Study of gel development during SON68 glass alteration using atomic force microscopy. Comparison with two simplified glasses

Literature mentions several physicochemical studies concerning the characterisation of the alteration films that are formed during the dissolution of the nuclear glasses. Up to now, however, no study had been undertaken on the evolution of the alteration film thickness by in situ technique. This study proposes to carry out atomic force microscopy (AFM) in liquid and dry conditions in order to measure the shrinkage or swelling of the alteration film. This work is performed on the glass SON68 and on two glasses with simplified compositions. The results obtained reveal a shrinkage of the alteration film for the simplified glasses and, in situ (underwater), a slight swelling for the SON68 glass caused by the formation of crystalline phase (phyllosilicates) on the surface. In all three cases, when alteration progresses, it increases the density of the gel and the volume occupied by the alteration products tends to be equal to the volume initially occupied by the glass (called isovolumetric alteration). Finally, the drying leads to an important shrinkage. These results could be used to evaluate the potential impact of the internal cracks of an industrial glass block.     

Borosilicate glass alteration driven by magnesium carbonates

The alteration of simplified synthetic glass, representative of the French reference nuclear glass R7T7, in presence of hydromagnesite has been experimentally investigated and modeled. Magnesium in solution is known to potentially enhance glass alteration; nuclear glass clayed host rocks contain magnesium and can dissolve to maintain the concentration of magnesium in solution. For modeling purposes, it was suitable to study a simple system. Hydromagnesite was therefore chosen as a simple model mineral in order to check the influence of an Mg-rich mineral on glass alteration. Since the models use thermodynamic and kinetic parameters measured in pure water and pH-buffered solutions, changing the solution composition or adding minerals is a key step towards the validation of the modeling assumptions before using the model for predictive purposes.Experiments revealed that glass alteration is enhanced in presence of hydromagnesite. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC reactive transport code. Modeling proved useful both for explaining the mechanisms involved and quantifying the impact on glass alteration: Mg coming from hydromagnesite dissolution reacts with Si provided by the glass in order to form magnesium silicates. This reaction decreases the pH down to neutral conditions where magnesium silicates are more soluble than at the natural alkali pH imposed by glass or hydromagnesite dissolution. The driving force of the magnesium silicate precipitation is eventually the interdiffusion of alkali within the altered amorphous glass layer as this mechanism consumes protons. The model’s ability to describe the concentrations of elements in solution and formed solids whatever the glass/hydromagnesite ratio strongly supports the basic modeling hypothesis.     

Nature and role of natural alteration gels formed on the surface of ancient volcanic glasses (Natural analogs of waste containment glasses)

This paper provides an overview of the geochemical alteration of basaltic glass, considered for over 20 years as a suitable natural analogue for nuclear borosilicate glasses. The available data show that natural basaltic glasses may survive for million of years under subsurface conditions. Mineralogical studies show that an alteration layer called palagonite forms on the surface of the basaltic in response to the chemical attack by water. Under some environmental conditions, the alteration layer consists of an amorphous gel-like material, leading many authors to suspect hydration of the glass by water permeation and alkali interdiffusion. In other cases, the alteration layer is crystallized to some extent and contains clay minerals (smectite). Such layers are formed mainly on the younger natural glass samples (<1 My) by a process of coprecipitation of the elements dissolved from the glass. On samples older than 1 My, the alteration layers also contain zeolites. In the presence of these hydrated aluminosilicates, a hydrated residual glass is systematically observed, which thus forms as a consequence of interdiffusion processes. Leach tests conducted under controlled laboratory conditions at temperatures up to 200 °C on both natural glass samples and synthetic basaltic glass provide identical kinetic results and alteration mechanisms. When compared with the data for SON68 nuclear borosilicate glass, the initial dissolution rates show the same activation energy (about 72 kJ mol⁻¹) and consequently similar dissolution mechanisms. Moreover, when altered under static conditions at high reaction progress, both basaltic glass and nuclear glass have similar behavior characterized by a significant drop in the dissolution rate, up to three to five orders of magnitude lower than the initial dissolution rate. The time-dependence of the thickness of the altered layers measured on natural glass samples confirms this kinetic trend over time: the long-term dissolution rate is very low. This decrease may be related to diffusion mechanisms involving key chemical species and controlled by the mineralogy of the palagonite layer.     

全体积R7T7型参考玻璃固化体裂隙初步研究

为从微观角度研究裂隙对玻璃固化体腐蚀影响,引入体视学方法对玻璃体裂隙进行了裂隙分布、腐蚀程度等初步研究。采用扫描电镜对结束1147d静态浸出实验后的全体积R7T7型参考玻璃的部分样品进行分析。根据分析得到的二维参数,通过体视学方法计算得到全体积玻璃体的裂隙率FR为41±13,腐蚀量为(3.88±1.20)×10^-4m³,约占玻璃体参与水相腐蚀反应总体积的(0.28±0.09)%。分析还发现,裂隙腐蚀产物厚度小于10μm的裂隙占裂隙总数的80%,这些裂隙导致的腐蚀仅占总腐蚀表面积的30%;同时,腐蚀产物厚度大于10μm的裂隙对样品总腐蚀表面积贡献了70%。     

A 25-year laboratory experiment on French SON68 nuclear glass leached in a granitic environment - First investigations

We have investigated a 25.75-year old leaching experiment to improve our understanding of the mechanisms controlling glass dissolution in geological disposal conditions. A SON68 glass block was leached in slowly renewed synthetic groundwater (at 90 °C, 100 bar) in contact with some pieces of granite and Ni-Cr-Mo alloy as environmental storage materials. One hundred and sixty-three samplings were carried out over the entire duration of the experiment and were used to calculate the mean thickness of the altered glass (28 (±9) μm) and the glass dissolution rate. After few months, the rate remained very constant at 6 × 10⁻³ g m⁻² d⁻¹ which is about 20 times higher than the residual rate measured in a batch reactor at the same temperature.At the end of the experiment, mainly SEM analyses were performed on the entire glass block. Surprisingly, the glass alteration layer has neither a homogeneous thickness, nor a homogeneous morphology. The location of the sampling valve (at half height of the glass block) seems to divide the glass block into two parts. In the upper half (above the sampling valve), the general morphology of the alteration layer consists in a relatively simple and uniform gel and some secondary phases which are rare-earth phosphates. The mean measured thickness of this alteration layer is 6.7 (±0.3) μm. However, in the lower half of the glass block, the gel is globally larger and frequently contains rounded shapes which are rare-earth phosphates. This section is edged by secondary phases bearing Mg, Na, Zn and Ni. The mean measured thickness is 81.3 (±1.1) μm in the lower half. In this experiment, the flow rate which leads to the hydrodynamic transport of the soluble species must be a key factor for the local glass alteration process. We have also shown that this unexpected behavior is likely due to heterogeneities of the chemistry of the solution. This conclusion is supported by the behavior of Mg. This element, supplied by the inlet solution, precipitates with Si and forms clay minerals and therefore weakens the passivating properties of the gel. Mg-rich clay minerals are only observed in the lower half of the glass block. Further investigations are necessary to better understand the coupling between the hydrodynamics and chemistry in this experiment. However, based on this study, we can conclude that glass in disposal should be very sensitive to the water renewal near the glass surface.     

CrAlN/TiAlN纳米多层膜界面结构的中子与X射线反射研究

采用反应磁控溅射技术在单晶硅基片上制备了CrN纳米单层膜和CrAlN/TiAlN纳米周期膜,利用非极化中子和X射线反射对膜层厚度、膜层界面粗糙度、界面扩散等表面、界面结构和性质进行了系统研究。中子反射测得的CrN纳米单层膜和CrAlN/TiAlN纳米周期膜的厚度与设计厚度的差别为3.8%～4.2%。散射长度密度（SLD）分析结果表明,膜层间和膜层与基底间界面较为清晰,扩散较少。X射线反射测得的膜层厚度较中子反射测得的膜层厚度偏高,对于较小调制周期的多层膜,界面弥散会对X射线反射结果产生较大误差。     

Study of 160 MeV Ni ion irradiation effects on electrodeposited polypyrrole films

Conducting polymer polypyrrole thin films doped with LiCF₃SO₃, [CH₃(CH₂)₃]₄NBF₄ and [CH₃(CH₂)₃]₄NPF₆ have been electrodeposited potentiodynamically on ITO coated glass substrate. The polymer films are irradiated with 160 MeV Ni¹²⁺ ions at three different fluences of 5 × 10¹⁰, 5 × 10¹¹ and 3 × 10¹² ions cm⁻². An increase in dc conductivity of polypyrrole films from 100 S/cm to 170 S/cm after irradiation with highest fluence is observed in four-probe measurement. X-ray diffractogram shows increase in the crystallinity of the polypyrrole films upon SHI irradiation, which goes on increasing with the increase in fluence. Absorption intensity increase in the higher wavelength region is observed in the UV–Vis spectra. The SEM studies show that the cauliflower like flaky microstructure of the surface of polypyrrole films turns globular upon SHI irradiation at fluence 5 × 10¹¹ ions cm⁻² and becomes smooth and dense at the highest fluence used. The cyclic voltammetry studies exhibit that the redox properties of the polypyrrole films do not change much on SHI irradiation.     

High level nuclear waste glass corrosion in synthetic clay pore solution and retention of actinides in secondary phases

The corrosion of the simulated high level waste glass GP WAK1 in synthetic clay pore solution was studied in batch-type experiments at 323 and 363 K with special focus on the effect of high carbonate concentration in solution. The corrosion rate after 130 days was <10⁻⁴ g m⁻² d⁻¹ - no significant effect of the carbonate was identified. During glass corrosion, crystalline secondary phases (powellite, barite, calcite, anhydrite and clay-like Mg(Ca,Fe)-silicates) were formed. To obtain a molecular level picture of radionuclide speciation within the alteration layer, spectroscopic methods have been applied including grazing incidence X-ray absorption spectroscopy (XAS) to study the structural changes in the coordination of uranyl upon alteration layer formation. The number of equatorial oxygen atoms increases from 4 in the bulk glass to 5 in the alteration layer. Furthermore, reduced coordination symmetry was found. Hectorite, a frequently observed secondary clay mineral within the glass alteration layer, was synthesized in the presence of trivalent f-elements (e.g. Eu) and structurally characterized using time-resolved laser fluorescence spectroscopy. Structural incorporation into the octahedral layer is indicated.     

松辽盆地白城地区中生界油气还原蚀变垂向分带的划分及其特征

对松辽盆地白城地区中油气对砂岩层后生还原蚀变的垂向分带进行了分析总结。按岩石颜色从下往上划分出灰黑-黑色带(泥岩、油浸砂带),蓝灰-绿灰色带(灰绿色带)和灰色带(黄铁矿化带和高岭石化带),其上为黄色带(氧化带),对各带特征进行了描述,分析了产生垂向分带的原因,指出了铀成矿的有利部位。     

Vitrification and testing of a Hanford high-level waste sample. Part 2: Phase identification and waste form leachability

A sample of Hanford high-level radioactive waste from Tank AZ-101 was vitrified into borosilicate glass and tested to demonstrate its compliance with regulatory requirements. Compositional aspects of this study were reported in Part 1 of this paper. This second and last part presents results of crystallinity and leachability testing. Crystallinity was quantified in a glass sample heat treated according to the calculated cooling curve of glass at the centerline of a Hanford Waste Treatment Plant canister. By quantitative X-ray diffraction analysis and image analysis applied to scanning electron microscopy micrographs, the sample contained 7 mass% of spinel, a solid solution of franklinite, trevorite, and other minor spinels. Glass leachability was measured with the product consistency test and the toxicity characteristic leaching procedure. Measured data and model estimates were in reasonable agreement. Leachability results were close to those obtained for the non-radioactive simulant. Models were used to elucidate the effects of glass composition of spinel formation and to estimate effects of spinel formation on glass leachability.     

Experimental Study on Fabrication Technique of a Ni/Ti Supermirror using the Electron Beam Evaporation System

Basic study on the fabrication technique of a Ni/Ti supermirror using the vacuum evaporation system with an electron gun has been carried out to improve the neutron reflectivity.

The substrate roughness dependency to the reflectivity was investigated using polished glass floats with different surface roughnesses using neutron reflectometry. It was concluded that the substrate roughness in the order of several sub-nanometers was very sensitive to the neutron reflectivity of the Ni/Ti supermirror. The reflectivity was improved to 80% for the Ni/Ti supermirror with an effective critical angle of 2 times that of natural nickel using fine polished glass substrate with a surface roughness of 0.51 nm rms.

The effect of oxidizing Ni and Ti layers to the neutron reflectivity, which were deposited by changing the oxygen gas conditions in the chamber, was investigated. The oxidation effect prevents the deformation of the Ni/Ti supermirror structure, and the reflectivity shows an increase of almost 20% for the Ni/Ti supermirror with an effective critical angle of 2.6 times that of natural nickel by depositing in an atmosphere of oxygen gas with a partial pressure of 1 × 10^?5 Torr.

From the depth profile by X-ray photoelectron measurement (XPM) and neutron reflectometry results, it was concluded that the reflectivity increase by oxidation mentioned is caused by decreasing the interface roughness and the interfacial diffusion between Ni and Ti layer, and it is not caused by forming a NiO compound which increases the scattering potential of the Ni layer.     

乌克兰米丘林铀矿床的成矿蚀变作用

米丘林铀矿床是乌克兰基洛沃格勒地区发现的第一个受构造-岩性和蚀变分带特征控制的典型钠交代型大型铀矿床。通过总结归纳前人对乌克兰米丘林铀矿床的铀矿化特征、蚀变作用及分带特征,对米丘林矿床的成矿蚀变作用进行分析探讨。米丘林矿床主要发育石榴石-黑云母片麻岩和钾质花岗岩两种岩石;矿床的围岩蚀变发育,主要表现出广泛的岩石退变质作用,如斜长石的绢云母化、微斜长石化、黑云母化、绿泥石化,沿断裂还发育有大规模、强烈的钠交代作用;铀矿化与钠交代作用密切相关,主要发育在花岗岩与片麻岩接触带的断裂带中,由沿断裂活动的流体交代片麻岩、花岗岩、糜棱岩和碎裂岩而形成,铀矿体主要产于钠交代岩体中。因此,钠交代岩控制着该类型铀的成矿作用,它的分布特征决定着铀矿体的规模大小,并对铀的成矿具有重要指示意义。     

Leach testing at 50 °C of α-doped SON68 glass alteration gels

Gels formed by altering α-doped (Np, Pu, Am) SON68 glass at 300 °C were leached during 1 year at 44 cm⁻¹ and 50 °C under oxidizing conditions (Eh_/NHE ≈ +150 mV) and under reducing conditions (Eh_/NHE ≈ −250 mV). After 3 days of leaching the gel dissolution was highly incongruent. The gel dissolution rate calculated from the silicon concentrations was 4.4 × 10⁻⁵ g m⁻² d⁻¹, except for the Am-doped gel, for which the rate was two times higher. During leaching, Np is weakly retained in the gel (35% under oxidizing conditions and 50% under reducing conditions) whereas Pu and Am are strongly retained (over 90%). The three lanthanides La, Ce, and Nd exhibit exactly the same leaching behavior, but different from that of actinides. Speciation and complexation calculations for neodymium showed that its solubility could be controlled by Nd(OH)₃ for periods beyond 3 months. Conversely, no simple chemical compound appears to control the solubility of the actinides.     

Structural role of molybdenum in nuclear glasses: an EXAFS study

The Mo environment has been investigated in inactive nuclear glasses using extended X-ray absorption spectroscopy (XAS). Mo is present in a tetrahedron coordinated to oxygen in the form of molybdate groups [MoO₄]²⁻ (d(Mo-O)=1.78 Å). This surrounding is not affected by the presence of noble metal phases in the nuclear glass. Relying on the XAS results, on the bond-valence model and on molecular dynamics simulations of a simplified borosilicate model glass, we show that these groups are not directly linked to the borosilicate network but rather located within alkali and alkaline-earth rich domains in the glass. This specific location in the glass network is a way to understand the low solubility of Mo in glasses melted under oxidizing conditions. It also explains the possible phase separation of a yellow phase enriched in alkali molybdates in molten nuclear glasses or the nucleation of calcium molybdates during thermal aging of these glasses. Boron coordination changes in the molten and the glassy states may explain the difference in the composition of the crystalline molybdates, as they exert a direct influence on the activity of alkalis in borosilicate glasses and melts.     

X-Ray Diffraction Study of Plasma Exposed and Annealed AlSb Bilayer Thin Film

Aluminum antimony seems to be a promising semiconducting material for high temperature applications, especially for transistors and P-N junction diodes. Additionally, it is a highly efficient solar material. This paper discusses the plasma induced bilayer diffusion of AlSb bilayer thin films using X-ray diffractogram. AlSb bilayer thin films were prepared on a glass substrate by vacuum evaporation technique. The effect of plasma exposure time and annealing temperature on the micro-structural parameters were investigated. X-ray diffraction studies show that the cubic crystals of Al orient along the (111) plane and the hexagonal crystals of Sb orient along the (003) plane. Newly formed cubic crystals of AlSb are oriented along the (200) plane and they are formed due to the simultaneous growth of Al and Sb crystals during plasma exposure.     

Ion-beam densification of hydroxyapatite thin films

The goal of this study is to demonstrate the feasibility of using ion irradiation to densify a porous ceramic film. Ion irradiation is a room-temperature process, and thus may be preferable to the use of conventional high temperature sintering, which is typically performed at temperatures in excess of 1000°C. Thin films of the bio-ceramic hydroxyapatite (HA), Ca₁₀(PO₄)₆(OH)₂, were deposited on silicon substrates using a sol–gel technique. The films processed in this study were 600 nm thick and had a density of 36% of fully dense HA, after drying at 620°C for 3 min. The dried films were irradiated with 1 and 2 MeV Si⁺⁺ ions with fluences ranging from 10¹⁴ to 6 × 10¹⁵ ions/cm². Samples irradiated with the largest fluence reached densities of 83% of that of fully dense HA. Rutherford backscattering spectrometry was used to verify the HA stoichiometry of the films and to obtain the areal density. Scratch testing showed that implantation led to a substantial improvement in scratch resistance. Nano-indentation was also used to characterize the mechanical properties of the films. The hardness was increased by a factor of 15 by the irradiation. X-ray diffraction was used to characterize the crystalline phases present in the film. Ion irradiation caused some decrease in the already small degree of crystallinity of the film. The advantage of ion-implantation over high temperature sintering is shown as no secondary crystalline phases appear after densification.     

Application of the GRAAL model to leaching experiments with SON68 nuclear glass in initially pure water

Based on a review of the current state of knowledge concerning the aqueous alteration of SON68 nuclear glass we have proposed a mechanistic model, GRAAL (Glass Reactivity with Allowance for the Alteration Layer) [P. Frugier, S. Gin, Y. Minet, T. Chave, B. Bonin, N. Godon, J.E. Lartigue, P. Jollivet, A. Ayral, L. De Windt, G. Santarini, J. Nucl. Mater. 380 (2008) 8]. This article describes how the GRAAL model hypotheses are solved using a calculation code coupling chemistry and transport. The geochemical solution of this model combines three major phenomena: chemical equilibria in solution, water and ion transport by convection or diffusion, and element diffusion through the passivating reactive interphase. The model results are compared with experimental data for SON68 glass leached in initially pure water both in a closed system and in renewed media. The comparison shows the model very satisfactorily accounts for variations in the pH and the element concentrations in solution as a function of time, the glass surface area in contact with solution, and the solution renewal rate. This success is due to the fact that the diffusion of elements through the alteration gel is taken into account in the model. This mechanism cannot be disregarded under most experimental conditions — if only to predict the solution pH — and must therefore be an integral part of the geochemical model.     

X-ray reflectivity investigation of near-surface density changes induced in Al–Au multilayers by high-current ion beam bombardment

Alternating Al–Au multilayers (typical thickness of each layer 150 nm) were deposited on polished glassy carbon substrates by evaporation under high-vacuum conditions at 278 K and subsequently interdiffused with high-current 2.0 MeV ⁴He⁺ ions. After ion beam bombardment, non-destructive X-ray reflectometry measurements reveal a significant decrease of the density in the near-surface region from 19 to 12 g/cm³. This change in density is caused by the Al–Au interdiffusion during ion beam bombardment, as measured with RBS and X-ray diffraction. Based on the advantage of X-ray reflectometry of no specific sample preparation, detailed integral information of the surface roughness is achieved, additionally. For example, the surface roughness of the interdiffused Al–Au layers increases from 3.1 to 4.1 nm accompanied by the appearance of a gradient layer at the surface that even increases in thickness after irradiation. In addition, the density of this gradient layer decreased from the as-deposited to the irradiated state.     

Raman and X-ray absorption spectroscopic studies of hydrothermally altered alkali-borosilicate nuclear waste glass

Raman spectroscopy and X-ray absorption spectroscopy (XAS) are used to characterize structural changes that took place in hydrothermally altered (Na,K)-alumina-borosilicate glasses with different Na/K ratios, formulated as part of a durability study to investigate the behavior of glasses for nuclear waste storage. The hydrothermal experiments, or vapor hydration tests (VHT), were performed on each glass for 3 and 20 days at 200 °C to accelerate and approximate long-term alteration processes that may occur in a nuclear waste repository. Results found for both glasses and their VHT altered counterparts show little, if any, structural influence from the different starting Na/K ratios. X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and Raman spectroscopy indicate that the altered samples are mostly amorphous with small amounts of analcime-like and leucite-like crystals within 200 μm of the sample surface and contain up to 9.7 wt.% water or OH. The Raman data are nearly identical for the amorphous portions of all altered VHT samples investigated, and indicate that two glass structural changes took place during alteration: one, partial depolymerization of the alumina-borosilicate network, and two, introduction of water or OH. Al and Si XAS data indicate tetrahedral AlO₄ and SiO₄ environments in the original glasses as well as in the altered samples. Small energy shifts of the Si K-edge also show that the altered VHT samples have less polymerized networks than the original glass. Na XAS data indicate expanded Na environments in the VHT samples with longer Na-O distances and more nearest-neighbor oxygen atoms, compared with the original glasses, which may be due to hydrous species introduced into the expanding Na-sites.     

Structural analysis of DC magnetron sputtered and spin coated thin films using RBS, TEM and X-ray reflectivity methods

Metallic thin films such as Au, Cr, Ag, etc., on silicon substrate have many technologically important applications as contact layers in microelectronic industry, as reflecting mirrors in synchrotron radiation research, etc. The native oxide layer on crystalline silicon surface inhibits wetting of few nm thick Au or Ag on native oxide/silicon systems. To obtain continuous thin metallic films (a few nm thick), a Cr layer was first deposited as a adhesion layer on the Si substrate. In this paper, Rutherford backscattering analysis (RBS) of Si/Cr/SiO₂/Si, Si/Au/SiO₂/Si, Si/Au/Cr/SiO₂/Si and Polystyrene (PS) polymer coated on some of these bi- or tri-layer structures has been reported. The X-ray reflectometry and transmission electron microscopy studies were carried out to complement the RBS measurements. The thickness, surface and interface roughness, and crystalline quality have been determined.