Plutonium solubility and self-irradiation effects in borosilicate glass

This article presents the limitations for the immobilization of plutonium in borosilicate glasses. A first one is related to the solubility of this element in glass. The effects of the temperature and redox conditions during glass processing were studied. Glass specimens containing plutonium and plutonium surrogates are fabricated. The results show that trivalent elements (La, Gd, Nd, etc.) exhibit greater solubility than tetravalent elements (Pu, Th, Hf). Fabricating the plutonium-doped glass samples under reductive conditions reduced the Pu to trivalent oxidation state and increased its solubility to 4 wt% PuO₂ without reaching the solubility limit. A structural approach based on the results of EXAFS and NMR spectroscopy suggests that the structural role of the trivalent and tetravalent elements corresponds to that of intermediate network modifiers and intermediate network formers, respectively.

The second factor is the effect of actinide decay on the long-term behavior of the glass. Borosilicate glass samples were doped with different curium contents (0.05, 0.5, 1.5 and 4.1 wt% of CmO₂). The macroscopic properties (density, microhardness and initial dissolution rate) of the glasses were characterized up to 4 × 10¹⁸  g⁻¹. No significant effect on the initial alteration rate was detected. The glass swelled slightly, saturating at about 0.5% after receiving a dose of about 2 × 10¹⁸  g⁻¹.

Further studies are ongoing to confirm the satisfactory long-term behavior of the borosilicate glass matrix at higher doses, and to determine the solubility limit of plutonium in reducing conditions.     

Self-reduction of dioxoplutonium VI: Characterization and modeling of radiolytic and disproportionation pathways

Kinetic modeling shows that self-reduction of dioxoplutonium VI is consistent with disproportionation of Pu(VI) and reaction of the Pu(VII) product with water, as well as with alpha-particle radiolysis of water and reaction of products with Pu(VI). Comparison of predicted and observed [Pu(VI)]–time data confirms that self-reduction of ²³⁸Pu(VI) at pH 0 is induced by radiolysis, but that self-reduction reactions of ²³⁹Pu(VI) at pH 1.5 and ²⁴²Pu(VI) at pH 6 are driven by disproportionation. Modeling of [Pu(VI)]–time behavior of solutions containing ²¹⁰Po as an alpha source shows that control of the reduction path changes from disproportionation to radiolytic over time at pH 0.7. Self-reduction of Pu(VI) consistently follows the most rapid path as determined by pH, Pu(VI) concentration, and the isotopic state of Pu. Chemistry and kinetics of the processes by which Pu(VI) self-reduction drives the decrease in average oxidation number of plutonium-containing solutions over time are discussed.     

福岛核事故向环境释放的Pu研究进展

福岛核事故向环境释放的放射性核素中包含了锕系元素Pu,其中以极毒组的239Pu、240Pu和高毒组的241Pu为主。本文总结并分析了针对福岛核事故向环境释放的Pu的相关研究。据估计,福岛核事故向环境中排放的239+240Pu总量约为109 Bq,是切尔诺贝利核事故排放量的万分之一。此次事故排放的Pu同位素原子比(240Pu/239Pu和241Pu/239Pu)及活度比(A(238Pu)/A(239+240Pu))明显异于全球沉降值,可作为事故中Pu溯源的判定依据。事故所排放的Pu全部来源于核电站1~3号反应堆堆芯而非乏燃料池。现有研究报道的数据表明,在福岛核电站周围30km范围内的陆地环境中存在来自核事故排放的Pu污染,污染相对严重的"热点"区域和该地区与核电站的相对位置没有明显关联,主要是受地形和降水的影响。而对于人们关心的海洋环境,来自福岛核事故的Pu污染非常小。核事故向海洋中排放的Pu相对于核事故前海洋环境中的Pu污染水平可忽略不计。     

西北太平洋表层海水中239+240Pu浓度及240Pu/239Pu同位素比

钚是与核工业密切相关的敏感元素,是来源于人类核活动、以痕量或超痕量水平存在于环境中的重要锕系元素。与陆地土壤中钚的环境行为不同,输入到海洋环境中的钚会随洋流路径进行远距离迁移扩散。因此,对于包括我国近海在内的西北太平洋区域海水,除受全球沉降影响外,还长期受到美国太平洋核试验场（PPG）所造成区域污染的显著影响。本文利用从相关报道中收集的数据,对西北太平洋表层海水中钚浓度及同位素比的分布特征进行了分析。结果表明,2000年至今,西北太平洋表层海水中^239+240Pu浓度和²⁴⁰Pu/²³⁹Pu同位素比分别在1.15~22.3 mBq/m³和0.184~0.31间变化,其中,^239+240Pu浓度分布与西北太平洋各区域的环境条件等密切相关,而²⁴⁰Pu/²³⁹Pu分布则相对均匀,后者在除中国南海以外的西北太平洋地区均值为0.247±0.025(1σ),据此估算得美国太平洋核试验场区域污染输入的钚对该海域表层海水中钚的贡献约占其总活度的45%。此外,本文还对福岛核电站附近海域中核事故前后钚的相关数据进行了分析对比,未观察到该事故对西北太平洋海域中钚分布的影响。     

Mechanism of dynamic strain aging and characterization of its effect on the low-cycle fatigue behavior in type 316L stainless steel

Low-cycle fatigue tests were carried out in air in a wide temperature range from 20 to 650 °C with strain rates of 3.2 × 10⁻⁵–1 × 10⁻² s⁻¹ for type 316L stainless steel to investigate dynamic strain aging (DSA) effect on the fatigue resistance. The regime of DSA was evaluated using the anomalies associated with DSA and was in the temperature range of 250–550 °C at a strain rate of 1 × 10⁻⁴ s⁻¹, in 250–600 °C at 1 × 10⁻³ s⁻¹, and in 250–650 °C at 1 × 10⁻² s⁻¹. The activation energies for each type of serration were about 0.57–0.74 times those for lattice diffusion indicating that a mechanism other than lattice diffusion is involved. It seems to be reasonable to infer that DSA is caused by the pipe diffusion of solute atoms through the dislocation core. Dynamic strain aging reduced the crack initiation and propagation life by way of multiple crack initiation, which comes from the DSA-induced inhomogeneity of deformation, and rapid crack propagation due to the DSA-induced hardening, respectively.     

熔岩玻璃体239Pu在地下水中的迁移模拟研究

针对内华达核试验场CHESHIRE地下核试验状况和近场水文地质参数,建立了熔岩玻璃体²³⁹Pu的溶解释放和迁移模型。估算了熔岩玻璃体释放产生²³⁹Pu的速率,将释放出的²³⁹Pu分为溶解态和胶体态,以软件FEFLOW作为建模工具,数值模拟了10万年内溶解态²³⁹Pu和胶体态²³⁹Pu在地下水中的污染羽分布。模拟结果表明,溶解态²³⁹Pu不能发生远距离迁移,影响迁移的关键参数是分配系数,当分配系数大于10 mL/g后,可忽略溶解态²³⁹Pu的远距离迁移;胶体态²³⁹Pu在爆心下游形成较固定的污染晕,距爆心1.3 km处的胶体态²³⁹Pu的模拟活度浓度长期处于10^-2 Bq/L;影响胶体态²³⁹Pu迁移的主要因素包括熔岩玻璃体的溶解速度、熔岩玻璃体释放²³⁹Pu形成胶体态²³⁹Pu的比例、岩层渗透系数。由模拟结果可见,只有当²³⁹Pu形成胶体粒子后才可能发生远距离迁移。     

Influence of ageing heat treatment on alloy A-286 microstructure and stress corrosion cracking behaviour in PWR primary water

The influence of ageing heat treatment on alloy A-286 microstructure and stress corrosion cracking behaviour in simulated Pressurized Water Reactor (PWR) primary water has been investigated. A-286 microstructure was characterized by transmission electron microscopy for ageing heat treatments at 670 °C and 720 °C for durations ranging from 5 h to 100 h. Spherical γ′ phase with mean diameters ranging from 4.6 to 9.6 nm and densities ranging from 8.5 × 10²² m⁻³ to 2 × 10²³ m⁻³ were measured. Results suggest that both the γ′ phase mean diameter and density quickly saturate with time for ageing heat treatment at 720 °C while the γ′ mean diameter increases significantly up to 100 h for ageing heat treatment at 670 °C. Grain boundary η phase precipitates were systematically observed for ageing heat treatment at 720 °C even for short ageing periods. In contrast, no grain boundary η phase precipitates were observed for ageing heat treatments at 670 °C except after 100 h. Hardening by γ′ precipitation was well described by the dispersed barrier hardening model with a γ′ barrier strength of 0.23. Stress corrosion cracking behaviour of A-286 was investigated by means of constant elongation rate tensile tests at 1.5 × 10⁻⁷ s⁻¹ in simulated PWR primary water at 320 °C and 360 °C. In all cases, initiation was transgranular while propagation was intergranular. Grain boundary η phase precipitates were found to have no significant effect on stress corrosion cracking. In contrast, yield strength and to a lesser extent temperature were found to have significant influences on A-286 susceptibility to stress corrosion cracking.     

Carbon ion-implanted optical waveguides in Nd:YLiF4 crystal: Refractive index profiles and thermal stability

We report on the optical planar waveguides in Nd:YLiF₄ laser crystals fabricated by 6.0 MeV C³⁺ ion implantation at doses of 1 × 10¹⁵ or 2.5 × 10¹⁵ ions/cm², respectively. The refractive index profiles, which are reconstructed according to the measured dark mode spectroscopy, show that the ordinary index had a positive change in the surface region, forming non-leaky waveguide structures. The extraordinary index is with a typical barrier-shaped distribution, which may be mainly due to the nuclear energy deposition of the incident ions into the substrate. In order to investigate the thermal stability of the waveguides, the samples are annealed at temperature of 200–300 °C in air. The results show that waveguide produced by higher-dose carbon implantation remains relatively stable with post-irradiation annealing treatment at 200 °C in air.     

Development of ceramic waste forms for actinide-rich waste— Radiation stability of perovskite and phase and chemical stabilities of ZR-and AL-based ceramics

Ceramics are considered as most promising materials for conditioning of long-lived radionuclides because of their outstanding durability for long term. The Japan Atomic Energy Research Institute (JAERI) has developed ceramic waste forms, e.g. Synroc and zirconia-based ceramics, for the actinide-rich wastes arising from partitioning and transmutation processes. In the present study, -decay damage effects on the density and leaching behavior of perovskite (one of three main minerals forming Synroc) were investigated by an accelerated experiment using the actinide doping technique. A decrease in density of Cm-doped perovskite reached 1.3 % at a dose of 9 × 10¹⁷ -decays·g⁻¹. The leach rates (MCC-1 leach test inpH 2 solution at 90°C for 2 months) of perovskite specimens with accumulated doses of 1.6 × 10¹⁷, 4.0 × 10¹⁷ and 8.3 × 10¹⁷ -decays·g⁻¹ were 1.7, 2.3 and 3.0 μ·m⁻²·day⁻¹, respectively. Application of zirconia- and alumina-based ceramics for incorporating actinides was also investigated by the experiments using non-radioactive elements (Ce and Nd) with an emphasis on crystallographic phase stability and chemical durability. The yttria-stabilized zirconia was stable crystallographically in the wide ranges of Ce and/ or Nd content and had excellent chemical durability.     

XPS and optical studies of Xe-implanted and annealed YSZ single crystals

Xe⁺ ion implantation with 200 keV was completed at room temperature up to a fluence of 1 × 10¹⁷ ion/cm² in yttria-stabilized zirconia (YSZ) single crystals. Optical absorption and X-ray photoelectron spectroscopy (XPS) were used to characterize the changes of optical properties and charge state in the as-implanted and annealed crystals. A broad absorption band centered at 522 or 497 nm was observed in the optical absorption spectra of samples implanted with fluences of 1 × 10¹⁶ ion/cm² and 1 × 10¹⁷ ion/cm², respectively. These two absorption bands both disappeared due to recombination of color centers after annealing at 250 °C. XPS measurements showed two Gaussian components of O_1s spectrum assigned to Zr–O and Y–O, respectively, in YSZ single crystals. After ion implantation, these two peaks merged into a single peak with the increasing etching depth. However, this single peak split into two Gaussian components again after annealing at 250 °C. The concentration of Xe decreased drastically after annealing at 900 °C. And the XPS measurement barely detected the Xe. There was no change in the photoluminescence of YSZ single crystals with a fluence of 1 × 10¹⁷ ion/cm² after annealing up to 900 °C.     

Time scales of transient enhanced diffusion: free and clustered interstitials

Transient enhanced diffusion (TED) and electrical activation after nonamorphizing Si implantations into lightly B-doped Si multilayers shows two distinct timescales, each related to a different class of interstitial defect. At 700°C, ultrafast TED occurs within the first 15 s with a B diffusivity enhancement of > 2 × 10⁵. Immobile clustered B is present at low concentration levels after the ultrafast transient and persists for an extended period ( 10²–10³ s). The later phase of TED exhibits a near-constant diffusivity enhancement of ≈ 1 × 10⁴, consistent with interstitial injection controlled by dissolving {113} interstitial clusters. The relative contributions of the ultrafast and regular TED regimes to the final diffusive broadening of the B profile depends on the proportion of interstitials that escape capture by {113} clusters growing within the implant damage region upon annealing. Our results explain the ultrafast TED recently observed after medium-dose B implantation. In that case there are enough B atoms to trap a large proportion of interstitials in Si---B clusters, and the remaining interstitials contribute to TED without passing through an intermediate {113} defect stage. The data on the ultrafast TED pulse allows us to extract lower limits for the diffusivities of the Si interstitial (D_I > 2 × 10⁻¹⁰ cm²s⁻¹) and the B interstitial(cy) defect (D_Bi > 2 × 10⁻¹³ cm²s⁻¹) at 700°C.     

Damage distributions in LiNbO3 crystal induced by MeV F tilted implantations

X-cut LiNbO₃ crystals have been implanted by 0.8, 1.0 and 1.2 MeV F⁺ tilted at angles of 15°, 45° and 60° with doses of 5 × 10¹⁴, 7 × 10¹⁴ and 5 × 10¹⁴ ions/cm², respectively. The Rutherford backscattering (RBS)/channeling technique was used to investigate the induced damage distributions. The damage profiles were deconvoluted from the measured spectra after considering the energy spread due to the different stopping power of channeled and nonchanneled ions. Good agreements were obtained between the measured damage profiles and the calculated defect profiles by TRIM'90 (transport of ions in matter, version 1990), except that the measured damage concentration was enhanced in the near-surface region. Information on the lateral and longitudinal damage spread in LiNbO₃ crystals was obtained from the damage profiles induced by tilted ion implantations and compared with TRIM'90 calculation.     

Radiation damage induced by 5 keV Si ion implantation in strained-Si/Si0.8Ge0.2

The damage distributions induced by ultra low energy ion implantation (5 keV Si⁺) in both strained-Si/Si_0.8Ge_0.2 and normal Si are measured using high-resolution RBS/channeling with a depth resolution better than 1 nm. Ion implantation was performed at room temperature over the fluence range from 2 × 10¹³ to 1 × 10¹⁵ ions/cm². Our HRBS results show that the radiation damage induced in the strained Si is slightly larger than that in the normal Si at fluences from 1 × 10¹⁴ to 4 × 10¹⁴ ions/cm² while the amorphous width is almost the same in both strained and normal Si.     

Photoluminescence of Au formed in 12CaO · 7Al2O3 single crystal by Au-implantation

Au⁺ ion implantation with fluences from 1 × 10¹⁴ to 3 × 10¹⁶ cm⁻² into 12CaO · 7Al₂O₃ (C12A7) single crystals was carried out at a sample temperature of 600 °C. The implanted sample with the fluence of 1 × 10¹⁵ cm⁻² exhibited photoluminescence (PL) bands peaking at 3.1 and 2.3 eV at 150 K when excited by He–Cd laser (325 nm). This was the first observation of PL from C12A7. These two PL bands are possibly due to intra-ionic transitions of an Au⁻ ion having the electronic configuration of 6s², judged from their similarities to those reported on Au⁻ ions in alkali halides. However, when the concentration of the implanted Au ions exceeded the theoretical maximum value of anions encaged in C12A7 (2.3 × 10²¹ cm⁻³), surface plasmon absorption appeared in the optical absorption spectrum, suggesting Au colloids were formed at such high fluences. These observations indicate that negative gold ions are formed in the cages of C12A7 by the Au⁺ implantation if an appropriate fluence is chosen.     

我国部分省份环境气溶胶中239+240 Pu的测定

采用阴离子交换树脂分离结合α谱仪测量的方法对我国7个省份环境气溶胶中^239+240Pu含量进行测定,实验全程回收率为60.8%～94.6%,对气溶胶中^239+240Pu的最小可探测限为0.008 μBq/m³。普通环境气溶胶采样量需要达到30 000 m³以上,在应急情况等特殊环境气溶胶采样量为10 000 m³可满足要求。一般情况下气溶胶中²¹⁰Po含量比^239+240Pu高4～6个数量级,在分析和测量中要关注²¹⁰Po对^239+240Pu测量的影响。测量结果显示,我国普通省份环境气溶胶中^239+240Pu含量为0.009～0.099 μBq/m³,与美国、韩国和西班牙等国家空气气溶胶中的Pu含量处于同一水平。     

Formation processes of nickel oxide nanoparticles in SiO2 by metal-ion implantation combined with thermal oxidation

Formation processes of nickel oxide (NiO) nanoparticles (NPs) in silica glass (SiO₂) by implantation of 60 keV Ni⁻ ions combined with thermal oxidation are studied using cross-sectional transmission electron microscopy (XTEM) and Rutherford backscattering spectrometry. In as-implanted state, Ni metallic NPs form within the surface layer of 80 nm thick. The mean depth z and the standard deviation (Δz)^21/2 of Ni atom distribution determined by XTEM were 43 and 15 nm, respectively. After the oxidation at 800 °C for 1 h, z and (Δz)^21/2 became 47 nm and 20 nm, respectively, i.e. the distribution was almost the same except a small diffusional shift to the deeper region. Mean volume of Ni- and NiO-NPs after heat treatments at 800 °C were 27 and 43 nm³, respectively. The larger mean volume of NiO-NPs is explained from the fact that NiO-NPs include both Ni and O atoms, i.e. approximately 2N atoms, while Ni-NPs include Ni atoms only, i.e. N atoms. Both the Ni- and NiO-NPs include 2.4 × 10³ Ni atoms per NP in average. These results indicate that NiO-NPs are formed by oxidation of Ni-NPs without pronounced redistribution of Ni atoms.     

Ion beam synthesis and recrystallization of amorphous SiGe/SiC structures

Si_1−xGe_x amorphous layers implanted with different doses of carbon (between 5 × 10¹⁵ and 2 × 10¹⁷ cm⁻² and annealed at 700°C and 900°C have been analyzed by Raman and Infrared spectroscopies, electron microscopy and Auger electron spectroscopy. The obtained data show the synthesis of amorphous SiC by implanting at the highest doses. In these cases, recrystallization only occurs at the highest annealing temperature (900°C). The structure of the synthesized SiC strongly depends on the implantation dose, in addition to the anneal temperature. For the highest dose (2 × 10¹⁷ cm⁻²), crystalline β-SiC is formed. Finally, a strong migration of Ge towards the Si substrate is observed from the region where SiC precipitation occurs.     

基于TOA萃取色层的土壤中238Pu/239,240Pu活度比的分析方法

核设施周边环境土壤样品中²³⁸Pu/^239,240Pu活度比的信息特征可用于评估核活动,为了获得准确的核素比,需要建立²³⁸Pu/^239,240Pu活度比的分析方法。在三正辛胺（TOA）萃取法分析Pu含量的基础上,考察了盐酸和硝酸洗涤以及洗涤用量对U、Th、Am等杂质元素的去除情况,并引入共沉淀步骤进行前处理流程的优化,建立起一个基于TOA萃取色层的土壤样品中²³⁸Pu/^239,240Pu活度比的分析方法。当土壤样品量为25 g时,该方法Pu的化学回收率大于70%,U、Th的去污因子大于10⁴,Am的去污因子大于10³,²³⁸Pu的最低检测比活度为（6.0±1.6）×10^-6 Bq/g,^239,240Pu的最低检测比活度为（6.4±0.4）×10^-6 Bq/g(n=3)。该方法可应用于环境土壤样品中²³⁸Pu/^239,240Pu活度比的分析,为军控核查和环境监测提供技术支持。     

Effects of 160 MeV Ni ion irradiation on polypyrrole conducting polymer electrode materials for all polymer redox supercapacitor

Electronically conducting polymers are suitable electrode materials for high performance supercapacitors, for their high specific capacitance and high dc conductivity in the charged state. Supercapacitors and batteries are energy storage and conversion systems which satisfies the requirements of high specific power and energy in a complementary way. Ion beam {energy > 1 MeV} irradiation on the polymer is a novel technique to enhance or alter the properties like conductivity, density, chain length and solubility.

Conducting polymer polypyrrole thin films doped with LiClO₄ are synthesized electrochemically on ITO coated glass substrate and are irradiated with 160 MeV Ni¹²⁺ ions at different fluence 5 × 10¹⁰, 5 × 10¹¹ and 3 × 10¹² ions cm⁻². Dc conductivity measurement of the irradiated films showed 50–60% increase in conductivity which is may be due to increase of carrier concentration in the polymer film as observed in UV–Vis spectroscopy and other effects like cross-linking of polymer chain, bond breaking and creation of defects sites. X-ray diffractogram study shows that the degree of crystallinity of polypyrrole increases in SHI irradiation and is proportionate to ion fluence. The capacitance of the irradiated films is lowered but the capacitance of the supercapacitors with irradiated films showed enhanced stability compared to the devices with unirradiated films while characterized for cycle life up to 10,000 cycles.     

Surface morphology of the Ar ion-irradiated Ag/Si(1 1 1) system

In the present study, a 500 Å thin Ag film was deposited by thermal evaporation on 5% HF etched Si(1 1 1) substrate at a chamber pressure of 8×10⁻⁶ mbar. The films were irradiated with 100 keV Ar⁺ ions at room temperature (RT) and at elevated temperatures to a fluence of 1×10¹⁶ cm⁻² at a flux of 5.55×10¹² ions/cm²/s. Surface morphology of the Ar ion-irradiated Ag/Si(1 1 1) system was investigated using scanning electron microscopy (SEM). A percolation network pattern was observed when the film was irradiated at 200°C and 400°C. The fractal dimension of the percolated pattern was higher in the sample irradiated at 400°C compared to the one irradiated at 200°C. The percolation network is still observed in the film thermally annealed at 600°C with and without prior ion irradiation. The fractal dimension of the percolated pattern in the sample annealed at 600°C was lower than in the sample post-annealed (irradiated and then annealed) at 600°C. All these observations are explained in terms of self-diffusion of Ag atoms on the Si(1 1 1) substrate, inter-diffusion of Ag and Si and phase formations in Ag and Si due to Ar ion irradiation.