Rheological study of polypropylene irradiated with polyfunctional monomers

The aim of this paper is to investigate the rheological properties of polypropylene (PP) modified by ionization radiation (gamma rays) in the presence of two different monomers. The samples were mixed in a twin-screw extruder with ethylene glycol dimethacrylate (EGDMA) or trimethylolpropane trimethacrylate (TMPTMA) with concentration in the range of 0.5-5.0 mmol. After that, they were irradiated with 20 kGy dose of gamma radiation. The structural modification of polypropylene was analyzed in the melt state by measuring melt flow rate (MFR), η* (complex viscosity) and G′ (storage modulus) in the angular frequency range of 10⁻¹ to 3 × 10² rad s⁻¹. From the oscillatory rheology data, one could obtain the values of η₀ (zero shear viscosity) that would be related to the molar mass. All results were discussed with respect to the crosslinking and degradation process that occur in the post-reactor treatment to produce controlled rheology polypropylene.The resulting polymeric materials were submitted the cytotoxicity in vitro test by neutral red uptake methodology with NCTC L 929 cell line from American Type Culture Collection bank. All modified PP samples presented no cytotoxicity.     

Effect of swift heavy ion irradiation on the surface morphology of highly c-axis oriented LSMO thin films grown by pulsed laser deposition

A detailed investigation of the surface morphology of the pristine and swift heavy ion (SHI) irradiated La_0.7Sr_0.3MnO₃ (LSMO) thin film using atomic force microscope (AFM) is presented. Highly c-axis oriented LSMO thin films were grown on LaAlO₃ (1 0 0) (LAO) substrates by the pulsed laser deposition (PLD) technique. The films were annealed at 800 °C for 12 h in air (pristine films) and subsequently, irradiated with SHI of oxygen and silver. The incident fluence was varied from 1 × 10¹² to 1 × 10¹⁴ ions/cm² and 1 × 10¹¹ to 1 × 10¹² ions/cm² for oxygen and silver ions, respectively. X-ray diffraction (XRD) studies reveal that the irradiated films are strained. From the AFM images, various details pertaining to the surface morphology such as rms roughness (σ), the surface rms roughness averaged over an infinite large image (σ_∞), fractal dimension (D_F) and the lateral coherence length (ξ) were estimated using the length dependent variance measurements. In case of irradiated films, the surface morphology shows drastic modifications, which is dependent on the nature of ions and the incident fluence. However, the surface is found to remain self-affine in each case. In case of oxygen ion irradiated films both, σ_∞ and D_F are observed to increase with fluence up to a dose value of 1 × 10¹³ ions/cm². With further increase in dose value both σ_∞ and D_F decreases. In case of silver ion irradiated films, σ_∞ and D_F decrease with increase in fluence value in the range studied.     

Surface characteristics and electrochemical corrosion behavior of fluorinated diamond-like carbon (F-DLC) films on the NiTi alloys

Fluorinated diamond-like carbon (F-DLC) films with different CF₄ flux were deposited on polished NiTi alloys by plasma immersion ion implantation and deposition (PIIID). The results show CF_x bond is formed in the F-DLC films. With the increase of the CF₄ flux, the fluorine content and surface hydrophilicity of the F-DLC films are increased, while their sp³/sp² ratio and surface roughness are decreased. The F-DLC films improve the surface corrosion resistance of NiTi alloys, and the corrosion resistance of the F-DLC films on the NiTi alloys first increase and then decrease with increasing the CF₄ flux. Moreover, the relationship between the corrosion resistance and its structure and surface hydrophilicity of the F-DLC films is also clarified.     

Growth of silicon nitride films by bombarding amorphous silicon with N ions: MD simulation

In this study, the molecular dynamics simulation method was employed to investigate the growth of silicon nitride films by using N⁺ ions, with energies of 50, 100, 150 and 200 eV, to bombard an amorphous silicon surface at 300 K. After an initial period of N⁺ bombardment, saturation of the number of N atoms deposited on the surface is observed, which is in agreement with experiments. During subsequent steady state deposition, a balance between uptake of N by the surface and sputtering of previously deposited N is established. The Si(N_x) (x = 1-4) and N(Si_y) (y = 1-3) bond configurations in the grown films are analyzed.     

Anisotropic proton-conducting membranes prepared from swift heavy ion-beam irradiated ETFE films

Poly(ethylene-co-tetrafluoroethylene) (ETFE) films were irradiated by swift heavy ion-beams of ¹²⁹Xe²³⁺ with fluences of 0, 3 × 10⁶, 3 × 10⁷, 3 × 10⁸ and 3 × 10⁹ ions/cm², followed by γ-ray pre-irradiation for radiation grafting of styrene onto the ETFE films and sulfonation of the grafted ETFE films to prepare highly anisotropic proton-conducting membranes. The fluence of Xe ions and the addition of water in the grafting solvent were examined to determine their effect on the proton conductivity of the resultant membranes. It was found that the polymer electrolyte membrane prepared by grafting the styrene monomer in a mixture of 67% isopropanol and 33% water to the ETFE film with an ion-beam irradiation fluence of 3.0 × 10⁶ ions/cm² was a highly anisotropic proton-conducting material, as the proton conductivity was three or more times higher in the thickness direction than in the surface direction of the membrane.     

Change in magnetic properties of MgB2 thin films after irradiation by 200 MeV Au ion beam

The SHI irradiation induced effects on magnetic properties of MgB₂ thin films are reported. The films having thickness 300-400 nm, prepared by hybrid physical chemical vapor deposition (HPCVD) were irradiated by 200 MeV Au ion beam (S_e ∼ 23 keV/nm) at the fluence 1 × 10¹² ion/cm². Interestingly, increase in the transition temperature T_c from 35.1 K to 36 K resulted after irradiation. Substantial enhancement of critical current density after irradiation was also observed because of the pinning provided by the defects created due to irradiation. The change in surface morphology due to irradiation is also studied.     

Characterization of gamma-stabilized PP with blends of hindered amine/phenolic stabilizers

In this work, the effect of γ radiation at doses of 25 and 50 kGy on polypropylene (PP) stabilized with a binary system of antioxidants of the phenol-hindered amine type (BHT-Chimassorb 994) at different compositions (0.1/0.2, 0.1/0.5, 0.1/0.8) was studied. The results showed that the carbonyl index (I_c) of the stabilized samples drastically decreases when compared to that of the pure PP sample. Nonetheless, the I_c values of the different stabilized samples were very similar after irradiation. On the other hand, the average molecular weights (M_w and M_n) and melt flow index (MFI) values decrease in all the samples after irradiation. This effect is less pronounced in PP with 0.1/0.8 of the binary blend of antioxidants. The melting and crystallization peak temperatures and the crystallinity degree remained almost unchanged and the tensile properties such as Young’s modulus and tensile strength did not vary either, except for the elongation at break, which decreases in less proportion in those blends of PP with the antioxidants, independently of the absorbed dose.     

Effect of 200 MeV Ag ion irradiation on structural and electrical transport properties of Fe3O4 thin films

Thin films of Fe₃O₄ have been deposited on single crystal MgO(1 0 0) and Si(1 0 0) substrates using pulsed laser deposition. Films grown on MgO substrate are epitaxial with c-axis orientation whereas, films on Si substrate are highly 〈1 1 1〉 oriented. Film thicknesses are 150 nm. These films have been irradiated with 200 MeV Ag ions. We study the effect of the irradiation on structural and electrical transport properties of these films. The fluence value of irradiation has been varied in the range of 5 × 10¹⁰ ions/cm² to 1 × 10¹² ions/cm². We compare the irradiation induced modifications on various physical properties between the c-axis oriented epitaxial film and non epitaxial but 〈1 1 1〉 oriented film. The pristine film on Si substrate shows Verwey transition (T_V) close to 125 K, which is higher than generally observed in single crystals (121 K). After the irradiation with the 5 × 10¹⁰ ions/cm² fluence value, T_V shifts to 122 K, closer to the single crystal value. However, with the higher fluence (1 × 10¹² ions/cm²) irradiation, T_V again shifts to 125 K.     

Synchrotron X-ray induced damage in polymer (PS) thin films

Thin polystyrene (PS) films (M_w = 234,000) are spin coated on silicon substrates with a Chromium (Cr) layer as a sandwiched metallic layer that produces photoelectrons (by synchrotron X-rays). Earlier studies on synchrotron radiation damage in PS films, without metallic layer, have shown a decrease in interfacial roughness and a slight increase in thickness, at temperatures below T_g [A.G. Richter, R. Guico, K. Shull, J. Wang, Macromolecules 39 (2006) 1545]. Similar trend is observed in the presence of a thin layer of Cr film (∼2.5 nm). For the sample with a thick Cr layer the opposite effect was observed for X-ray radiation damage. For the 50 nm thick Cr film system thickness of the polystyrene film decreased by ≈4.4% which amount to a loss of about 0.021 nm³ per incident photon in the fluence range studied (6.8 × 10⁹ photons mm⁻² to 1 × 10¹⁴ photons mm⁻²). Interfacial roughness also increased from about 1.0 nm to 2.1 nm in the process. These effects are explained by invoking the presence of more number of X-ray induced photoelectrons and secondary electrons for 50 nm thick Cr film case compared to 2.5 nm thin film case.     

The investigation of energy loss and damage in polycarbonate induced by MeV carbon clusters

Carbon cluster ions (n = 1-5) and Cl⁺, Ti⁺, Ni⁺ ions were used to bombard polycarbonate (PC) films. By comparing the electronic energy loss and the number of chromophores at a fixed wavelength, we obtained the electronic energy loss S_e of carbon cluster ions in PC.     

IBA of ZrO2:Yb/Si thin films produced by the spray pyrolysis method

A spray pyrolysis method was used to produce thin films of ZrO₂ doped with different Yb concentrations on Si(1 0 0). The films of these ionic semiconductors have potential applications as solid electrolytes in modern ceramic fuel cells of second generation. The determination of the atomic composition of the films is very important because it strongly affects the chemical and thermal stability, as well as electrical properties of the films. A combination of two Ion Beam Analysis (IBA) methods was applied to obtain the atomic composition of the films. A nuclear reaction analysis (NRA) method using a low energy deuterium beam was applied to measure the oxygen content of the films. Heavy ion Rutherford backscattering (HI-RBS) method using a ¹²C³⁺ beam was applied to measure the Yb and Zr atomic profiles of the samples. X-ray diffraction (XRD) and ellipsometry were also employed to determine structural properties and refractive index of the films, respectively. The IBA, XRD and the ellipsometry supply a wide range of information about the film layers, which can be used for qualification as well as for feedback to the films production.     

Radiation-induced grafting of inorganic particles onto polymer backbone: A new method to design polymer-based nanocomposite

Polypropylene/polyhedral oligomeric silsesquioxane (PP/POSS) nanocomposites were prepared by in situ radiation-induced grafting of POSS onto PP. Radiation-induced grafting of POSS was confirmed by FT-IR spectroscopy. The mechanical property of PP/POSS nanocomposites increased with the increase in POSS content and with the increase in absorption dose up to 5 kGy, above which it started to decrease. The reduction of mechanical property at high doses can be attributed to the chain scission of PP by radiation. The degree of reduction in decomposition temperature of irradiated PP/POSS nanocomposites was found to be much less than that of neat PP due to the covalent grafting of POSS onto PP by radiation.     

MeV-ion beam analysis of the interface between filtered cathodic arc-deposited a-carbon and single crystalline silicon

Amorphous carbon (a-C) films were deposited on Si(1 0 0) wafers by a filtered cathodic vacuum arc (FCVA) plasma source. A negative electrical bias was applied to the silicon substrate in order to control the incident energy of carbon ions. Effects of the electrical bias on the a-C/Si interface characteristics were investigated by using standard Rutherford backscattering spectrometry (RBS) in the channeling mode with 2.1-MeV He²⁺ ions. The shape of the Si surface peaks of the RBS/channeling spectra reflects the degree of interface disorder due to atomic displacement from the bulk position of the Si crystal. Details of the analysis method developed are described. It was found that the width of the a-C/Si interface increases linearly with the substrate bias voltage but not the thickness of the a-C film.     

RBS and ion channeling studies of Ag-doped YBa2Cu3O7−δ targets and films

The location of Ag in Ag-doped YBa₂Cu₃O_7−δ (YBCO) films and other high-T_c materials (such as Ag-doped BiSrCaCuO films and Ag-sheathed textured BiSrCaCuO wires) is a very important issue for improving high-T_c materials. In this work, laser ablated and DC magnetron sputtered YBCO films on (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃ were prepared from sintered Ag-YBCO composite targets (nominally containing 5 wt% Ag) and studied by Rutherford Backscattering Spectrometry (RBS) and ion channeling techniques using 2.0 MeV⁴He⁺ and ⁷Li⁺ beams. We have found that the Ag-YBCO targets contain about 3 wt% Ag and most of the retained Ag atoms form some small size Ag precipitates with a typical size smaller than a few microns. We have demonstrated that in very good single crystalline YBCO films, the percentage of retained Ag in substitutional sites can be estimated by ion channeling technique. For example, we have found that about 1.2 wt% Ag atoms remain in the laser ablated Ag-doped films prepared from the Ag-YBCO target and about two-thirds of the retained Ag atoms occupy substitutional sites. The sputtered films contain less retained Ag atoms since the deposition temperature is higher and deposition time is longer than those for laser ablated films.     

Microstructure evolution of Ge implanted silicon oxide thin films upon annealing treatments

The structural evolution of silicon oxide films with Ge⁺ implantation was traced with a positron beam equipped with positron annihilation Doppler broadening and lifetime spectrometers. Results indicate that the film structure change as a function of the annealing temperature could be divided into four stages: (I) T < 300 °C; (II) 300 °C ? T ? 500 °C; (III) 600 °C ? T ? 800 °C; (IV) T ? 900 °C. In comparison with stage I, the increased positron annihilation Doppler broadening S values during stage II is ascribed to the annealing out of point defects and coalescence of intrinsic open volumes in silicon oxides. The obtained long positron lifetime and high S values without much fluctuation in stage III suggest a rather stable film structure. Further annealing above 900 °C brings about dramatic change of the film structure with Ge precipitation. Positron annihilation spectroscopy is thereby a sensitive probe for the diagnosis of microstructure variation of silicon oxide thin films with nano-precipitation.     

Ion irradiation effects on surface mechanical behavior and shrinkage of hybrid sol-gel derived silicate thin films

A study of the effects of ion irradiation on the surface mechanical behavior and shrinkage of organic/inorganic modified silicate thin films was performed. The films were synthesized by sol-gel processing from tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES) precursors and spin-coated onto Si substrates. The sol viscosity and the spin velocity were adjusted so that the films produced had a final thickness ranging from 580 to 710 nm after heat treatment. The ion species and incident energies used were selected such that the projected ion range was greater than the film thickness, resulting in fully irradiated films. After heat treatment at 300 °C for 10 min, the films were irradiated with 125 keV H⁺, 250 keV N²⁺ and 2 MeV Cu⁺ ions with fluences ranging from 1 × 10¹⁴ to 1 × 10¹⁶ ions/cm². Both hardness and reduced elastic modulus were seen to exhibit a monotonic increase with fluence for all three ion species. Also, H loss was found to increase monotonically with increase in fluence, while the film thickness was found to decrease with increase in fluence.     

Annihilation characteristics of positrons in free-standing thin metal and polymer films

Annihilation characteristics of positrons and positronium (Ps) in thin metal and polymer films were studied. Monoenergetic positrons were implanted into free-standing thin W and Au films and the annihilation γ-rays of positron-electron pairs were measured as a function of the incident energy of positrons. At the front-side surfaces of the films, an emission of Ps into vacuum and a resultant self-annihilation of ortho-Ps (o-Ps) were observed. At the backside surfaces, the Ps emission was found to be enhanced by an increase in the numbers of epithermal positrons and/or secondary electrons introduced by the impact of energetic positrons. For thin polymer films (polyester and polystyrene), the emission rate of o-Ps from the backside surfaces was higher than that from the metal films, which was attributed to the out-diffusion of o-Ps formed in the films. Those results suggested that the emission rate of Ps into vacuum was sensitive to the Ps formation process in the bulk and at the surface.     

Effects of ion irradiation on the mechanical properties of SiNawOxCyHz sol-gel derived thin films

A study of the effects of ion irradiation of hybrid organic/inorganic modified silicate thin films on their mechanical properties is presented. NaOH catalyzed SiNa_wO_xC_yH_z thin films were synthesized by sol-gel processing from tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES) precursors and spin-coated onto Si substrates. After drying at 300 °C, the films were irradiated with 125 keV H⁺ or 250 keV N²⁺ at fluences ranging from 1 × 10¹⁴ to 2.5 × 10¹⁶ ions/cm². Nanoindentation was used to characterize the films. Changes in hardness and reduced elastic modulus were examined as a function of ion fluence and irradiating species. The resulting increases in hardness and reduced elastic modulus are compared to similarly processed acid catalyzed silicate thin films.     

Incorporation of oxygen during oxidative annealing of thermally evaporated In films

The paper describes studies on compositional, morphological and optical characteristics of thin indium oxide films prepared by annealing thermally evaporated indium metal films in 423-723 K temperature range in air. The incorporation of oxygen in the films has been probed by depth profiling oxygen using ¹⁸O(p, α)¹⁵N nuclear reaction and 3.05 MeV ¹⁶O(α, α)¹⁶O resonant scattering. The morphology of the films has been examined by atomic force microscopy while their structure by glancing incidence X-ray diffraction. As grown In films are polycrystalline and consist of well-aligned (In) hillocks. The hillocks in thin films (∼12 nm) are nanosized and conical in shape while those in thicker films (∼130 nm) are micron-sized with rather flat tops. Nanosized hillocks impart films enhanced reactivity towards oxygen. Consequently thinner films contain high amount of adsorbed oxygen in as-deposited state and undergo facile oxidation. The hillocks are obliterated in the process. The enhanced reactivity is attributed to high surface energy, generally associated with nanoparticles, and residual stress. These films exhibit high transmission (>90%) on annealing beyond 473 K. Micro-sized hillocks, on the other hand lend pronounced roughness to the films. Roughness and lower surface free energy which manifests in the form of flatter hillock tops, make the films oxidation-resistant. Depth profile measurements in thicker films show that oxidation starts at the surface and proceeds into the interiors of the film with increase in the duration of annealing. The films are deficient in oxygen, even as X-ray diffraction shows the formation of polycrystalline indium oxide. These have low transmission (<30%) and their band gaps increase with the temperature and duration of annealing. The increase in band gap is attributed to the gradual oxidation of interior regions that are initially significantly deficient in oxygen and improvement in crystallinity.     

Studies on the high electronic energy deposition in polyaniline thin films

We report here the physico-chemical changes brought about by high electronic energy deposition of gold ions in HCl doped polyaniline (PANI) thin films. PANI thin films were synthesized by in situ polymerization technique. The as-synthesized PANI thin films of thickness 160 nm were irradiated using Au⁷⁺ ion of 100 MeV energy at different fluences, namely, 5 × 10¹¹ ions/cm² and 5 × 10¹² ions/cm², respectively. A significant change was seen after irradiation in electrical and photo conductivity, which may be related to increased carrier concentration, and structural modifications in the polymer film. In addition, the high electronic energy deposition showed other effects like cross-linking of polymer chains, bond breaking and creation of defect sites. AFM observations revealed mountainous type features in all (before and after irradiation) PANI samples. The average size (diameter) and density of such mountainous clusters were found to be related with the ion fluence. The AFM profiles also showed change in the surface roughness of the films with respect to irradiation, which is one of the peculiarity of the high electronic energy deposition technique.