Influence of titanium ions implantation on corrosion behavior of zirconium in 1 M H2SO4

In order to study the effect of titanium ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted with titanium ions with fluence ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc (MEVVA) source at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zirconium in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zirconium implanted with titanium ions. The larger the fluence, the better is the corrosion resistance of implanted sample. Finally, the mechanism of the corrosion behavior of titanium-implanted zirconium was discussed.     

Impact of yttrium ion implantation on corrosion behavior of laser beam welded zircaloy-4 in sulfuric acid solution

In order to study the effect of yttrium ion implantation on the aqueous corrosion behavior of laser beam welded zircaloy-4 (LBWZr4), The butt weld joint of zircaloy-4 was made by means of a carbon dioxide laser, subsequently the LBWZr4 samples were implanted with yttrium ion using a MEVVA source at an energy of 40 keV, with a fluence range from 1 × 10¹⁶ to 4 × 10¹⁶ ions/cm² at about 150 °C. Three-sweep potentiodynamic polarization measurement was employed to evaluate the aqueous corrosion behavior of yttrium-implanted LBWZr4 in a 0.5 M H₂SO₄ solution. Scanning electron microscopy (SEM) was used to examine the surface topographic character of the yttrium-implanted LBWZr4 before and after the potentiodynamic polarization measurement. The valences of the carbon, yttrium, and zirconium in the surface layer were analyzed by X-ray photoemission spectroscopy (XPS). It was found that a significant improvement was achieved in the aqueous corrosion resistance of yttrium-implanted LBWZr4 compared with that of the un-implanted LBWZr4. The mechanism of the corrosion resistance improvement of the yttrium-implanted LBWZr4 is probably due to the addition of the yttrium oxide dispersoid into the zirconium matrix.     

Surface analysis and oxidation behavior of Y-ion implanted AZ31 magnesium alloys

AZ31 samples were implanted with yttrium ions with fluences of 5 × 10¹⁶, 1 × 10¹⁷ and 5 × 10¹⁷ ions/cm², using a metal vapor vacuum arc source at an extraction voltage of 45 kV. The surfaces of the implanted samples were then analyzed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It was found that after treatment a pre-oxidation layer was formed, and the higher the fluence, the thicker the pre-oxidation layer was. The valence states showed that yttrium existed in the form of Y₂O₃. Isothermal oxidation tests have been conducted in pure oxygen at 773 K for 90 min to evaluate the oxidation behavior of the implanted samples. The results indicate that after implantation the oxidation resistance of the samples was significantly improved. Moreover, the greater the fluence, the better the oxidation resistance has been achieved. The characterization of the implanted layers after isothermal oxidation was examined by SEM, AES and XPS. From the results, it can be found that the thickness of the oxide scale formed on the implanted surfaces have been greatly decreased, and there is no obvious change for both the thickness of the pre-oxidation layer and the valence states of the elements after oxidation.     

Modification of medical metals by ion implantation of copper

The effect of copper ion implantation on the antibacterial activity, wear performance and corrosion resistance of medical metals including 317 L of stainless steels, pure titanium, and Ti-Al-Nb alloy was studied in this work. The specimens were implanted with copper ions using a MEVVA source ion implanter with ion doses ranging from 0.5 × 10¹⁷ to 4 × 10¹⁷ ions/cm² at an energy of 80 keV. The antibacterial effect, wear rate, and inflexion potential were measured as a function of ion dose. The results obtained indicate that copper ion implantation improves the antibacterial effect and wear behaviour for all the three medical materials studied. However, corrosion resistance decreases after ion implantation of copper. Experimental results indicate that the antibacterial property and corrosion resistance should be balanced for medical titanium materials. The marked deteriorated corrosion resistance of 317 L suggests that copper implantation may not be an effective method of improving its antibacterial activity.     

Change of sheet resistance of high purity alumina ceramics implanted by Cu and Ti ions

High purity alumina ceramics (99% Al₂O₃) was implanted by copper ion and titanium ion in a metal vapour vacuum arc (MEVVA) implanter, respectively. The influence of implantation parameters was studied varying ion fluence. The samples were implanted by 68 keV Cu ion and 82 keV Ti ion with fluences from 1 × 10¹⁵ to 1 × 10¹⁸ ions/cm², respectively. The as-implanted samples were investigated by scanning electron microscopy (SEM), glancing X-ray diffraction (GXRD), scanning Auger microscopy (SAM), and four-probe method. Different morphologies were observed on the surfaces of the as-implanted samples and clearly related to implantation parameters. For both ion implantations, the sheet resistances of the alumina samples implanted with Cu and Ti ion fluences of 1 × 10¹⁸ ions/cm², respectively, reached the corresponding minimum values because of the surface metallization. The experimental results indicate that the high-fluence ion implantation resulted in conductive layer on the surface of the as-implanted high purity alumina ceramics.     

Corrosion behavior of tin ions implanted zirconium in 1N H2SO4

In order to study the effect of tin ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted with tin ions to a fluence ranging from 1 × 10²⁰ to 5 × 10²¹ ions/m², using a metal vapor vacuum arc source (MEVVA) at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer were analyzed by X-ray photoelectron spectroscopy (XPS) and auger electron spectroscopy (AES) respectively. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to examine the micro-morphology and microstructure of tin-implanted samples. When the fluence was greater than 1 × 10²⁰ ions/m², many small tin balls were produced in the implanted surface. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zirconium in a 1N H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zirconium implanted with 1 × 10²⁰ ions/m². When the fluence is higher than 1 × 10²⁰ ions/m², the corrosion resistance of zirconium implanted with tin ions decreased compared with that of the non-implanted zirconium. Finally, the mechanism of the corrosion behavior of the tin-implanted zirconium is discussed.     

Impact of 100 MeV Au on the surface of relaxed Si0.5Ge0.5 alloy films studied by atomic force microscopy

We demonstrate a gradual surface modification process of relaxed Si_0.5Ge_0.5 alloy films by 100 MeV Au beam with fluence varying between 5 × 10¹⁰ and 1 × 10¹² ions/cm² at 80 K by means of atomic force microscopy (AFM). Presence of Ge quantum dots (QDs) was found in the virgin sample. The disappearance of the QDs were noticed when the samples were irradiated with a fluence of 5 × 10¹⁰ ions/cm². Craters were found developing at a fluence of 1 × 10¹¹ ions/cm². Apart from the evolution of the craters, blisters were also detected at a fluence of 1 × 10¹² ions/cm². Variation of the average root mean square value of the surface roughness as a function of fluence was examined.     

Structure and tribological performance by nitrogen and oxygen plasma based ion implantation on Ti6Al4V alloy

Ti6Al4V alloy was implanted with nitrogen-oxygen mixture by using plasma based ion implantation (PBII) at pulsed voltage −10, −30 and −50 kV. The implantation was up to 6 × 10¹⁷ ions/cm² fluence. The changes in chemical composition, structure and hardness of the modified surfaces were studied by XPS and nanoindentation measurements. According to XPS, it was found that the modified layer was predominantly TiO₂, but contained small amounts of TiO, Ti₂O₃, TiN and Al₂O₃ between the outmost layer and metallic substrate. Surface hardness and wear resistance of the samples increased significantly after PBII treatment, the wear rate of the sample implanted N₂-O₂ mixture at −50 kV decreased eight times than the untreated one. The sample implanted N₂-O₂ mixture showed better wear resistance than that of the sample only implanted oxygen at − 50 kV. The wear mechanism of untreated sample was abrasive-dominated and adhesive, and the wear scar of the sample implanted at −50 kV was characterized by abrasive wear-type ploughing.     

锆离子注入锆-4合金缺陷的慢正电子研究

采用慢正电子束多普勒展宽谱研究了Zr离子注入Zr-4合金产生的缺陷及其退火回复行为，发现经过大于离子注入剂量为1×10¹⁶cm^-2的样品所产生的缺陷在注入过程中已经回复，而对剂量为1×10¹⁵cm^-2样品做300℃退火处理，其缺陷基本回复，得出合金缺陷回复能较低的结论. 考虑到材料的缺陷含量越高，其抗腐蚀性能越差，在辐照环境下通过给材料保持一定温度，即可使其缺陷得到较好回复，从而提高材料的抗腐蚀性能.     

Structural and photoluminescence properties of Si nanoclusters obtained by ion implantation into Si3N4 films

In the present paper we report structural and photoluminescence (PL) results from samples obtained by Si implantation into stoichiometric silicon nitride (Si₃N₄) films. The Si excess was introduced in the matrix by 170 keV Si implantation performed at different temperatures with a fluence of Φ=1×10¹⁷ Si/cm². The annealing temperature was varied between 350 and 900 °C in order to form the Si precipitates. PL measurements, with a 488 nm Ar laser as an excitation source, show two superimposed broad PL bands centered around 760 and 900 nm. The maximum PL yield is achieved for the samples annealed at 475 °C. Transmission electron microscopy (TEM) measurements show the formation of amorphous nanoclusters and their evolution with the annealing temperature.     

Thermoluminescence and photoluminescence of LiNaSO4:Eu irradiated with 24 and 48 MeV Li ion beam

Thermoluminescence (TL) of LiNaSO₄:Eu phosphor, irradiated with 24 and 48 MeV ⁷Li ions at different fluences in the range 5×10⁹-1×10¹² ion/cm², has been studied. The samples from the same batch were also exposed to γ-rays from a Cs¹³⁷ source for comparative studies. The TL glow curves of the materials, irradiated with ⁷Li ions, have similar structures to that of γ-irradiated sample. They have a simple structure with a prominent peak at 412 K along with small one at around 481 K. The intensity ratios of 412-481 K peaks have been observed to increase with fluence increasing, while that of γ-irradiated sample shows a reverse trend. This could be attributed to the changes in the recombination center populations due to ⁷Li ions, that have been implanted inside the matrix of LiNaSO₄:Eu, during irradiation and might also act as a source for new trapping and luminescent centers. The implantation has been confirmed by TRIM calculations. The penetration depths (where the ion comes to rest) are found to be 145 and 463 μm corresponding to 24 and 48 MeV ion beam energies, respectively, which are less than the thickness of the sample chips (∼800 μm). The efficiencies of LiNaSO₄:Eu to 24 and 48 MeV ⁷Li ions measured relative to γ-rays of Cs¹³⁷ are found to be 0.007 and 0.024, respectively. Theoretical analysis of the glow curves of the samples irradiated by ⁷Li ions and γ-rays were done by glow curve deconvolution method to determine trapping parameters of various peaks. The experimentally observed linearity/sublinearity has been discussed in the frame of track interaction model. Photoluminescence studies in the ⁷Li ions irradiated and un-irradiated samples show that europium ions have incorporated in the host in their divalent (emission at 440 nm) as well as trivalent (emissions at 594, 615 and 700 nm) forms. The intensities of the emission bands of these ions have been observed to increase with fluence increasing.     

Influence of Ni deposition and subsequent N ion implantation at different substrate temperatures on nano-structure and corrosion behaviour of type 316 and 304 stainless steels

Ni thin films of 250 nm thicknesses were coated on type 304 and 316 stainless steels and post N⁺ ion implanted at 15 keV energy with a fluence of 5 × 10¹⁷ N⁺ cm⁻² at different substrate temperatures. Surface nano-structure of the samples were analysed using X-ray diffraction (XRD), atomic force microscopy (AFM) before corrosion test and scanning electron microscopy (SEM) after corrosion test. Corrosion behaviour of the samples in 1.0 M H₂SO₄ solution was investigated by means of potentiodynamic technique. Nano-structure and crystallography of the films showed the development of Ni₃N(1 1 1) and Ni₄N(2 0 0) orientations with a minimum surface roughness and grain size at 400 K substrate temperature. The highest corrosion resistance with a corrosion current of 0.01 μA cm⁻² (for SS(316)) and 0.56 μA cm⁻² (for SS(304)) was achieved in case of samples which were N⁺ ion implanted at 400 K. Results for both types of stainless steels showed good agreement and the better performance of SS(316) was attributed to the 2% molybdenum contents in the alloy composition of this type of stainless steel, which enhances the effectiveness of nitrogen in retarding the corrosion process.     

Well-confined Yb:GdVO4 laser waveguide formed by MeV C ion implantation

The planar waveguide in x-cut Yb:GdVO₄ crystal has been fabricated by 6.0 MeV carbon ion implantation with the fluence of 1 × 10¹⁴ ions/cm² at room temperature. The modes of the waveguide were measured by the prism-coupling method with the wavelength of 633 nm and 1539 nm, respectively. An enhanced ordinary refractive index region was formed with a width of about 4.0 μm beneath the sample surface to act as a waveguide structure. By performing a modal analysis on the observed transverse magnetic polarized modes, it was found that all the transverse magnetic polarized modes can be well-confined inside the waveguide. Strong Yb-related photoluminescence in Yb:GdVO₄ waveguide has been observed at room temperature, which reveals that it exhibits possible applications for integrated active photonic devices.     

Room temperature magnetic properties of Fe and C implanted ZnO films

ZnO films prepared by radio frequency magnetron sputtering were singly or sequentially implanted with 120 keV Fe ions at a fluence of 5 × 10¹⁶ ions/cm² and 20 keV C ions at a fluence of 3 × 10¹⁵ ions/cm². Magnetic and optical properties as well as structures of the films have been investigated using various techniques. Magnetic measurements show that the as-deposited ZnO film presents room temperature ferromagnetism. Single Fe or C ion implantation has no contribution to enhancement in the film magnetism, while magnetic moment increases distinctly in the Fe and C ions sequentially implanted film. Results from structural measurements reveal that Fe nanoparticles are formed in the Fe singly implanted ZnO film. The post C implantation induces dissolution of Fe nanoparticles and promotes Fe atoms to substitute Zn atoms in the lattice. Based on the structural results, the effect of magnetic enhancement has been tentatively interpreted.     

Creation of nanoparticles and luminescence in Al2O3 crystal by Zn ion implantation

Single crystal α-Al₂O₃ wafers were implanted with 45 keV Zn ions up to a fluence of 1×10¹⁷ ions/cm², and were then subjected to furnace annealing in oxygen atmosphere at different temperatures. Various techniques have been applied to study the creation of nanoparticles (NPs), defects and their thermal evolutions, as well as their effects on optical properties of Al₂O₃. Our results clearly show that Zn NPs have been synthesized in the as-implanted sample and they begin to be oxidized at 500 °C. Two broad photoluminescence bands appear in the Zn ion-implanted samples and their intensities depend on the annealing temperatures. The results have been interpreted in view of creation of the defects and NPs, Zn atoms diffusion as well as their thermal evolution during annealing.     

Optical waveguide with homogeneous refractive index profile in LiNbO3 by double-low-energy Oxygen ion implantation

We report on the formation of the planar waveguide by 550 keV O ion followed by 250 keV O ion implantation in lithium niobate (LiNbO₃), at fluences of 6 × 10¹⁴ ions/cm² and 3 × 10¹⁴ ions/cm², respectively. The Rutherford backscattering/channeling spectra have shown the atomic displacements in the damage region before and after annealing. A broad and nearly homogeneous damage layer has been formed by double-energy ion implantation after annealing. Both the dark mode spectra and the data of refractive index profile verified that the extraordinary refractive index was enhanced in the ion implanted region of LiNbO₃. A homogeneous near-field intensity profile was obtained by double-low-energy ion implantation. There is a reasonable agreement between the simulated modal intensity profile and the experimental data. The estimated propagation loss is about 0.5 dB/cm.     

Synthesis of molybdenum silicide by both ion implantation and ion beam assisted deposition

Two groups of Mo/Si films were deposited on surface of Si(1 0 0) crystal. The first group of the samples was prepared by both ion beam assisted deposition (IBAD) and metal vapor vacuum arc (MEVVA) ion implantation technologies under temperatures from 200 to 400 °C. The deposited species of IBAD were Mo and Si, and different sputtering Ar ion densities were selected. The mixed Mo/Si films were implanted by Mo ion with energy of 94 keV, and fluence of Mo ion was 5 × 10¹⁶ ions/cm². The second group of the samples was prepared only by IBAD under the same test temperature range. The Mo/Si samples were analyzed by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), sheet resistance, nanohardness, and modulus of the Mo/Si films were also measured. For the Mo/Si films implanted with Mo ion, XRD results indicate that phase of the Mo/Si films prepared at 400 and 300 °C was pure MoSi₂. Sheet resistance of the Mo/Si films implanted with Mo ion was less than that of the Mo/Si films prepared without ion implantation. Nanohardness and modulus of the Mo/Si films were obviously affected by test parameters.     

Thermal evolution of vacancy defects induced in sintered UO2 disks by helium implantation

A slow positron beam coupled with Doppler broadening (DB) spectrometer was used to measure the low- and high-momentum annihilation fractions, S and W, respectively, as a function of positron energy in UO₂ disks implanted with different 1 MeV ³He fluences and annealed in ArH₂ or in vacuum. The S(E) and W(E) behaviors indicate that for fluences in the range from 2 × 10¹⁴ to 2 × 10¹⁶³He cm⁻², the vacancy defects distribution evolves with the annealing temperature in the range from 264 to 700 °C under ArH₂. This evolution is found to be dependent on the ³He fluence implanted in the sintered UO₂ disks. For the lowest fluence of 2 × 10¹⁴³He cm⁻², the S(W) plot with positron energy as the running parameter suggests that only the concentration of vacancy defects decreases when annealing temperature increases. For the highest implantation fluences (from 5 × 10¹⁵ to 2 × 10¹⁶³He cm⁻²) the S(W) plot suggests that the nature of the vacancy defects changes in the annealing temperature range from 260 to 400 °C. Measurements performed in implanted UO₂ disks annealed in vacuum have revealed a partial recovery of the vacancy defects possibly due to their recombination with mobile oxygen interstitials. The role of the hydrogen infusion into the disk is also discussed.     

Intralamellar structural modifications related to the proton exchanging in K4Nb6O17 layered phase

Basic structural aspects about the layered hexaniobate of K₄Nb₆O₁₇ composition and its proton-exchanged form were investigated mainly by spectroscopic techniques. Raman spectra of hydrous K₄Nb₆O₁₇ and H₂K₂Nb₆O₁₇·H₂O show significant modifications in the 950-800 cm⁻¹ region (Nb-O stretching mode of highly distorted NbO₆ octahedra). The band at 900 cm⁻¹ shifts to 940 cm⁻¹ after the replacement of K⁺ ion by proton. Raman spectra of the original materials and the related deuterated samples are similar suggesting that no isotopic effect occurs. Major modifications were observed when H₂K₂Nb₆O₁₇ was dehydrated: the relative intensity of the band at 940 cm⁻¹ decreases and new bands seems to be present at about 860-890 cm⁻¹. The H⁺ ions should be shielded by the hydration sphere what preclude the interaction with the layers. Removing the water molecules, H⁺ ions can establish a strong interaction with oxygen atoms, decreasing the bond order of Nb-O linkage. X-ray absorption near edge structure studies performed at Nb K-edge indicate that the niobium coordination number and oxidation state remain identical after the replacement of potassium by proton. From the refinement of the fine structure, it appears that the Nb-Nb coordination shell is divided into two main contributions of about 0.33 and 0.39 nm, and interestingly the population, i.e., the number of backscattering atoms is inversed between the two hexaniobate materials.     

Investigation on upconversion photoluminescence of Bi3TiNbO9:Er:Yb thin films

Bi₃TiNbO₉:Er³⁺:Yb³⁺ (BTNEY) thin films were fabricated on fused silica by pulsed laser deposition. It was demonstrated that different laser fluence and substrate temperature during growth of BTNEY upconversion photoluminescence (UC-PL) samples control the film’s grain size and hence influences the UC-PL properties. The average grain size of BTNEY thin films deposited on fused silica substrates with laser fluence 4, 5, 6, and 7 J/cm² are 30.8, 35.9, 40.6, and 43.4 nm, respectively. The 525 nm emission intensities increase with the deposition laser fluence and the emission intensities of BTNEY thin film deposited under 700 and 600 °C are almost 24 and 4 times, respectively, as strong as those of samples under 500 °C. The grain size of BTNEY thin film increases with the increasing temperature. UC-PL of BTNEY films is enhanced by increasing grain size of the films.