Effect of yttria addition on the stability of porous chromium oxide ceramics in supercritical water

Porous chromium oxide (Cr₂O₃) ceramics were prepared by oxidizing highly porous chromium carbides that were obtained by a reactive sintering method, and were evaluated at temperatures ranging from 375 °C to 625 °C in supercritical water (SCW) environments with a fixed pressure of 25–30 MPa. Reactive element yttrium was introduced to the porous oxide ceramic by adding various amounts of yttria of 5, 10 and 20 wt.%, respectively, prior to reactive sintering. The exposure in SCW shows that the porous chromium oxide is quite stable in SCW at 375 °C. However, the stability decreased with increasing temperature. It is well known that chromium oxide can be oxidized to soluble chromium (VI) species in SCW when oxygen is present. Adding yttria increases the stability of chromium oxide in SCW environments. However, adding yttria higher than 5 wt.% increased the weight loss of porous chromium oxide samples because of the direct dissociation of Y₂O₃ in SCW.     

Early stage of the crystallization in amorphous Fe–Si layers: Formation and growth of metastable α-FeSi2

Crystallization processes of amorphous Fe–Si layers have been investigated using transmission electron microscopy (TEM). Si(1 1 1) substrates were irradiated with 120 keV Fe ions at ?150 °C to a fluence of 1.0 × 10¹⁷ cm². An Fe-rich amorphous layer embedded in an amorphous Si was formed in the as-irradiated sample. Plan-view TEM observations revealed that a part of the amorphous Fe–Si layer crystallized to the metastable α-FeSi₂ after thermal annealing at 350 °C for 8 h. The lattice parameter of c-axis decreased with thermal annealing. It was considered that the change in the lattice parameter originates from the decrease of the Fe occupancy at (0, 0, 1/2) and its equivalent positions in the unit cell of the metastable α-FeSi₂.     

Oxygen distribution in the heteroepitaxially grown Y2O3 films on Si substrates

Crystallographic features of the heteroepitaxially grown yttrium oxide films on Si (1 0 0) and Si (1 1 1) substrates by ultra-high vacuum ionized cluster beam (UHV-ICB) were investigated by non-Rutherford backscattering spectrometry/channeling. The heteroepitaxially grown Y₂O₃ films with 1080 Å thick on Si (1 0 0) and Si (1 1 1) were completely stoichiometric with the composition ratio of Y/O=1/1.5 regardless of substrates. Channeling minimum yields of Y₂O₃ films on Si (1 0 0) and Si (1 1 1) are 0.39 and 0.10, respectively, which were much smaller values than the minimum values (>0.8) of Y₂O₃ films on Si substrates deposited by other methods. The results of non-Rutherford backscattering spectrometry/channeling show that the oxygen atoms in heteroepitaxially grown Y₂O₃ on Si (1 1 1) substrates have reasonable crystallinity, but those on Si (1 0 0) substrates are displaced from the regular sub-lattice sites.     

SHI induced re-crystallization of Ge implanted SiO2 films

Ge nanocrystals embedded in SiO₂ matrix have been synthesized by swift heavy ion irradiation of Ge implanted SiO₂ films. In the present study, 400 keV Ge⁺ ions were implanted into SiO₂ films at dose of 3 × 10¹⁶ ions/cm² at room temperature. The as-implanted samples were irradiated with 150 MeV Ag¹²⁺ ions with various fluences. Similarly 400 keV Ge⁺ ions implanted into Silicon substrate at higher fluence at 573 K have been irradiated with 100 MeV Au⁸⁺ ions at room temperature (RT). These samples were subsequently characterized by XRD and Raman to understand the re-crystallization behavior. The XRD results confirm the presence of Ge crystallites in the irradiated samples. Rutherford backscattering spectrometry (RBS) was used to quantify the concentration of Ge in the SiO₂ matrix. Variation in the nanocrystal size as a function of ion fluence is presented. The basic mechanism of ion beam induced re-crystallization has been discussed.     

Investigation of hydrogen concentration and hardness of ion irradiated organically modified silicate thin films

A study of the effects of ion irradiation of organically modified silicate thin films on the loss of hydrogen and increase in hardness 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. Elastic Recoil Detection (ERD) was used to investigate resulting hydrogen concentration as a function of ion fluence and irradiating species. Nanoindentation was used to measure the hardness of the irradiated films. FT-IR spectroscopy was also used to examine resulting changes in chemical bonding. The resulting hydrogen loss and increase in hardness are compared to similarly processed acid catalyzed silicate thin films.     

Influence of HIP pressure on tensile properties of a 14Cr ODS ferritic steel

An oxide dispersion strengthened ferritic steel with a nominal composition of Fe–14Cr–2W–0.3Ti–0.3Y₂O₃ (in wt.%) was consolidated by hot isostatic pressing at 1150 °C under various pressures in the range of 185–300 MPa for 3 h. The microstructure, microhardness and high temperature tensile properties of the steel were investigated. With increasing compaction pressure the density of specimens also increased, however OM and SEM observations revealed residual porosity in all tested specimens and similar ferritic microstructure with bimodal-like grains and numerous of large oxide particles, located at the grain boundaries. Mechanical testing revealed that compaction pressure has negligible influence on the hardness and tensile strength of the ODS steel, however improves the material ductility.     

Light particle irradiation effects in Si nanocrystals

Si nanocrystals, formed by Si ion implantation into SiO₂ layers and subsequent annealing at 1150°C, were irradiated at room temperature either with He⁺ions at energies of 30 or 130 keV, or with 400 keV electrons. Transmission electron microscopy (TEM) and photoluminescence (PL) studies were performed. TEM experiments revealed that the Si nanocrystals were ultimately amorphized (for example at ion doses ∼10¹⁶ He cm⁻²) and could not be recrystallized by annealing up to 775°C. This contrasts with previous results on bulk Si, in which electron- and very light ion-irradiation never led to amorphization. Visible photoluminescence, usually ascribed to quantum-size effects in the Si nanocrystals, was found to decrease and vanish after He⁺ ion doses as low as 3 × 10¹²–3 × 10¹³ He cm⁻² (which produce about 1 displacement per nanocrystal). This PL decrease is due to defect-induced non-radiative recombination centers, possibly situated at the Si nanocrystal/SiO₂ interface, and the pre-irradiation PL is restored by a 600°C anneal.     

A broad chemical and structural characterization of the damaged region of carbon implanted alumina

As candidate materials for future thermonuclear fusion reactors, isolating ceramics will be submitted to high energy gamma and neutron radiation fluxes together with an intense particle flux. Amorphization cannot be tolerated in ceramics for fusion applications, due to the associated volume change and the deterioration of mechanical properties. Therefore, a comprehensive study was carried out to examine the effects of carbon beam irradiation on polycrystalline aluminium oxide (Al₂O₃), a ceramic component of some diagnostic and plasma heating systems. Complementary techniques have allowed a complete chemical and structural surface analysis of the implanted alumina. Implantation with 75 keV, mono-energetic carbon ions at doses of 1 × 10¹⁷ and 5 × 10¹⁷ ions/cm² was performed on polished and thermally treated ceramic discs. The alumina targets were kept below 120 °C. The structural modifications induced during ion irradiation were studied by the GXRD and TEM techniques. Under these conditions, alumina is readily amorphized by carbon ions, the thickness of the ion-beam induced disordered area increasing with the ion dose. Matrix elements and ion implanted profiles were followed as a function of depth by using ToF-SIMS, indicating the maximum concentration of implanted ions to be in the deeper half of the amorphous region. Ion distribution and chemical modifications caused in the Al₂O₃ substrate by carbon irradiation were corroborated with XPS. The amount of oxygen in the vicinity of the implanted alumina surface was reduced, suggesting that this element was selectively sputtered during carbon irradiation. The intensity of those peaks referring to Al–O bonds diminishes, while contributions of reduced aluminium and metal carbides are found at the maximum of the carbon distribution. TEM observations on low temperature thermally annealed specimens indicate partial recovery of the initial crystalline structure.     

Controlling the microstructure of ZnO nanoparticles embedded in Sapphire by Zn ion implantation and subsequent annealing

(0 0 0 1) α-Al₂O₃ single crystals (sapphire) were implanted with Zn ions of 60 keV at a fluence of 1 × 10¹⁷ ions/cm². Transmission electron microscopy and optical absorption spectroscopy studies show the formation of ZnO nanoparticles in the sapphire substrate after the implanted sample was annealed at 700 °C in oxygen ambient. The photoluminescence spectrum of the annealed sample indicates the formation of ZnO nanoparticles with perfect lattice structure. The selected-area electron diffraction pattern proves that the ZnO nanoparticles have the (0 0 0 2) orientation which follows the orientation of Al₂O₃ substrate. The result shows that the crystallographic orientation of nanoparticles obtained through ion implantation is defined by the substrate.     

Lattice location and annealing studies of Hf implanted CaF2

Hafnium ions were implanted into calcium fluoride single crystals. The lattice damage introduced by the implantation was investigated with the Rutherford backscattering (RBS) channelling technique. The lattice location of the implanted ions was determined by performing channelling measurements for the 〈1 1 0〉 crystal direction. A comparison of the angular scan with Monte Carlo simulations leads to the conclusion that >90% of the Hf ions are on Ca sites directly after implantation. Subsequent annealing of the samples was performed in a rapid thermal annealing apparatus. Perturbed angular correlation (PAC) measurements with ¹⁸¹Hf(¹⁸¹Ta) show quadrupole interactions with ν_Q1 = 300(3) MHz (η = 0.00), ν_Q2 = 1285(13) MHz (η = 0.43) and ν_Q3 = 1035(10) MHz (η = 0.00) after annealing up to 1200 K.     

Oxidation of Zircaloy-4 by oxygen and the production of water

The interaction of isotopic oxygen (¹⁸O₂) with Zircaloy-4 (Zry-4) at 150 and 300 K has been studied using Auger electron spectroscopy (AES) and temperature-programmed desorption (TPD) methods. AES reveals the oxidation of the Zry-4 surface, reflected in shifts of the Zr(MNV) and Zr(MNN) features by about 5.5 and 3.0 eV, respectively, for both adsorption temperatures. The O(KLL)/Zr(MNN) Auger peak-to-peak height ratios as a function of exposure show the same trends at both temperatures. Following ¹⁸O₂ adsorption at 150 or 300 K, TPD experiments show hydrogen desorption near 400 K that is attributed to the presence of a surface-stabilized form of hydrogen. Additionally, water (H₂¹⁸O and H₂¹⁶O) desorption below 200 K and above 700 K is observed after 150 K oxygen adsorption. However, after oxygen adsorption at 300 K the only significant desorption features are from isotopic water (H₂¹⁸O). These findings indicate that mass transport involving the near-surface region contributes to the observed desorption, and that this behavior is dependent on the original adsorption temperature. Charging experiments using D₂ prior to and after ¹⁸O₂ adsorption were also performed and support our conclusions about the role of surface–subsurface mass transport in this system.     

The use of NRA to study thermal diffusion of helium in (U, Pu)O2

A lot of work has been already done on helium atomic diffusion in UO₂ samples, but information is still lacking about the fate of helium in high level damaged UOX and MOX matrices and more precisely their intrinsic evolutions under alpha self irradiation in disposal/storage conditions.The present study deals with helium atomic diffusion in actinide doped samples versus damage level. The presently used samples allow a disposal simulation of about 100 years of a UOX spent fuel with a 60 MW d kg^?1 burnup or a storage simulation of a MOX spent fuel with a 47.5 MW d kg^?1 burnup.For the first time, nuclear reaction analysis of radioactive samples has been performed in order to obtain diffusion coefficients of helium in (U, Pu)O₂. Samples were implanted with ³He⁺ and then annealed at temperatures ranging from 1123 K to 1273 K. The evolution of the ³He depth profiles was studied by the mean of the non-resonant reaction: ³He(d, p)⁴He. Using the SIMNRA software and the second Fick’s law, thermal diffusion coefficients have been measured and compared to the ³He thermal diffusion coefficients in UO₂ found in the literature.     

High-speed processing with Cl2 cluster ion beam

Cluster ion beam processes can produce high rate sputtering with low damage compared with monomer ion beam processes. Cl₂ cluster ion beams with different size distributions were generated with controlling the ionization conditions. Size distributions were measured using the time-of-flight (TOF) method. Si substrates and SiO₂ films were irradiated with the Cl₂ cluster ions at acceleration energies of 10–30 keV and the etching ratio of Si/SiO₂ was investigated. The sputtering yield increased with acceleration energy and was a few thousand times higher than that of Ar monomer ions. The sputtering yield of Cl₂ cluster ions was about 4400 atoms/ion at 30 keV acceleration energy. The etching ratio of Si/SiO₂ was above eight at acceleration energies in the range 10–30 keV. Thus, SiO₂ can be used as a mask for irradiation with Cl₂ cluster ion beam, which is an advantage for semiconductor processing. In order to keep high sputtering yield and high etching ratio, the cluster size needs to be sufficiently large and size control is important.     

Compatibility of erbium oxide coating with liquid lithium–lead alloy and corrosion protection effect of iron layer

Li–Pb compatibility of Er₂O₃ and Er₂O₃-Fe two-layer coatings has been explored for an understanding of corrosion behaviors and effects of the protection layer. The coatings were peeled off after static Li–Pb immersion test at 600 °C due to the degradation of adhesion between the coating–substrate interface. A loss of Er and then subsequent corrosion of Er₂O₃ were shown after immersion at 500 °C for 500 and 1505 h. However, the outer Fe layer played a role to decrease corrosion rate of the coatings by comparing with the results of Er₂O₃ single layer coatings. Deuterium permeation measurements after corrosion tests at 500 °C showed that the Er₂O₃ coatings kept permeation reduction factors of 10²–10³ after 500 h immersion, but seriously degraded after 1505 h immersion. Corrosion mechanisms suggest that corrosion protection properties will be modified by an optimization of the outer Fe layer and a control of oxygen concentration in Li–Pb.     

Thermal and irradiation induced interdiffusion in Fe3O4/MgO(0 0 1) thin film

The interface reactions in an epitaxial 10 nm-thick Fe₃O₄/MgO(0 0 1) film were investigated by using Rutherford Backscattering spectrometry (RBS), channeling (RBS-C) and X-ray reflectometry (XRR). The as-grown film had a good crystallinity indicated by the minimum yield and the half-angle value for Fe, respectively, χ_min(Fe) = 22% and ψ_1/2(Fe) = 0.62°. Annealing the films under partial argon pressure up to 600 °C led to a large enhancement of Mg out-diffusion into the film forming a wustite-type phase, but the total layer thickness did not change much. Ion irradiation of the film by 1 MeV Ar ion beam caused a strong Fe ion mixing resulting in a large interfacial zone with a thickness of 23 nm.     

Er+ implantation in SnO2:SiO2 layers: Structure changes and light emission

Structure changes and light emission behavior in Er⁺ implanted SnO₂:SiO₂ layers are studied, using transmission electron microscopy (TEM), Rutherford backscattering (RBS) and cathodoluminescence (CL). SnO₂:SiO₂ layers of different composition deposited with RF magnetron sputtering on Si wafers were implanted with 200 keV Er⁺ to a fluence of 3 × 10¹⁵ cm^?2 at room temperature. The implanted structures were then annealed at 600–1000 °C for 30 min, resulting in the formation of crystalline SnO₂ nanoclusters. Cross-section TEM revealed a strong reduction of the SnO₂ crystallite size down to several nanometers in the implanted area of the SnO₂:SiO₂ layer as compared to the undoped layer. In addition, a very narrow layer of SnO₂ nanocrystals appears at the SiO₂/Si interface. Several narrow CL emission peaks and wide bands were found which could be related to the decay of SnO₂ free excitons, to oxygen deficiency centers in SiO₂ and to transitions between the energy levels in the Er ions, apparently located at nanoclusters. The mechanisms of nanostructuring as well as the emission process are discussed.     

High energy Si ions bombardment effects on the properties of nano-layers of SiO2/SiO2 + Ag

We grew 50 periodic SiO₂/SiO₂ + Ag multi-layers by electron beam deposition technique. The co-deposited SiO₂ + Ag layers are 7.26 nm, SiO₂ buffer layers are 4 nm, and total thickness of film was determined as 563 nm. We measured the thickness of the layers using in situ thickness monitoring during deposition, and optical interferometry afterwards. The concentration and distribution of Ag in SiO₂ were determined using Rutherford backscattering spectrometry (RBS). In order to calculate the dimensionless figure of merit, ZT, the electrical conductivity, thermal conductivity and the Seebeck coefficient of the layered structure were measured at room temperature before and after bombardment with 5 MeV Si ions. The energy of the Si ions was chosen such that the ions are stopped deep inside the silicon substrate and only electronic energy due to ionization is deposited in the layered structure. Optical absorption (OA) spectra were taken in the range 200–900 nm to monitor the Ag nanocluster formation in the thin layers.     

Microstructure of ion-implanted region in TiNi alloy

TiNi alloy samples implanted with various fluences of 3 MeV Cu²⁺ ions were characterized by transmission electron microscope (TEM) and X-ray diffractometer. Cross-sectional TEM images of the samples showed that amorphous region was seen at the fluence of 10¹⁴ ions cm^?2 in case of ion implantation at 300 K of the substrate temperature, but in case of ion implantation at 100 K it did not appear even at 10¹⁵ ions cm^?2. These results were also confirmed by X-ray diffraction profiles of the same samples. Consequently, the extent of microstructure change of TiNi alloy by ion implantation was different depending on the substrate temperature.     

Micro-Raman studies of swift heavy ion irradiation induced structural and conformational changes in polyaniline nanofibers

Polyaniline (PAni) nanofibers doped with camphor sulfonic acid have been irradiated with 90 MeV O⁷⁺ ions at different fluences (3 × 10¹⁰?1 × 10¹² ions/cm²) using a 15UD Pelletron accelerator under ultra-high vacuum. XRD studies reveal a decrease in the domain length and an increase in the strain upon SHI irradiation. The increase in d-spacing corresponding to the (1 0 0) reflection of PAni nanofibers with increasing irradiation fluence has been attributed to the increase in the tilt angle of the chains with respect to the (a, b) basal plane of PAni. Decrease in the integral intensity upon SHI irradiation indicates amorphization of the material. Micro-Raman (μR) studies confirm amorphization of the PAni nanofibers and also show that the PAni nanofibers get de-doped upon SHI irradiation. μR spectroscopy also reveals a benzenoid to quinoid transition in the PAni chain upon SHI irradiation. TEM results show that the size of PAni nanofibers decreases with the increase in irradiation fluence, which has been attributed to the fragmentation of PAni nanofibers in the core of amorphized tracks caused by SHI irradiation.