Effect of gamma-irradiation on thermal decomposition kinetics,X-ray diffraction pattern and spectral properties of tris(1,2-diaminoethane)nickel(II)sulphate

Tris(1,2-diaminoethane)nickel(II)sulphate was prepared, and characterised by various chemical and spectral techniques. The sample was irradiated with ⁶⁰Co gamma rays for varying doses. Sulphite ion and ammonia were detected and estimated in the irradiated samples. Non-isothermal decomposition kinetics, X-ray diffraction pattern, Fourier transform infrared spectroscopy, electronic, fast atom bombardment mass spectra, and surface morphology of the complex were studied before and after irradiation. Kinetic parameters were evaluated by integral, differential, and approximation methods. Irradiation enhanced thermal decomposition, lowering thermal and kinetic parameters. The mechanism of decomposition is controlled by R₃ function. From X-ray diffraction studies, change in lattice parameters and subsequent changes in unit cell volume and average crystallite size were observed. Both unirradiated and irradiated samples of the complex belong to trigonal crystal system. Decrease in the intensity of the peaks was observed in the infrared spectra of irradiated samples. Electronic spectral studies revealed that the M–L interaction is unaffected by irradiation. Mass spectral studies showed that the fragmentation patterns of the unirradiated and irradiated samples are similar. The additional fragment with m/z 256 found in the irradiated sample is attributed to S₈⁺. Surface morphology of the complex changed upon irradiation.     

Electron induced modification in poly(ethylene terephthalate)

Abstract

The effect of 100 kGy dose of 2 MeV electron irradiation on Poly(ethylene terepthalate) (PET) has been studied by different characterisation techniques such as the Fourier transformed IR spectroscopy, electron spin resonance spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction analysis. Oxidative degradation leading to amorphisation of the polymer has been observed from spectral analysis. The thermal stability of the polymer was found to decrease due to electron irradiation. The thermal decomposition temperature as well as the melting temperature in case of irradiated PET was found to be decreased due to electron bombardment. A decrease in crystallinity of the polymer has also been observed after irradiation.     

Gamma-photon induced modifications in Polyvinylchloride (PVC) film

Gamma photon induced modifications in Polyvinylchloride (PVC) polymer have been studied in the dose range of 10¹-10⁶Gy at room temperature. Polyvinylchloride films have been irradiated with different doses of gamma radiation from a ⁶⁰Co source. To monitor the chemical and structural changes caused by gamma radiation IR and UV-Vis spectroscopy of pristine and irradiated PVC have been performed and using the spectral data some changes in the properties have been investigated. The spectral studies have indicated that at a dose of 10⁶Gy scissioning of the C-a bonds takes place. This scissioning of the chain initiates decomposition at a lower temperature. Thermal stability of the polymer reduces due to irradiation but the decomposition patterns remain the same. The optical band-gap is found to decrease due to irradiation at doses bigher than 10³Gy.     

Proton induced modification in Poly(ethylene terephthalate)

A systematic investigation of 62 r MeV proton irradiated Poly(ethylene terephthalate) (PET) has been carried out using Fourier Transformed Infrared Spectroscopy, thermogravimetric analysis, differential scanning calorimetry and X-ray diffraction spectroscopy. The experiments revealed a restoration of the crystalline matrix and simultaneous decrease in thermal stability in the irradiated polymer as a function of dose, indicating that PET underwent both degradation and cross-linking by proton irradiation.     

Interaction of oxygen (O+7) ion beam on polyaniline thin films

High-energy ion beam irradiation of the polymers is a good technique to modify the properties such as electrical conductivity, structural behaviour and mechanial properties. Polyaniline thin films doped with hydrochloric acid (HCl) were prepared by oxidation of ammonium persulphate. The effect of Swift Heavy Ions irradiation on the electrical and structural properties of polyaniline has been measured in this study. Polyaniline films were irradiated by oxygen ions (energy 80 MeV, charge state O⁺⁷) with fluence varying from 1 × 10¹⁰ to 3 × 10¹² ions/cm². The studies on electrical and structural properties of the irradiated polymers were investigated by measuring V-I using four probe set-up and X-ray diffraction (XRD) using Bruker AXS, X-ray powder diffractometer. V-I measurements shows an increase in the conductivity of the film, XRD pattern of the polymer shows that the crystallinity improved after the irradiation with Swift Heavy Ions (SHI), which could be attributed to cross linking mechanism.      

Sonochemical synthesis of a novel nanoscale 1D lead(II) [Pb2(L)2(I)4]n coordination Polymer,survey of temperature,reaction time parameters

One new lead(II) coordination supramolecular complex (CSC) (1D), [Pb₂(L)₂(I)₄]_n, L = C₄H₆N₂ (1-methyl imidazole), has been synthesized under different experimental conditions. Micrometric crystals (bulk) or nano-sized materials have been obtained depending on using the branch tube method or sonochemical irradiation. All materials have been characterized by scanning electron microscopy (SEM), powder X-ray diffraction (PXRD) and FT-IR spectroscopy. Single crystal X-ray analyses on complex 1 showed that Pb²⁺ ion is 4-coordinated. Topological analysis shows that the complex 1 is 2,3,5C2 net. Finally, the role of reaction time and temperature on the growth and final morphology of the structures obtained by sonochemical irradiation have been studied.     

Influence of 120 MeV Si9+ ion irradiation on ZnTe semiconductor thin films

ABSTRACT

ZnTe (Zinc Telluride) is a potential semiconducting material for many optoelectronic devices like solar cells and back contact material for CdTe-based solar cells. In the present study, ZnTe thin films were prepared by thermal evaporation technique and then irradiated with 120?MeV Si⁹⁺ ions at different fluences. These films are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV–Visible spectroscopy techniques. XRD study confirms increased crystallinity and grain growth for post-irradiated ZnTe thin films for fluences, up to 1?×?10¹¹ ions cm^?2. However, the grain size and crystallinity decreased for higher fluence-exposed samples. SEM images confirm the observed structural properties. Modification of the surface morphology of the film due to the ion irradiation with different fluences is studied. Optical band gap of film is decreased from 2.31?eV (pristine) to 2.17?eV after irradiation of Si⁹⁺ ions.     

The study of gamma irradiation effects on poly (glycolic acid)

We have investigated the effects of gamma irradiation on chemical structure, thermal and morphological properties of biodegradable semi-crystalline poly (glycolic acid) (PGA). PGA samples were subjected to irradiation treatment using a ⁶⁰Co gamma source with a delivered dose of 30, 60 and 90?kGy, respectively. Gamma irradiation induces cleavage of PGA main chains forming ～O?H₂ and ?H₂COO～ radicals in both amorphous and crystalline regions. The free radicals formed in the amorphous region abstract atmospheric oxygen and convert them to peroxy radicals. The peroxy radical causes chain scission at the crystal interface through hydrogen abstraction from methylene groups forming the ～?HCOO～ (I) radical. Consequently, the observed electron spin resonance (ESR) doublet of irradiated PGA is assigned to (I). The disappearance of the ESR signal above 190°C indicates that free radicals are formed in the amorphous region and decay below the melting temperature of PGA. Fourier transform infrared and optical absorption studies confirm that the groups are not influenced by gamma irradiation. Differential scanning calorimetry (DSC) studies showed that the melting temperature of PGA decreased from 212°C to 202°C upon irradiation. Degree of crystallinity increased initially and then decreased with an increase in radiation as per DSC and X-ray diffraction studies. Irradiation produced changes in the physical properties of PGA as well as affecting the morphology of the material.     

Lattice damage and Al-metal precipitation in 2.5 MeV-electron-irradiated AlH3

AlH₃ powder was bombarded with energetic electrons at 20 K and at room temperature and investigated by EPR, NMR, X-ray diffractometry, and microwave dielectric-constant measurements. The EPR spectra of the irradiated powder and of a selected single crystal cuboid of mm edge show a complex asymmetric line centered at g = 2.009, with a Curie-like temperature dependence, attributed to radiation-induced color centers and/or their agglomerates. At the same time, the grains, which have become shiny black after irradiation, exhibit an increase of both the real and the imaginary part of . ²⁷Al-NMR spectra of the irradiated powder present a Knight-shifted line at 1600(50) ppm, close to the position of bulk metallic Al, and corresponding to a concentration of c(Al) . In addition, the main hydride line differs from that before irradiation, demonstrating an alteration of environmental symmetry. The irradiation induces also a change in shape and width of the ¹H-NMR line, another indication of symmetry change in the lattice. Finally, a refined X-ray single-crystal structure analysis of the irradiated cuboid indicates a change of structure from trigonal R -3 c to R -3, with a loss of mirror symmetry for the two Al sites caused by the introduction of Al-defects in the vicinity of one of them. Received: 20 October 1997 / Revised: 24 December 1997 / Accepted: 30 January 1998     

Sonochemical effect on two new Ruthenium(II) complexes with ligand (E)-N-((6-bromopyridin-2-yl)methylene)-4-(methylthio)aniline precursors for synthesis of RuO2 nanoparticles

Two novel Ru(II) complexes [(η⁶-p-cymene)RuCl(L2)]PF₆ (R2) and [(η⁶-C₆H₆)RuCl(L2)]PF₆ (R4), with ligand (E)-N-((6-bromopyridin-2-yl)methylene)-4-(methylthio)aniline (L2), were synthesized and characterized by elemental analysis, ¹H NMR, ¹³C NMR and IR spectroscopy. Based on X-ray crystallography studies, complexes R2 and R4 have coordination environments with formulated (η⁶-p-cymene)Ru(N₂Cl) and (η⁶-C₆H₆)Ru(N₂Cl), respectively. The thermal stabilities of compounds R2 and R4 were studied by thermal gravimetric (TG) and differential scanning calorimetry (DSC). Thermal decomposition of these complexes was at 280 °C and 260 °C under air atmosphere respectively. The interaction of these complexes with calf thymus DNA (CT-DNA) was explored through electronic absorption spectra, fluorescence and redox behavior studies. The results showed that the complexes bind to CT-DNA with electrostatic interactions. Nanoparticles of RuO₂ were prepared by calcination of R2 and R4. Also the role of the ultrasound waves on the characteristics of the RuO₂ nanoparticles was studied. The nanoparticles were characterized by IR spectroscopy and X-ray diffraction (XRD). Also size and morphology of nanoparticles were studied by scanning electron microscopy (SEM).     

A study of the effect of gamma and laser irradiation on the thermal,optical and structural properties of CR-39 nuclear track detector

A comparative study of the effect of gamma and laser irradiation on the thermal, optical and structural properties of the CR-39 diglycol carbonate solid state nuclear track detector has been carried out. Samples from CR-39 polymer were classified into two main groups: the first group was irradiated by gamma rays with doses at levels between 20 and 300 kGy, whereas the second group was exposed to infrared laser radiation with energy fluences at levels between 0.71 and 8.53 J/cm². Non-isothermal studies were carried out using thermogravimetry, differential thermogravimetry and differential thermal analysis to obtain activation energy of decomposition and transition temperatures for the non-irradiated and all irradiated CR-39 samples. In addition, optical and structural property studies were performed on non-irradiated and irradiated CR-39 samples using refractive index and X-ray diffraction measurements. Variation in the onset temperature of decomposition T _o, activation energy of decomposition E _a, melting temperature T _m, refractive index n and the mass fraction of the amorphous phase after gamma and laser irradiation were studied.

It was found that many changes in the thermal, optical and structural properties of the CR-39 polymer could be produced by gamma irradiation via degradation and cross-linking mechanisms. Also, the gamma dose has an advantage of increasing the correlation between thermal stability of the CR-39 polymer and bond formation created by the ionizing effect of gamma radiation. On the other hand, higher laser-energy fluences in the range 4.27–8.53 J/cm² decrease the melting temperature of the CR-39 polymer and this is most suitable for applications requiring molding of the polymer at lower temperatures.     

Effect of ion beam irradiation on palladium (II) acetyl acetonate dispersed in polymer matrix

Composites, containing different concentrations of palladium (II) acetylacetonate in polymethyl methacrylate (PMMA) matrix were prepared by vigorous mixing. PMMA was prepared by solution polymerization technique. The composites were irradiated with a 120 MeV Ni¹⁰⁺ beam at two different fluences of 1×10¹¹ and 5×10¹² ions/cm² to study ion-induced effects on their dielectric, structural properties and surface morphology. AC electrical properties of these samples were studied in the frequency range 100 Hz to 10 MHz. The dielectric permittivity/loss shows frequency dependent behavior and it obeys the universal law of dielectric (i.e. ?α f ^n?1) for pristine and irradiated samples at high frequency. The crystalline size and crystallinity of the composites were studied by X-ray diffraction analysis. Decrease in peak intensity after irradiation signifies the amorphization which is also responsible for decrease in T _g as obtained by means of differential scanning calorimetry measurement. Fourier transform infrared spectra also support this result. Surface roughness increases upon irradiation as observed from scanning electron microscopy.     

Study of structure and optical luminescence of C+6 (80 MeV) ion irradiated CdS: Fe system

Iron doped CdS nanocrystals have been synthesized by using aqueous solution precipitation method. Samples of CdS:Fe have been subjected to irradiation using C⁺⁶ (80 MeV) under of 1×10¹³ ions/cm². For characterization, X-ray diffraction (XRD), Photoluminescence (PL) and Optical absorption studies have been performed. The system has been found in hexagonal phase having particle size distribution 18–20 nm. Photoluminescence intensity has been found to decrease, while optical band gap has been found to increase in irradiated samples.     

Sonochemical synthesis of a new nano-sized cerium(III) supramolecular compound; Precursor for nanoceria

Using a sonochemical method, nanoparticles of a new Ce(III) supramolecular compound, (NAMH⁺)₂[Ce₄(pydc)₆(pydcH)₂(H₂O)₈]·8H₂O (1), (H₂pydc = 2,6-pyridinedicarboxylic acid, NAM = nicotinamide), have been synthesized. Compound 1 was characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRPD), FT-IR spectroscopy and elemental analyses, and its structure was determined by X-ray crystallography. It has been revealed that its structure consists of tetra-nuclear building units that extend to a 3D supramolecular network via non-covalent interactions mainly hydrogen bonding. The thermal stability of complex 1 both for its crystals and nanostructures has been studied by the thermal gravimetric (TG) method and compared with each other. The role of ultrasound irradiation power and the concentration of initial reactants on the size and morphology of the nano-structured complex 1, has been investigated. Ceria nanoparticles were obtained upon the calcination of complex 1 at 800 °C under atmospheric air. Furthermore, the fluorescent properties of complex 1 at room temperature were studied.     

Effects of atomic oxygen irradiation on the surface properties of phenolphthalein poly(ether sulfone)

To study the effects of low earth orbit environment on the surface properties of polymers, phenolphthalein poly(ether sulfone) (PES-C) blocks were irradiated by atomic oxygen in a ground-based simulation system. The surface properties of the pristine and irradiated blocks were studied by attenuated total-reflection FTIR (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM). It was found that atomic oxygen irradiation induced the destruction of PES-C molecular chains, including the scission and oxidation of PES-C molecular chains, as evidenced by FTIR and XPS results. The scission of PES-C molecular chains decreased the relative concentration of C in the surface, while the oxidation increased the relative concentration of O in the surface. The changes in surface chemical structure and composition also changed the surface morphology of the block, which shifted from smooth structure before irradiation to “carpet-like” structure after irradiation.     

Cadmium (II) pyrrolidine dithiocarbamate complex as single source precursor for the preparation of CdS nanocrystals by microwave irradiation and conventional heating process

The complex of cadmium with pyrrolidine dithiocarbamate Cd(pdtc)₂ has been used as single source precursor for the synthesis of CdS nanoparticles. The formation of CdS nanostructures was achieved by thermal decomposition of the complex under microwave irradiation and conventional heating in presence of hexadecylamine. The CdS nanoparticles with disordered close-packed structure were obtained under microwave irradiation, whereas wurtzite hexagonal phase CdS nanorods were obtained by conventional heating method (up to 150 °C). Scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and high resolution transmission electron microscopy (HRTEM) studies also were carried out to study the structure and morphology of nanoparticles. The optical property of the CdS nanoparticles was studied by UV-visible and fluorescence emission spectral studies. Fluorescence measurements on the CdS nanoparticles show a strong emission spectrum with two sub bands that are attributed to band-edge and surface-defect emissions. The reduction of a suitable cadmium metal complex is considered to be one of the single pot methods to generate CdS semiconductor nanoparticles with different shapes and high yield.     

A Co-Crystallised Cobalt(II) Cluster of Pyridinedicarboxylic Acid (PDC) as a Luminescent Material for Selective Sensing of Methanol

A luminescent Cobalt(II) co-crystal [Co₁₃(PDC)₁₆(H₂O)₂₄.7H₂O] 1 (where H₂PDC?=?2,6-pyridinedicarboxylic acid) have been prepared by oven-heating and slow evaporation of solvent. Single crystal X-ray diffraction (SCXRD) analysis revealed that 1 is a mixture of complexes that crystallizes in the triclinic space group P-1 and the geometry around the Co(II) ions is octahedral. The structure is extensively imbued with hydrogen bonding that helps in stabilizing the complex. Thermogravimetric analysis indicates that 1 is thermally stable up to 364 ^οC. The luminescence properties of 1 revealed a strong emission centered at 437 nm (λex?=?345 nm) assigned to ligand to metal charge transfer (LMCT). The luminescence sensing of 1 towards volatile organic molecules were also examined. However, 1 displayed a turn off towards methanol compared to other molecules with high quenching efficiency and low limit of detection (3.5?×?10^?4 vol%). The results show excellent selectively and high sensitivity. Powder X-ray diffraction studies revealed that the structural integrity of the complex was maintained after exposure to methanol vapour. Theoretical studies also revealed small binding energy (?413.2 au) and low energy gap (1.19) for 1-CH₃OH adduct.

     

Comparative study on low energy ion beam modification of thermoplastic polymers

ABSTRACT

Polycarbonate (PC) and polyethylene terephthalate (PET) thermoplastic polymer films were irradiated by low energy ion beams such as 100 keV Hydrogen (H⁺) ions and 350 keV Nitrogen (N⁺) ions at varied fluence from 1?×?10¹³ ions/cm² to 5?×?10¹⁴ ions/cm². The depth profile concentration of ions was calculated using Stopping and Range of Ions in Matter (SRIM) software code. Fourier Transform Infrared (FTIR) technique shows decrement in the intensity of peaks and disappearance of peaks mainly related to carbonyl stretching at 1770?cm^?1 and C–C stretching at 1500?cm^?1. Scanning electron microscopy (SEM) of irradiated polymers showed the formation of pores. X-ray diffraction (XRD) analysis has showed decrease in the intensity indicating the decrease in crystallinity after irradiation. Mechanical studies revealed that the molecular weight and microhardness decrease with increase in ion fluence due to increase in chain scission. The contact angle increased with increase in ion fluence indicating the hydrophobic nature of polymer after irradiation. Antibiofilm activity test of irradiated films shows resistance to Salmonella typhi (S. typhi) pathogen responsible for typhoid. The study shows that Nitrogen ion induces more damage compared to Hydrogen ions and PC films get more modified than PET films.     

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.     

Magnetic Study of Nanocrystalline Ferrites and the Effect of Swift Heavy Ion Irradiation

100 MeV Si⁺⁷ irradiation induced modifications in the structural and magnetic properties of Mg_0.95Mn_0.05Fe₂O₄ nanoparticles have been studied by using X-ray diffraction, Mössbauer spectroscopy and a SQUID magnetometer. The X-ray diffraction patterns indicate the presence of single-phase cubic spinel structure of the samples. The particle size was estimated from the broadened (311) X-ray diffraction peak using the well-known Scherrer equation. The milling process reduced the average particle size to the nanometer range. After irradiation a slight increase in the particle size was observed. With the room temperature Mössbauer spectroscopy, superparamagnetic relaxation effects were observed in the pristine as well as in the irradiated samples. No appreciable changes were observed in the room temperature Mössbauer spectra after ion irradiation. Mössbauer spectroscopy performed on a 12 h milled pristine sample (6 nm) confirmed the transition to a magnetically ordered state for temperatures less than 140 K. All the samples showed well-defined magnetic ordering at 5 K, whereas, at room temperature they were in a superparamagnetic state. From the magnetization studies performed on the irradiated samples, it was concluded that the saturation magnetization was enhanced. This was explained on the basis of SHI irradiation induced modifications in surface states of the nanoparticles.