Hydronium Ions in Soda‐lime Silicate Glass Surfaces

The presence of leachable alkali ions, or their hydrated sites in the glass, is believed to be a determining factor for the interfacial water structure at the glass surface, influencing the surface properties of glass. The interfacial water structure on soda‐lime silicate glass in humid ambience at room temperature was analyzed with sum‐frequency‐generation (SFG) vibration spectroscopy, which can probe the interfacial water layer without spectral interferences from the gas phase water. The soda‐lime glass surface exposed to water vapor shows three sharp SFG peaks at 3200, 3430, and 3670 cm^?1 in SFG, which is drastically different from the SFG spectra of the water layers on the fused quartz glass surface and the liquid water/air interface. The sharp peak at 3200 cm^?1 is believed to be associated with the hydronium ions in the Na⁺‐leached silicate glass surface. The 3200 cm^?1 peak intensity varies with the relative humidity, indicating its equilibrium with the gas phase water. It is proposed that the hydronium ions in the Na⁺‐leached sites produce compressive stress in the silicate glass surface; thus the growth of hydronium ions with increasing humidity might be responsible for the increased wear resistance of soda‐lime glass surfaces in near‐saturation humidity conditions.     

The influence of iodide on glass transition temperature of high-pressure nuclear waste glasses

The glass transition temperature (T_g) is a key parameter to investigate for application in nuclear waste immobilization in borosilicate glasses. T_g for several glasses containing iodine (I) has been measured in order to determine the I effect on T_g. Two series of glass composition (ISG and NH) containing up to 2.5 mol% I and synthesized under high pressure (0.5 to 1.5 GPa) have been investigated using differential scanning calorimetry (DSC). The I local environment in glasses has been determined using X-ray photoelectron spectroscopy and revealed that I is dissolved under its iodide form (I⁻). Results show that T_g is decreased with the I addition in the glass in agreement with previous results. We also observed that this T_g decrease is a strong function of glass composition. For NH, 2.5 mol% I induces a decrease of 24°C in T_g, whereas for ISG, 1.2 mol% decreases the T_g by 64°C. We interpret this difference as the result of the I dissolution mechanism and its effect on the polymerization of the boron network. The I dissolution in ISG is accompanied by a depolymerization of the boron network, whereas it is the opposite in NH. Although ISG corresponds to a standardized glass, for the particular case of I immobilization it appears less adequate than NH considering that the decrease in T_g for NH is small in comparison to ISG.     

Application of fiber optic reflectance spectroscopy for the detection of historical glass deterioration

Historical alkali silicate glass is prone to deterioration over time due to the uptake of atmospheric water and subsequent hydrolysis of the silicate matrix. Recent studies of historical glass have provided insight into the mechanism of alteration; however, few techniques can assess early onset glass alteration noninvasively. Herein, we present fiber optic reflectance spectroscopy (FORS) as an invaluable tool to analyze historical glass alteration. We study a series of artificially aged model potash glasses and assess the nature of the alkali-depleted alteration layer by microscopy, scanning electron microscopy (SEM) with energy dispersive spectroscopy, and FORS. We find that the model glass FORS spectra demonstrate peaks associated with hydroxide, liquid-like water, and bound water. FORS was able to detect an alteration layer as thin as 0.66 µm. The model glass data were then used to generate a hydration thickness prediction curve in order to predict the alteration layer thickness of twenty-one 19th-century glass flutes of similar composition. In the one case that an actual flute sample was available, the predicted value was in good agreement with previous SEM measurement. The results indicate the ability of FORS to noninvasively assess glass deterioration and to understand the nature of absorbed water in historical glass objects.     

Hydration of C3S thin films

Thin films of C₃S of a few tens of nanometers were produced by electron beam evaporation. After verification that the chemical composition of the bulk material remained unchanged, the samples were hydrated with water vapor in a reaction chamber under saturated pressure and temperature conditions, and were kept isolated from atmospheric exposure throughout the whole duration of the experiment. Analyses by X-ray photoelectron spectroscopy at different stages of hydration evidence a shift of the Si peaks to higher energies and a subsequent decrease of the Ca–Si binding energy distance, indicating silicate polymerization expected upon formation of C–S–H. The measured molar Ca/Si ratio evolves from that of a jennite-like material, of about 1.55, at the beginning of the experiment (attributed to pre-hydration of the thin films), to a tobermorite-like ratio of 0.85 after 3 h of hydration.     

Glass Surface Layer Density by Neutron Depth Profiling

Several lithium-disilicate ( Li₂O∙2SiO₂ ) glass samples were synthesized, polished and subjected to static leach tests for varying periods of time in an HCl solution (pH 4) at 90°C. The presence of an alteration layer on the leached specimens was independently confirmed using infrared spectroscopy. These samples were then analyzed with neutron depth profiling (NDP), and for all exposure times between 1 and 20 h, a leached layer was detected by NDP. The residual concentration of ⁶Li in the alteration layer was observed to be approximately 10% of the bulk glass value. The 7.5 h and 17.5 h samples were cross-sectioned using focused ion beam milling, and the thickness of the alteration layer on the samples was measured directly using scanning electron microscopy to be 9.8 and 22.9 μm, respectively. The areal density of the gel layers — determined by deconvolution of the NDP spectra — was coupled with the SEM measurement to give densities of 1.46 ± 0.08 g/cm³ for the 7.5 h specimen and 1.46 ± 0.05 g/cm³ for the 17.5 h specimen. This preliminary work shows that NDP can be used to determine the average density of gel layers formed owing to leaching of alkali-silicate glass.     

Effects of Al:Si and (Al + Na):Si ratios on the properties of the international simple glass,part I: Physical properties

Understanding composition-structure-property relationships of high-alumina nuclear waste glasses are important for vitrification of nuclear waste at the Hanford Site. Two series of glasses were designed, one with varying Al:Si ratios and the other with (Al + Na):Si ratios based on the international simple glass (ISG, a simplified nuclear waste model glass), with Al₂O₃ ranging from 0 to 23 mol% (0 to 32 wt%). The glasses were synthesized and characterized using electron probe microanalysis, X-ray photoelectron spectroscopy, small angle X-ray scattering, high-temperature oxide melt solution calorimetry, and infrared spectroscopy. Glasses were crystal free, and the lowest Na₂O and Al₂O₃ glass formed an immiscible glass phase. Evolution of various properties—glass-transition temperature, percentage of 4-coordinated B, enthalpy of glass formation—and infrared spectroscopy results indicate that structural effects differ based on the glass series.     

Novel high-resistance clinkers with 1.10 < CaO/SiO2 < 1.25: production route and preliminary hydration characterization

New amorphous calcium silicate binders, hydraulically active, were produced by a process consisting in fully melting and rapid cooling of a mixture of typical raw materials (limestone, sand, fly-ash and electric furnace slag) with overall CaO/SiO₂ molar ratios (C/S) comprised between 1.1 and 1.25. Pastes were produced from these materials by mixing them with water in a water/binder ratio of 0.375. Compressive strength was determined at the ages of 7, 28 and 90 days and the hydration of these pastes was followed during this period by XRD, FTIR and ²⁹Si MAS-NMR. Tobermorite-like structures with low C/S and semi-crystalline character were observed to develop upon hydration of these new amorphous calcium silicate hydraulic binders. Moreover, no Portlandite was formed during hydration of these materials. The maximum compressive strength after 90 days is above 40 MPa. TGA was performed in order to determine the amount of structural water present in the pastes and their content related to the amount of hydrated products obtained. The relation between compressive strength and the amount of hydration products was investigated and some considerations about the mechanical properties of the hydration products and paste microstructure were inferred.     

99Tc- and 239Pu-Doped Glass Leaching Experiments: Residual Alteration Rate and Radionuclide Behavior

The long-term behavior of high-level nuclear glass subjected to alpha/beta radiation by long-life radionuclides must be investigated with respect to geological disposal. This study focuses on the effects of alpha and beta radiations on the chemical reactivity of R7T7 glass with pure water, mainly on the residual alteration rate regime. Glass specimens doped with 0.85 wt% ²³⁹PuO₂ (α emitter) and 0.24 wt% ⁹⁹TcO₂ (β emitter) that simulate alpha and beta dose rate corresponding to long-term disposal conditions are leached under static conditions in argon atmosphere at 90°C, in initially pure water and at a high surface-area-to-volume ratio (S/V = 20/cm). The alteration rate is monitored by the release of glass alteration tracer elements (B, Na, and Li). Radiation effects on the leached glass and its gel network are characterized by SEM and TEM analyses. Plutonium and technetium releases are also measured by radiometry, and their chemical oxidation state is assessed by measuring the pH and reduction–oxidation potential of the leachates. The results do not highlight any significant effect of alpha/beta radiation on the residual alteration of these doped glasses. These observations are consistent with solid characterizations, which show that a protective layer can be formed under such irradiation fields. Under our experimental conditions (Eh~380 mV/SHE, pH_90°C = 8–8.6), very low concentrations of soluble plutonium are measured in the leachate, indicating strong plutonium retention, whereas technetium performs as a soluble element and is not retained in the altered layer.     

Physico-chemical properties of international simple glass (ISG) nuclear waste simulants: Luminescence baseline study

Borosilicate glass has been adopted internationally for the treatment of nuclear waste with the object of long-term stabilization through vitrification. Aiming to facilitate experimental comparisons across laboratories, the six-component international simple glass (ISG) was developed as benchmark. The original ISG produced by Mo-SCI Corporation (Rolla, MO) was distributed and characterized for different physical properties thus serving as reference for further studies. Still, photoluminescence (PL) properties, which may be useful for scrutinizing radiation-induced damage, have not been reported. Further, the original ISG contained significant iron impurities, which may present interference in various studies (e.g., optical). Consequently, two new ISG analogs lacking iron impurities (labeled ISG-1 [closest composition to original ISG] and ISG-2 [some MgO added at expense of CaO]) were synthesized by Corning Inc. (Corning, NY) (also doped with lanthanum for subsequent corrosion tests involving atom probe tomography), which remain to be fully characterized. Accordingly, this work was undertaken to perform a comprehensive study comparing the three ISG specimens. Various characterizations were then performed on the pristine glasses: X-ray diffraction and vibrational spectroscopy (structural properties); static-leach product consistency test (PCT, dissolution behavior); dilatometry and calorimetry measurements (thermal properties); and optical absorption with Tauc and Urbach plots analysis, followed by PL spectroscopy with decay kinetics assessment (optical properties). While the general structural features appeared similar among the glasses, the deconvolution of Raman spectra suggested a lower degree of connectivity in the silica network for ISG-2. In addition, some differences were indicated from the PCT results and thermal properties assessed, which were discussed based on compositional variations. Further on, the optical properties were shown to be the most distinct. The optical absorption of the original ISG was characterized by Fe²⁺/Fe³⁺ impurities not detected for ISG-1 and ISG-2. The glasses all exhibited two main PL features (∼1.8 and 2.5 eV) with multiexponential decay behavior apparently of intrinsic origin. In addition, ISG-1 and ISG-2 showed a third high-energy (∼3.4 eV) fast-decaying contribution tentatively credited to tin impurities, which appeared most significantly for ISG-1. The results are expected to serve as baseline for future studies simulating the effects of radioactive element decay.     

Improved evidence for the existence of an intermediate phase during hydration of tricalcium silicate

Tricalcium silicate (Ca₃SiO₅) with a very small particle size of approximately 50 nm has been prepared and hydrated for a very short time (5 min) by two different modes in a paste experiment, using a water/solid-ratio of 1.20, and by hydration as a suspension employing a water/solid-ratio of 4000. A phase containing uncondensed silicate monomers close to hydrogen atoms (either hydroxyl groups or water molecules) was formed in both experiments. This phase is distinct from anhydrous tricalcium silicate and from the calcium-silicate-hydrate (C-S-H) phase, commonly identified as the hydration product of tricalcium silicate. In the paste experiment, approximately 79% of silicon atoms were present in the hydrated phase containing silicate monomers as determined from ²⁹Si{¹H} CP/MAS NMR. This result is used to show that the hydrated silicate monomers are part of a separate phase and that they cannot be attributed to a hydroxylated surface of tricalcium silicate after contact with water. The phase containing hydrated silicate monomers is metastable with respect to the C-S-H phase since it transforms into the latter in a half saturated calcium hydroxide solution. These data is used to emphasize that the hydration of tricalcium silicate proceeds in two consecutive steps. In the first reaction, an intermediate phase containing hydrated silicate monomers is formed which is subsequently transformed into C-S-H as the final hydration product in the second step. The introduction of an intermediate phase in calculations of the early hydration of tricalcium silicate can explain the presence of the induction period. It is shown that heterogeneous nucleation on appropriate crystal surfaces is able to reduce the length of the induction period and thus to accelerate the reaction of tricalcium silicate with water.     

On the Glass Formation in the Na2O–SiO2–H2O System

The glass formation in the Na₂O–SiO₂–H₂O system is considered in the framework of the free volume theory of glasses. The boundaries of the glass transition range in the given system are determined from the dependences of the specific volume and the degree of connectivity on the water content in the system. The differences in the structure of hydrated glasses prepared by different methods are revealed. It is demonstrated that the molecular packing coefficients of the structures formed by drying of sodium silicate solutions are smaller than those of glasses prepared by hydration of anhydrous glasses. The densities are determined and the molar volumes are calculated for hydrated glasses in the Na₂O–SiO₂–H₂O system with a water content of 12–23 wt % (33–51 mol %) at a constant molar ratio SiO₂ : Na₂O = 2.8. The correlation relationship for the partial molar volume of water as a component of hydrated glasses is proposed as a function of the water content in the system. The use of this dependence allows one to calculate the molar volumes (densities) of hydrated glasses with different water contents.     

Structural modifications of nanostructured ceria CeO2,xH2O during dehydration process

Hydrated nanostructured cerium dioxide CeO₂, xH₂O (hydrated nanoceria) has been synthesized in room conditions via a precipitation route. This hydrated nanoceria phase has been subjected to thermal decomposition in the temperature range from 25 °C to 800 °C. At least three decomposition steps have been observed in thermal and thermogravimetric analyses. Three different samples of cubic nanoceria respectively obtained at room temperature (RT-nanoceria), 80 °C (80-nanoceria) and 600 °C (600-nanoceria) have been studied by X-Ray diffraction, Raman spectroscopy and scanning electron microscopy analyses. The analyses of X-ray diffraction profiles and Raman vibrational bands have clearly shown that dehydration is accompanied by increasing crystallite size, lattice parameter contraction. The cubic structure of hydrated RT-nanoceria might be associated with a complex chemical formula unit involving Ce⁴⁺, Ce³⁺ mixed valences, oxygen vacancies, lattice and surface water and OH^? proton species.     

Hydrations and water properties in the super salt-resistive gel probed by FT-IR

The so-called “Super Salt-Resistive Gel”, i.e., poly(4-vinyl phenol) (P4VPh) hydrogel, of different water contents (H = 95-40%) was prepared by crosslinking with different amounts of ethylene glycol diglycidyl ether (EGDGE). FT-IR spectroscopy was used to investigate the hydration and hydrogen bond (HB) properties of water in the gel samples. The OH stretching band around 3300 cm⁻¹ was deconvoluted into four sub-bands. On the basis of the relative band area and the peak wave number, it was suggested that HB of water in the gel is most stabilized when the acidic proton of the phenol residue is intact, being free from the chemical crosslinking. Difference spectra for the water band obtained in the presence of salts suggested that only sulfate systems specifically affect polymer hydrations in the gel phase. The sulfate systems were also specific in the perturbation on the main chain CH₂ stretching band; namely, with increasing the salt concentration, the peak showed a significant blue shift, which means that the hydrophobic hydration is stabilized by the typical salting-out divalent anion. All the experimental results on the FT-IR spectroscopy for the P4VPh hydrogel seem to be consistent with our previous ¹H NMR data on the water T₂ (Sakai Y, Kuroki S, Satoh M. Langmuir 2008; 24:6981-7.) as well as the specific stabilization of water (HB and hydration) in the gel that has been suggested on the basis of the swelling behavior.     

Influence of polymer on cement hydration in SBR-modified cement pastes

The influence of styrene-butadiene rubber (SBR) latex on cement hydrates Ca(OH)₂, ettringite, C₄AH₁₃ and C-S-H gel and the degree of cement hydration is studied by means of several measure methods. The results of DSC and XRD show that the Ca(OH)₂ content in wet-cured SBR-modified cement pastes increases with polymer-cement ratio (P/C) and reaches a maximum when P/C is 5%, 10% and 10% for the pastes hydrated for 3 d, 7 d and 28 d, respectively. With wet cure, appropriate addition of SBR promotes the hydration of cement, while the effect of SBR on the content of Ca(OH)₂ and the degree of cement hydration is not remarkable in mixed-cured SBR-modified cement pastes. XRD results illustrate that SBR accelerates the reaction of calcium aluminate with gypsum, and thus enhances the formation and stability of the ettringite and inhibits the formation of C₄AH₁₃. The structure of aluminum-oxide and silicon-oxide polyhedron is characterized by ²⁷Al and ²⁹Si solid state NMR spectrum method, which shows that tetrahedron and octahedron are the main forms of aluminum-oxide polyhedrons in SBR-modified cement pastes. There are only [SiO₄]⁴⁻ tetrahedron monomer and dimer in the modified pastes hydrated for 3 d, but there appears three-tetrahedron polymer in the modified pastes hydrated for 28 d. The effect of low SBR dosage on the structure of aluminum-oxide and silicon-oxide polyhedron is slight. However, the combination of Al³⁺ with [SiO₄]⁴⁻ is restrained when P/C is above 15%, and the structure of Al³⁺ is changed obviously. Meantime, the polymerization of the [SiO₄]⁴⁻ tetrahedron in C-S-H gel is controlled.     

Thermal release of hydrogen retained in multilayer graphene films prepared by mist-chemical vapor deposition

In this study, we investigated the absorption and thermal desorption processes of H and H₂O and the thickness of multilayer graphene films deposited on Cu foils using a mist-chemical vapor deposition method. Ion beam analysis techniques such as nuclear reaction analysis (NRA), elastic recoil detection (ERD), and Rutherford backscattering spectrometry (RBS) were employed. The RBS measurements revealed that the thickness of the multilayer graphene films was approximately 8 ± 3 nm (24 ± 9 layers). The depth distribution of H was analyzed using NRA and ERD. Based on these measurements, the residual H/C ratio for multilayer graphene was estimated to be approximately 0.03 in the bulk and 0.88 on the top-most surface. Additionally, the thermal desorption temperature for H from the multilayer graphene film was less than 373 K, which was much lower than that from isotropic graphite bulk (approximately 673 K). These results suggest that the thermal release of H did not occur because of desorption from sp²- and sp³-hybridized C atoms, such as intercalation and defect sites. Instead, it occurred owing to the desorption of H₂O adsorbed near the surface.     

Permeability of water and water vapor through cellulosic membranes

To elucidate the water transport mechanism through homogeneous membranes, water and water vapor permeation through crosslinked cellulose membranes, cellulose diacetate, and cellulose triacetate membranes are studied. It is found that the water flux increases with the degree of hydration; and as for cellulose membranes, the degree of hydration is an increasing function of the degree of crosslinking. Activation energy of hydraulic permeability (K_w) is not equal to that of purely viscous flow, and is smaller than that of the water vapor diffusion coefficient (D?) for all membranes. The free-volume concept relating the molar frictional coefficient to temperature and to degree of hydration explains reasonably the temperature dependence of hydraulic permeability and of water vapor diffusion coefficient and gives adequate values for the fractional free volume of the system. The critical volume V^*, appearing in the Cohen-Turnbull expression between friction coefficient and free volume fraction, may be considered as the size of the cluster of water molecules. The value of V^* in the case of hydraulic permeability is larger than that for water vapor diffusion by several times. Furthermore, the value V^* increases with increase of degree of hydration for water permeation and water vapor diffusion.     

Hydration of dibarium silicate II. rate of hydration

The rate of hydration of dibarium silicate (Ba²SiO₄) in paste form at room temperature was investigated. The uncombined barium hydroxide produced in the reaction, determined by a modified Franke method, was used as a measure of the extent of hydration. The linear relationship obtained between the uncombined barium hydroxide and the chemically combined water confirms that similar hydration products are formed at all stages of hydration, and either may be used as a measure of the degree of hydration. The rate of hydration of dibarium silicate was found to be lower than that of tricalcium aluminate, but higher than those of alite, tricalcium silicate and β-dicalcium silicate. The effect of water/solid ratio on the rate of hydration was also investigated. Dibarium silicate was completely hydrated after 30 days when it was mixed with a water/solid weight ratio > 0.7:1.     

EQCM study of electrodeposited PbO2: Investigation of the gel formation and discharge mechanisms

Lead dioxide thin films were electrodeposited on gold substrates and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The mass change occurring upon immersion in a H₂SO₄ electrolyte and during electrochemical reduction was observed in situ by electrochemical quartz crystal microbalance (EQCM). A hydrated PbO₂ gel-type layer is formed at the surface of electrodeposited PbO₂. The concentration of the H₂SO₄ electrolyte does not affect the composition of the gel nor the amount of lead dioxide involved in the hydration process. It is established that 1.3 × 10⁻⁷ mol cm⁻² of β-PbO₂ are hydrated at the surface of an electrodeposited film and that the hydration reaction occurs according to the following reaction: PbO₂^(crystal) + xH₂O ↔ (PbO(OH)₂·(x − 1)H₂O)^(gel), where x = 8.1. The mass change occurring during the first and subsequent discharge of PbO₂ was recorded. It is shown that both PbO₂^(crystal) and PbO(OH)₂·(7.1)H₂O)^(gel) are reduced to PbSO₄ during the first discharge.     

The Interaction Between Nuclear Waste Glass and Ordinary Portland Cement

The interaction between simulated reference waste glasses SON68 and SM539, and cement has been studied in suspensions of ordinary Portland cement and synthetic cement water with pH 13.5 at 30°C. The cement appears to trigger glass dissolution by consumption of glass matrix components. This leads to fast glass dissolution at a constant rate with formation of a porous gel layer on the glass. A glass dissolution model has been proposed considering that the silicon coming from the glass reacts with portlandite to form C-S-H phases. The transformation of C-S-H into C-A-S-H phases is a second parallel driving force especially for the Al-rich SM539 glass. After consumption of the portlandite, the glass alteration rate is expected to decrease.     

NMR study of starch based polymer gel electrolytes: Humidity effects

In this work, nuclear magnetic resonance spectroscopy (NMR) was used to study the effect of water absorption in polymer gel electrolytes formed by amylopectin rich starch, plasticized with glycerol and containing lithium perchlorate. The position of the ⁷Li spin-lattice relaxation rate maximum is shifted progressively towards lower temperatures with increasing hydration, reflecting an increase of the lithium mobility. The mechanism responsible for the spin-lattice relaxation of the ⁷Li nuclei in the gel electrolytes are the fluctuations of the quadrupolar interaction due to the lithium motions. The ⁷Li relaxation results of the gel electrolyte hydrated with 2.2 water per complex unit suggest that the lithium ions are almost decoupled from the polymer chain and coordinate, hence preferring the water molecules.