Permeability of hydrogen and deuterium of Hastelloy XR

Permeation of hydrogen isotope through a high-temperature alloy used as heat exchanger and steam reformer pipes is an important problem in the hydrogen production system connected to be a high-temperature engineering test reactor (HTTR). An experiment of hydrogen (H₂) and deuterium (D₂) permeation was performed to obtain permeability of H₂ and D₂ of Hastelloy XR, which is adopted as heat transfer pipe of an intermediate heat exchanger of the HTTR. Permeability of H₂ and D₂ of Hastelloy XR were obtained as follows. The activation energy E₀ and pre-exponential factor F₀ of the permeability of H₂ were E₀=67.2±1.2 kJ mol⁻¹ and F₀=(1.0±0.2)×10⁻⁸ m³(STP) m⁻¹ s⁻¹ Pa^−0.5, respectively, in the pipe temperature ranging from 843 K (570 °C) to 1093 K (820 °C). E₀ and F₀ of the permeability of D₂ were respectively E₀=76.6±0.5 kJ mol⁻¹ and F₀=(2.5±0.3)×10⁻⁸ m³(STP) m⁻¹ s⁻¹ Pa^−0.5 in the pipe temperature ranging from 943 K (670 °C) to 1093 K (820 °C).     

Radiolysis studies of aqueous κ-carrageenan

The effects on N₂O and N₂ gas on the radiation degradation yield of aqueous kappa (κ-) carrageenan were investigated. The G_d of solution saturated with N₂O solution was expectedly much higher than in air (1.7 and 1.2 × 10⁻⁷ mol J⁻¹). On the other hand, a lower G_d of 1.1 × 10⁻⁷ mol J⁻¹ was obtained from κ-carrageenan solution saturated with N₂.The rate constant of reaction of OH radicals with sonicated and irradiated κ-carrageenan were determined using e-beam pulse radiolysis. The rate constant of OH interaction with sonicated κ-carrageenan decreased with decreasing molecular weight. On the other hand, the OH interaction with irradiated κ-carrageenan decreased but did not vary significantly with decreasing molecular weight. Metal ion (Na⁺) induced conformational transition into helical form decreased the rate constant of OH reaction with κ-carrageenan. Likewise, the G_d in aqueous form was affected by the conformational state of κ-carrageenan. The helical conformation gave a lower G_d (7 × 10⁻⁸ mol J⁻¹) than the coiled conformation (G_d = 1.2 × 10⁻⁷ mol J⁻¹).     

Behaviour of chromium steels in liquid Pb-55.5Bi with changing oxygen content and temperature

The behaviour of protective oxide layers on P122 steel and its welds and of ODS steel in liquid Pb_44.5Bi_55.5 (LBE) is examined under conditions of changing temperatures and oxygen concentrations. P122 (12Cr) and its welded joints are exposed to LBE at 550 °C for 4000 h with oxygen concentrations of 10⁻⁶ and 10⁻⁸ wt% (p(O₂) = 8.1 × 10⁻²³ bar and 5.2 × 10⁻²⁷ bar) which change every 800 h. It is found that like in case of constant oxygen concentration of 10⁻⁶ wt% a protective spinel layer (Fe(Fe_1−xCr_x)₂O₄) was maintained on P122 and also on its welded joint. Two experiments with exposure times of 4800 h are conducted on ODS steel, both with temperatures changing from 550 to 650 °C and back every 800 h, one experiment with 10⁻⁶ the other with 10⁻⁸ wt% oxygen in LBE. Both experiments show strong local dissolution attack after 4800 h which is in agreement with the behaviour of ODS in LBE at a constant temperature of 650 °C. However, dissolution attack is less in LBE with 10⁻⁸ wt% oxygen (p(O₂) = 3.0 × 10⁻²⁵ bar).     

Radiation damage in ZnO ion implanted at 15 K

Commercial O-face (0 0 0 1) ZnO single crystals were implanted with 200 keV Ar ions. The ion fluences applied cover a wide range from 5 × 10¹¹ to 7 × 10¹⁶ cm⁻². The implantation and the subsequent damage analysis by Rutherford backscattering spectrometry (RBS) in channelling geometry were performed in a special target chamber at 15 K without changing the target temperature of the sample. To analyse the measured channelling spectra the computer code DICADA was used to calculate the relative concentration of displaced lattice atoms.Four stages of the damage evolution can be identified. At low ion fluences up to about 2 × 10¹³ cm⁻² the defect concentration increases nearly linearly with rising fluence (stage I). There are strong indications that only point defects are produced, the absolute concentration of which is reasonably given by SRIM calculations using displacement energies of E_d(Zn) = 65 eV and E_d(O) = 50 eV. In a second stage the defect concentration remains almost constant at a value of about 0.02, which can be interpreted by a balance between production and recombination of point defects. For ion fluences around 5 × 10¹⁵ cm⁻² a second significant increase of the defect concentration is observed (stage III). Within stage IV at fluences above 10¹⁶ cm⁻² the defect concentration tends again to saturate at a level of about 0.5 which is well below amorphisation. Within stages III and IV the damage formation is strongly governed by the implanted ions and it is appropriate to conclude that the damage consists of a mixture of point defects and dislocation loops.     

Light ion irradiation effects on stuffed Lu2(Ti2−xLux)O7−x/2 (x = 0, 0.4 and 0.67) structures

We have recently synthesized “stuffed” (i.e., excess Lu) Lu₂(Ti_2−xLu_x)O_7−x/2 (x = 0, 0.4 and 0.67) compounds using conventional ceramic processing. X-ray diffraction measurements indicate that stuffing more Lu³⁺ cations into the oxide structure leads eventually to an order-to-disorder (O-D) transition, from an ordered pyrochlore to a disordered fluorite crystal structure. At the maximum deviation in stoichiometry (x = 0.67), the Lu³⁺ and Ti⁴⁺ ions become completely randomized on the cation sublattices, and the oxygen “vacancies” are randomized on the anion sublattice. Samples were irradiated with 400 keV Ne²⁺ ions to fluences ranging from 1 × 10¹⁵ to 1 × 10¹⁶ ions/cm² at cryogenic temperatures (∼77 K). Ion irradiation effects in these samples were examined by using grazing incident X-ray diffraction. The results show that the ion irradiation tolerance increases with disordering extent in the non-stoichiometric Lu₂(Ti_2−xLu_x)O_7−x/2.     

Corrosion of alkali-borosilicate waste glass K-26 in non-saturated conditions

Experimental data obtained during long term environmental tests of a nuclear waste alkali-borosilicate glass K-26 in an experimental near-surface repository are examined. Average leaching rates of the radionuclides were calculated: the leach rates gradually diminished from 9.4 × 10⁻⁷ g cm⁻² day⁻¹ over the first year to 2.2 × 10⁻⁷ g cm⁻² day⁻¹ over 16 years of tests. Radionuclide losses obey a square root time dependence indicating a diffusion-controlled release mechanism. The main parameters, which control the corrosion of waste glass K-26 in the near-surface repository, are the effective diffusion coefficient of radiocaesium D_Cs and the rate of glass hydrolysis r_h. Analysis of 16 years experimental data gave D_Cs = 4.5 × 10⁻¹² cm² day⁻¹ and r_h = 0.1 μm years⁻¹. Diffusion is predicted to be dominant for 16.4 years after which diffusion and hydrolytic dissolution are expected to be similarly important. This mixed stage is predicted continue for 262 years after which hydrolytic dissolution will be the dominant mechanism.     

Refractive index tailoring in congruent Lithium Niobate by ion implantation

Refractive index profiles of ion-implanted Lithium Niobate waveguides are investigated. Z⁺ and z⁻ congruent Lithium Niobate samples have been implanted with C³⁺ ions at a fluence of 4 × 10¹⁴ ions/cm². Dark m-lines measurements have been performed on ordinary (n_o) and extraordinary (n_e) indexes for three different wavelengths (532 nm, 632.8 nm, 818 nm) before and after the annealing process. A reconstruction of refractive index profiles by Reflectivity Calculation Method (RCM) is presented and commented. The literature data for nuclear damage regime have been collected and critically examined. n_o and n_e curves as function of the density of energy released in nuclear collisions, E_d, describing the effects of ion implantation on LN refractive indexes has been obtained on the basis of literature data. n_o depth profile, predicted according to n_o(E_d) curve, is in good agreement with the RCM reconstructed one. In the case of n_e, a satisfactory agreement has been reached only slightly modifying the n_e(E_d) curve and considering an alternative RCM profile structure.     

Thermal conductivities of hypostoichiometric (U, Pu, Am)O2−x oxide

The thermal conductivities of (U_0.68Pu_0.30Am_0.02)O_2.00−x solid solutions (x = 0.00-0.08) were studied at temperatures from 900 to 1773 K. The thermal conductivities were obtained from the thermal diffusivities measured by the laser flash method. The thermal conductivities obtained experimentally up to about 1400 K could be expressed by a classical phonon transport model, λ = (A + BT)⁻¹, A(x) = 3.31 × x + 9.92 × 10⁻³ (mK/W) and B(x) = (−6.68 × x + 2.46) × 10⁻⁴ (m/W). The experimental A values showed a good agreement with theoretical predictions, but the experimental B values showed not so good agreement with the theoretical ones in the low O/M ratio region. From the comparison of A and B values obtained in this study with the ones of (U,Pu)O_2−x obtained by Duriez et al. [C. Duriez, J.P. Alessandri, T. Gervais, Y. Philipponneau, J. Nucl. Mater. 277 (2000) 143], the addition of Am into (U, Pu)O_2−x gave no significant effect on the O/M dependency of A and B values.     

Oxidation kinetics and oxygen diffusion in low-tin Zircaloy-4 up to 1523 K

This paper deals with the study of oxidation kinetics and the identification of oxygen diffusion coefficients of low-tin Zy-4 alloy at intermediate (973 K ? T ? 1123 K) and high temperatures (T ? 1373 K). Two different cases were considered: dissolution of a pre-existing oxide layer in the temperature range 973 K ? T ? 1123 K and oxidation at T ? 1373 K. The results are the following ones: in the temperature range 973-1123 K, the oxygen diffusion coefficient in α_Zr phase can be expressed as D_α = 6.798 exp(−217.99 kJ/RT) cm²/s. In the temperature range 1373-1523 K, the oxygen diffusion coefficients in α_Zr, β_Zr and ZrO₂, were determined using an ‘inverse identification method’ from experimental high temperature oxidation data (i.e., ZrO₂, and α_Zr(O) layer thickness measurements); they can be expressed as follows: D_α = 1.543 exp(−201.55 kJ/ RT) cm²/s, D_β = 0.0068 exp(−102.62 kJ/ RT) cm²/s and D_ZrO2=0.115exp(−143.64kJ/RT)cm²/s. Finally an oxygen diffusion coefficient in α_Zr in the temperature range 973 K ? T ? 1523 K was determined, by combining the whole set of results: D_α = 4.604exp(−214.44 kJ/RT) cm²/s. In order to check these calculated diffusion coefficients, oxygen concentration profiles were determined by Electron Probe MicroAnalysis (EPMA) in pre-oxidized low-tin Zy4 alloys annealed under vacuum at three different temperatures 973, 1073 and 1123 K for different times, and compared to the calculated profiles. At last, in the framework of this study, it appeared also necessary to reassess the Zr-O binary phase diagram in order to take into account the existence of a composition range in the two zirconia phases, α_ZrO2 and β_ZrO2.     

Enthalpy measurements of La2Te3O9 and La2Te4O11

Enthalpy increment measurements on La₂Te₃O₉(s) and La₂Te₄O₁₁(s) were carried out using a Calvet micro-calorimeter. The enthalpy values were analyzed using the non-linear curve fitting method. The dependence of enthalpy increments with temperature was given as: H°(T) − H°(298.15 K) (J mol⁻¹) = 360.70T + 0.00409T² + 133.568 × 10⁵/T − 149 923 (373 ? T (K) ? 936) for La₂Te₃O₉ and H°(T) − H°(298.15 K) (J mol⁻¹) = 331.927T + 0.0549T² + 29.3623 × 10⁵/T − 114 587 (373 ? T (K) ? 936) for La₂Te₄O₁₁.     

Thermal conductivity of (U,Pu,Np)O2 solid solutions

The thermal conductivities of (U_,Pu_,Np)O₂ solid solutions were studied at temperatures from 900 to 1770 K. Thermal conductivities were obtained from the thermal diffusivity measured by the laser flash method. The thermal conductivities obtained below 1400 K were analyzed with the data of (U,Pu,Am)O₂ obtained previously, assuming that the B-value was constant, and could be expressed by a classical phonon transport model, λ = (A + BT)⁻¹, A(z₁, z₂) = 3.583 × 10⁻¹ × z₁ + 6.317 × 10⁻² × z₂ + 1.595 × 10⁻² (m K/W) and B = 2.493 × 10⁻⁴ (m/W), where z₁ and z₂ are the contents of Am- and Np-oxides. It was found that the A-values increased linearly with increasing Np- and Am-oxide contents slightly, and the effect of Np-oxide content on A-values was smaller than that of Am-oxide content. The results obtained from the theoretical calculation based on the classical phonon transport model showed good agreement with the experimental results.     

Structural studies of silicon oxynitride layers formed by low energy ion implantation

Silicon oxynitride (Si_xO_yN_z) layers were synthesized by implanting ¹⁶O₂⁺ and ¹⁴N₂⁺ 30 keV ions in 1:1 ratio with fluences ranging from 5 × 10¹⁶ to 1 × 10¹⁸ ions cm⁻² into single crystal silicon at room temperature. Rapid thermal annealing (RTA) of the samples was carried out at different temperatures in nitrogen ambient for 5 min. The FTIR studies show that the structures of ion-beam synthesized oxynitride layers are strongly dependent on total ion-fluence and annealing temperature. It is found that the structures formed at lower ion fluences (∼1 × 10¹⁷ ions cm⁻²) are homogenous oxygen-rich silicon oxynitride. However, at higher fluence levels (∼1 × 10¹⁸ ions cm⁻²) formation of homogenous nitrogen rich silicon oxynitride is observed due to ion-beam induced surface sputtering effects. The Micro-Raman studies on 1173 K annealed samples show formation of partially amorphous oxygen and nitrogen rich silicon oxynitride structures with crystalline silicon beneath it for lower and higher ion fluences, respectively. The Ellipsometry studies on 1173 K annealed samples show an increase in the thickness of silicon oxynitride layer with increasing ion fluence. The refractive index of the ion-beam synthesized layers is found to be in the range 1.54-1.96.     

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.     

Study of silver diffusion in silicon carbide

Diffusion of silver in 6H-SiC and polycrystalline CVD-SiC was investigated using α-particle channeling spectroscopy and electron microscopy. Fluences of 2 × 10¹⁶ cm⁻² of ¹⁰⁹Ag⁺ were implanted with an energy of 360 keV at room temperature, at 350 °C and 600 °C, producing an atomic density of approximately 2% at the projected range of about 110 nm. The broadening of the implantation profile and the loss of silver through the front surface during vacuum annealing at temperatures up to 1600 °C was determined. Fairly strong silver diffusion was observed after an initial 10 h annealing period at 1300 °C in both polycrystalline and single crystalline SiC, which is mainly due to implant induced radiation damage. After further annealing at this temperature no additional diffusion took place in the 6H-SiC samples, while it was considerably reduced in the CVD-SiC. The latter was obviously due to grain boundary diffusion and could be described by the Fick diffusion equation. Isochronal annealing of CVD-SiC up to 1400 °C exhibited an Arrhenius type temperature dependence, from which a frequency factor D_o ∼ 4 × 10⁻¹² m² s⁻¹ and an activation energy E_a ∼ 4 × 10⁻¹⁹ J could be extracted. Annealing of 6H-SiC above 1400 °C shifted the silver profile without any broadening towards the surface, where most of the silver was released at 1600 °C. Electron microscopy revealed that this process was accompanied by significant re-structuring of the surface region. An upper limit of D < 10⁻²¹ m² s⁻¹ was estimated for 6H-SiC at 1300 °C.     

Deuterium retention in sintered boron carbide exposed to a deuterium plasma

Depth profiles of deuterium up to a depth of 10 μm have been measured using the D(³He,p)⁴He nuclear reaction in a resonance-like technique after exposure of sintered boron carbide, B₄C, at elevated temperatures to a low energy (≈200 eV/D) and high ion flux (≈10²¹ m⁻² s⁻¹) D plasma. The proton yield was measured as a function of incident ³He energy and the D depth profile was obtained by deconvolution of the measured proton yields using the program SIMNRA. D atoms diffuse into the bulk at temperatures above 553 K, and accumulate up to a maximum concentration of about 0.2 at.%. At high fluences (?10²⁴ D/m²), the accumulation in the bulk plays a major role in the D retention. With increasing exposure temperature, the amount of D retained in B₄C increases and exceeds a value of 2 × 10²¹ D/m² at 923 K. The deuterium diffusivity in the sintered boron carbide is estimated to be D = 2.6 × 10⁻⁶exp{−(107 ± 10) kJ mol⁻¹/RT} m² s⁻¹.     

核级不锈钢焊接接头钝化膜耐蚀性能和半导体特性研究

采用电化学阻抗谱(EIS)、场发射扫描电子显微镜(SEM)、Auger扫描能谱仪(AES)以及容抗测试技术(M-S曲线),研究了316LN/316L不锈钢焊接接头在模拟压水堆一回路高温高压水中形成的钝化膜的耐蚀性能和半导体特性。结果表明,焊缝区、热影响区和母材区形成的钝化膜的耐蚀性能不同,热影响区钝化膜开路电位及电化学阻抗等均低于其他区域,说明热影响区钝化膜的耐蚀性能最差,这主要与钝化膜的致密程度、厚度及Cr氧化物的含量有关。M-S曲线表明,母材区钝化膜平带电位为-0.7V,较其他区域(-0.4V)负移,表明有BO-3等阴离子在钝化膜表面吸附,加之具有较低的施主和受主浓度,可排斥侵蚀离子的腐蚀,使之较其他区域有更强的耐蚀性能。     

Study of surface activation of PET by low energy (keV) Ni and N ion implantation

Polyethyleneterephthalate (PET) has been modified by 100 keV Ni⁺ and N⁺ ions using metal ion from volatile compound (MIVOC) ion source to fluence ranging from 1 × 10¹⁴ to 1 × 10¹⁶ ions/cm². The increasing application of polymeric material in technological and scientific field has motivated the use of surface treatment to modify the physical and chemical properties of polymer surfaces. When a material is exposed to ionization radiation, it suffers damage leading to surface activation depending on the type. The surface morphology was observed by atomic force microscopy (AFM). That show the roughness increases with fluence in both the cases. The Ni particles as precipitation in PET were observed by cross-section transmission electron microscopy (XTEM). The optical band gap (E_g) deduced from absorption spectra; was calculated by Tau’c relation. Raman spectroscopy shows quantitatively the chemical nature at the damage caused by the Ni⁺ and N⁺ bombardment. The ration of I_D/I_G shows graphite-like structure is formed on the surface. A layer of hydrogenated amorphous carbon is formed on the surface, which has confirmed by XPS results also.     

Formation of silicon hydride using hyperthermal negative hydrogen ions (H) extracted from an argon-seeded hydrogen sheet plasma source

An E × B probe (a modified Wien filter) is constructed to function both as a mass spectrometer and ion implanter. The device, given the acronym EXBII selects negative hydrogen ions (H⁻) from a premixed 10% argon-seeded hydrogen sheet plasma. With a vacuum background of 1.0 × 10⁻⁶ Torr, H⁻ extraction ensues at a total gas feed of 1.8 mTorr, 0.5 A plasma discharge. The EXBII is positioned 3 cm distance from the sheet core as this is the region densely populated by cold electrons (T_e ∼ 2 eV, N_e ∼ 3.4 × 10¹¹ cm⁻³) best suited for H⁻ formation. The extracted H⁻ ions of flux density ∼0.26 A/m² are segregated, accelerated to hyperthermal range (<100 eV) and subsequently deposited into a palladium-coated 1.1 × 1.1 cm², n-type Si (1 0 0) substrate held at the rear end of the EXBII, placed in lieu of its Faraday cup. The palladium membrane plays the role of a catalyst initiating the reaction between Si atoms and H⁻ ions simultaneously capping the sample from oxidation and other undesirable adsorbents. AFM and FTIR characterization tests confirm the formation of SiH₂. Absorbance peaks between 900-970 cm⁻¹ (bending modes) and 2050-2260 cm⁻¹ (stretching modes) are observed in the FTIR spectra of the processed samples. It is found that varying hydrogen exposure time results in the shifting of wavenumbers which may be interpreted as changes in the frequencies of vibration for SiH₂. These are manifestations of chemical changes accompanying alterations in the force constant of the molecule. The sample with longer exposure time exhibits an additional peak at 2036 cm⁻¹ which are hydrides of nano-crystalline silicon.     

Frequency dependence studies on the interface trap density and series resistance of HfO2 gate dielectric deposited on Si substrate: Before and after 50 MeV Li ions irradiation

We report the first investigation of the frequency dependent effect of 50 MeV Li³⁺ ion irradiation on the series resistance and interface state density determined from capacitance-voltage (C-V) and conductance-voltage (G-V) characteristics in HfO₂ based MOS capacitors prepared by rf-sputtering. The samples were irradiated by 50 MeV Li³⁺ ions at room temperature. The measured capacitance and conductance were corrected for series resistance. The series resistance was estimated at various frequencies from 1 KHz to 1 MHz before and after irradiation. It was observed that the series resistance decreases from 6344.5 to 322 Ω as a function of frequency before irradiation and 8954-134 Ω after irradiation. The interface state density D_it decreases from 1.12 × 10¹² eV⁻¹ cm⁻² before irradiation to 3.67 × 10¹¹ eV⁻¹ cm⁻² after ion irradiation and further decreases with increasing frequency.     

Method to measure composition modifications in polyethylene terephthalate during ion beam irradiation

Matter losses of polyethylene terephthalate (PET, Mylar) films induced by 1600 keV deuteron beams have been investigated in situ simultaneously by nuclear reaction analysis (NRA), deuteron forward elastic scattering (DFES) and hydrogen elastic recoil detection (HERD) in the fluence range from 1 × 10¹⁴ to 9 × 10¹⁶ cm⁻². Volatile degradation products escape from the polymeric film, mostly as hydrogen-, oxygen- and carbon-containing molecules. Appropriate experimental conditions for observing the composition and thickness changes during irradiation are determined. ¹⁶O(d,p₀)¹⁷O, ¹⁶O(d,p₁)¹⁷O and ¹²C(d,p₀)¹³C nuclear reactions were used to monitor the oxygen and carbon content as a function of deuteron fluence. Hydrogen release was determined simultaneously by H(d,d)H DFES and H(d,H)d HERD. Comparisons between NRA, DFES and HERD measurements show that the polymer carbonizes at high fluences because most of the oxygen and hydrogen depletion has already occured below a fluence of 3 × 10¹⁶ cm⁻². Release curves for each element are determined. Experimental results are consistent with the bulk molecular recombination (BMR) model.