV/Vis spectra and morphological characters revealed by transmission electron microscopy indicated the generation of Au nanoparticles. The PVA film embedded with Au nanoparticles was prepared by flow casting method and characterized by thermogravimetric analysis, differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectra, and X-ray photoelectron spectroscopy. The results showed that Au nanoparticles embedded in PVA film can improve the thermal stability of the film under investigation, leading to interesting technological applications.     

Modification induced by gamma irradiation in Bayfol CR 1-4 polycarbonate

Bayfol CR 1-4 polycarbonate is a class of polymeric solid state nuclear track detector which has many applications in various radiation detection fields. Samples from sheets of Bayfol have been irradiated with gamma doses ranging from 100 to 620 kGy. The structural modifications in the gamma-irradiated Bayfol samples have been studied as a function of dose, using different characterization techniques such as X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, intrinsic viscosity and refractive index. The results indicate that the carbonyl group (C?O) degraded under irradiation up to 200 kGy. This degradation, reported by FTIR spectroscopy enhanced the degree of ordering in the degraded samples as revealed by the XRD technique. Above 200 and up to 620 kGy, cross-linking is achieved, leading to an increase in the intrinsic viscosity from 0.41 to 0.78 at 35°C, indicating an increase in the average molecular mass. On the other hand, the resultant effect of gamma irradiation on the thermal properties of Bayfol has been investigated using thermo-gravimetric analysis, results indicating that the gamma irradiation in the dose range 200–620 kGy led to a more compact structure of Bayfol polymer, which resulted in an improvement in its thermal stability with an increase in the activation energy of thermal decomposition due to cross-linking. In addition, the V–I characteristics of the polymer samples were performed, results indicated that at higher voltage, the conduction mechanism of Bayfol CR 1-4 was identified as the Poole–Frenkel type.     

Effective thermal conductivity of condensed polymeric nanofluids (nanosolids) controlled by diffusion and interfacial scattering

Thermal properties of polymeric nanosolids, obtained by condensing the corresponding nanofluids, are investigated using photothermal techniques. The heat transport properties of two sets of polyvinyl alcohol (PVA) based nanosolids, TiO₂/PVA and Cu/PVA, prepared by condensing the respective nanofluids, which are prepared by dispersing nanoparticles of TiO₂ and metallic copper in liquid PVA, are reported. Two photothermal techniques, the photoacoustic and the photopyroelectric techniques, have been employed for measuring thermal diffusivity, thermal conductivity and specific heat capacity of these nanosolids. The experimental results indicate that thermal conduction in these polymer composites is controlled by heat diffusion through the embedded particles and interfacial scattering at matrix–particle boundaries. These two mechanisms are combined to arrive at an expression for their effective thermal conductivity. Analysis of the results reveals the possibility to tune the thermal conductivity of such nanosolids over a wide range using the right types of nanoparticles and right concentration.     

ZnS纳米微粒的形貌结构对其光学特性的影响

报道在聚乙烯醇（PVA）膜上采用离子络合法镶嵌的ZnS纳米微粒的形貌结构与光学特性。透射电子显微镜结果表明，在聚乙烯醇膜中的ZnS纳米微粒分布比较均匀，粒径可控制在2－7nm的范围内；电子衍射分析表明，ZnS纳米微粒具有类似于β－ZnS体材料的晶体结构。室温下的光发射峰的位置在414～440nm范围内。着重分析了ZnS纳米形貌结构与其发射波长和强度之间的关系，并探讨了其不同的发射机理。     

CdS/ZnS core–shell nanoparticles in arachidic acid LB films

Core–shell CdS/ZnS nanoparticles in arachidic acid film were prepared through a novel Langmuir–Blodgett (LB) approach. Post-deposition treatment of the precursor LB multilayers of cadmium arachidate with H₂S gas followed by intercalation of Zn²⁺ ions and further sulfidation result in the formation of CdS/ZnS nanoparticles in the LB film. The formation of these nanoparticles and resulting changes in layered structures were studied by FTIR and X-ray reflection measurements. The optical properties were studied using UV–vis absorption and photoluminescence spectroscopy. A red-shift in the absorption spectrum and enhancement of CdS excitonic emission together with reduction of surface states emission suggest that after the intercalation step, a thin layer of ZnS surrounds the CdS nanoparticles, thus forming a core–shell structure. Subsequent to the second sulfidation, a further red-shift in absorption suggests the formation of a thicker ZnS coating on CdS. Electron diffraction of CdS nanoparticles coated with thicker ZnS showed the diffraction patterns of only ZnS, as expected for core–shell structures.     

Effect of gamma irradiation on hydrothermally synthesized barium titanate nanoparticles

The effect of gamma irradiation on hydrothermally synthesized BaTiO₃ nanoparticles has been investigated. Gamma irradiation was carried out at room temperature from 0, 50, 100, 150, 200?kGy to a maximum dose up to 250?kGy, source being ⁶⁰Co gamma radiations. The structure, size and chemical changes of the BaTiO₃ were studied using X-ray diffraction, Fourier-transform infrared spectrophotometry (FTIR) techniques and scanning electron microscopy (SEM). The optical band gap has been computed by UV–Visible spectroscopy data. From the results obtained, it is evident that the gamma irradiation increases the crystallinity, whereas the particle size of BaTiO₃ nanoparticles is altered. UV–Visible spectroscopy shows a noticeable change in the energy band gap due to gamma irradiation. Significant changes in anharmonicity constant computed using FTIR data due to irradiation has been observed. SEM shows the size and deviation from uniformity of particles.     

X-ray irradiation-induced structural modifications in PM-355 polymeric nuclear track detector film

Samples from sheets of the polymeric material PM-355 have been exposed to X-rays from a 50 kV X-ray tube in the dose range of 10–300 kGy. The resultant effect of X-ray irradiation on the structural properties of PM-355 has been investigated using different techniques such as X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Vickers hardness and refractive index measurements. The results indicate that the X-ray irradiation of PM-355 in the dose range of 10–20 kGy causes initially chain scission. Above 20 and up to 100 kGy, the active free radicals produced from scission contribute to chemical reactions that lead to the crosslinking. Thus, the X-ray irradiation in the dose range of 20–100 kGy leads to a more compact structure of the PM-355 polymer, resulting in an enhancement of its Vickers hardness and refractive index. Moreover, the irradiation in the dose range of 100–300 kGy leads to the predominance of the degradation. This degradation is reported by FTIR spectroscopy and enhances the degree of ordering in the degraded samples as revealed by XRD technique. Additionally, it decreases both the Vickers hardness and refractive index of the PM-355 samples.     

Thermal and optical properties of electron beam irradiated cellulose triacetate

Samples from Cellulose triacetate (CTA) sheets were irradiated with electron beam in the dose range 10–200 kGy. Non-isothermal studies were carried out using thermogravimetric analysis (TGA) to obtain the activation energy of thermal decomposition for CTA polymer. The CTA samples decompose in one main break down stage. The results indicate that the irradiation by electron beam in the dose range 80–200 kGy increases the thermal stability of the polymer samples. Also, the variation of melting temperatures with the electron dose has been determined using differential thermal analysis (DTA). The CTA polymer is characterized by the appearance of one endothermic peak due to melting. It is found that the irradiation in the dose range 10–80 kGy causes defects generation that splits the crystals depressing the melting temperature, while at higher doses (80–200 kGy), the thickness of crystalline structure (lamellae) is increased, thus the melting temperature increases. In addition, the transmission of these samples in the wavelength range 200–2500 nm, as well as any color changes, were studied. The color intensity ΔE* was greatly increased on increasing the electron beam dose, and accompanied by a significant increase in the blue color component.      

Ultrasonic-assisted synthesis of polyvinyl alcohol/phytic acid polymer film and its thermal stability,mechanical properties and surface resistivity

In this paper, polyvinyl alcohol/phytic acid polymer (PVA/PA polymer) was synthesized through esterification reaction of PVA and PA in the case of acidity and ultrasound irradiation and characterized, and PVA/PA polymer film was prepared by PVA/PA polymer and characterized, and the influence of dosage of PA on the thermal stability, mechanical properties and surface resistivity of PVA/PA polymer film were researched, and the influence of sonication time on the mechanical properties of PVA/PA polymer film was investigated. Based on those, it was concluded that the hydroxyl group on the chain of PVA and the phosphonic group on PA were connected together in the form of phosphonate bond, and the hydroxyl group on the chain of PVA were connected together in the form of ether bond after the intermolecular dehydration; in the meantime, it was also confirmed that PVA/PA polymer film prepared from 1.20 mL of PA not only had the high thermal stability and favorable ductility but also the low surface resistivity in comparison with PVA/PA polymer film with 0.00 mL of PA, and the ductility of PVA/PA polymer film was very sensitive to the sonication time.     

Effect of annealing temperature on optical and magnetic properties of Cr doped ZnS nanoparticles

ZnS:Cr (3 at.%) nanoparticles were synthesized by chemical co-precipitation method using EDTA as capping agent. The samples were annealed in air for 3 h in steps of 100 °C in the temperature range of 200–700 °C. The effect of annealing temperatures on the structural and photoluminescence properties of Cr doped ZnS nanoparticles was investigated using X-ray Diffraction (XRD), a Scanning Electron Microscope (SEM), Energy Dispersive X-ray spectroscopy (EDS), Diffuse Reflectance Spectra (DRS), Vibrating Sample Magnetometer (VSM) and Photoluminescence (PL) techniques. EDS spectra confirmed the presence of Cr in the samples with expected stoichiometry. XRD studies confirmed the formation of ZnO above 500 °C. Photoluminescence studies on ZnS:Cr nanoparticles indicated that the emission wavelength is tunable in the range of 440–675 nm as a function of annealing temperature. VSM results indicated a decrease in ferromagnetism with increase in annealing temperature, perhaps due to appreciable variation in structural defects that are sensitive to annealing temperature.     

Zinc sulfide nanoparticles: Spectral properties and photocatalytic activity in metals reduction reactions

Formation of zinc sulfide nanocrystals in aqueous solutions of various polymers has been studied. Spectral properties of ZnS nanoparticles have been investigated, the structure of the long-wave edge of the fundamental absorption band of ZnS nanocrystals has been analyzed. It has been shown that the variation of the synthesis conditions (stabilizer nature and concentration, solution viscosity, ZnS concentration, etc.) allows tailoring of the ZnS nanocrystals size in the range of 3–10 nm. Photochemical processes in colloidal ZnS solutions, containing zinc chloride and sodium sulfite, have been investigated. It has been found that the irradiation of such solutions results in the reduction of Zn(II), the rate of this reaction growing at a decrease in the size of ZnS nanoparticles. Kinetics of photocatalytic Zn(II) reduction has been studied. It has been concluded that two-electron reduction of adsorbed Zn(II) species is the rate-determining stage of this reaction. Photocatalytic activity of ZnS nanoparticles in KAu(CN)₂ reduction in aqueous solutions has been discovered. Spectral characteristics and kinetics of ZnS/Au⁰ nanocomposite formation have been studied. It has been shown that the photoreduction of gold(I) complex is the equilibrium reaction due to the reverse oxidation of gold nanoparticles by ZnS valence band holes.     

Effect of gamma irradiation on the structural,thermal and optical properties of Makrofol BL 2–4

Makrofol BL 2–4 is an extrusion film based on Makrolon polycarbonate. It comprises excellent die-cutting performance combined with high light transmission and moderate light scattering properties. It is a class of polymeric solid state nuclear track detectors which has many applications in various radiation detection fields. In the present work, Makrofol samples were irradiated using different gamma doses ranging from 10 to 350 kGy. The structural modifications in the gamma-irradiated Makrofol samples have been studied as a function of dose using different characterization techniques such as X-ray diffraction, intrinsic viscosity, Fourier transform infrared spectroscopy, thermogravimetric analysis, refractive index and color difference studies. The gamma irradiation in the dose range 20–200 kGy led to a more compact structure of Makrofol polymer, which resulted in an improvement in its thermal stability with an enhancement in its structural and optical properties.     

Luminescence properties of co-doped ZnS:Ni,Mn and ZnS:Cu,Cd nanoparticles

Transition metal doped ZnS:Ni and ZnS:Cu and co-doped ZnS:Ni, Mn and ZnS:Cu, Cd nanoparticles were synthesized through the chemical precipitation method in an air atmosphere. The XRD analysis of co-doped samples shows the formation of cubic phase. The average size of nanoparticles ranges from 3.6 to 5.5 nm. The formation of co-doped nanoparticles was confirmed by XRD and PL analysis. The PL spectra show that the obtained nanoparticles have good crystal quality. An optimum concentration of transition metals was selected in co-doped ZnS nanoparticles.     

Increased porous morphology and thermal degradation of electron beam-irradiated PVDF-HFP/LiCLO4 polymer electrolyte

The effect of 8?MeV energy electron beam radiation at 40, 80 and 120?kGy dosage on surface morphology and thermal properties of lithium perchlorate-doped poly (vinylidene fluoride-co-hexafluoropropylene) polymer electrolyte films have been studied. The field emission scanning electron microscopic image shows small-porous structured morphology for unirradiated film, but it changed drastically into large and deep porous structure as well as the size of spherulites is reduced for 120?kGy confirming the influence of irradiation on morphology. The atomic force microscope reveals the significantly changed surface roughness of unirradiated film from 116.8 to 123.4?nm with a hill-like pattern morphology for 120?kGy confirming the increased amorphousity after irradiation. The thermal study confirmed that the decrease in the melting point of unirradiated film 160.86–155.24°C for 120?kGy doses is attributed to the formation of defects by the chain scissioning process resulting in the degradation of polymer electrolytes at high dose.     

Study of thermal diffusivity of nanofluids with bimetallic nanoparticles with Au(core)/Ag(shell) structure

The thermal diffusivity of Au/Ag nanoparticles with core/shell structure, at different compositions (Au/Ag = 3/1, 1/1, 1/3, 1/6), was measured by using the mismatched mode of the dual-beam thermal lens (TL) technique. This study determines the effect of the bimetallic composition on the thermal diffusivity of the nanofluids. In these results we find a lineal increment of the nanofluid it thermal diffusivity when the Ag shell thickness is increased. Our results show that the nanoparticle structure is an important parameter to improve the heat transport in composites and nanofluids. These results could have importance for applications in therapies and photothermal deliberation of drugs. Complementary measurements with UV-vis spectroscopy and TEM, were used to characterize the Au(core)/Ag(shell) nanoparticles.     

Preparation and characterization of poly(vinyl alcohol)/graphene nanofibers synthesized by electrospinning

We report on the synthesis and characterization of electrospun polyvinyl alcohol (PVA)/graphene nanofibers. The samples produced were characterized by Raman spectroscopy for structural and defect density analysis, scanning electron microscopy (SEM) for morphological analysis, and thermogravimetric (TGA) for thermal analysis. SEM measurements show uniform hollow PVA fibers formation and excellent graphene dispersion within the fibers, while TGA measurements show the improved thermal stability of PVA in the presence of graphene. The synthesized polymer reinforced nanofibers have potential to serve in many different applications such as thermal management, supercapacitor electrodes and biomedical materials for drug delivery.