Growth of Surface Layer During the Leaching of The Simulated Waste Glass and its Barrier Effects on the Leaching

1982 ◽  
Vol 15 ◽  
Author(s):  
K. Ishiguro ◽  
N. Kawanishi ◽  
N. Sasaki ◽  
H. Nagaki ◽  
M. Yamamoto

ABSTRACTThe growth of surface layers on simulated waste glass during two different types of leaching has been studied in conjunction with their corrosion kinetics. Static and Soxhlet leach tests were performed in distilled water at a temperature of 100°C. Auger and ESCA analyses of solid samples after leaching showed that the layers consisted of two or three sublayers which were distinguished by their different components. The transition elements Fe and Ni, the rare-earths Nd and La, and Zn were concentrated in the layers, while Si, B and alkali were depleted in most of the layers. Growth kinetics of the layers followed approximately linear relations for the two types of leaching. Growth rates and elemental profiles of the layers depended upon the leaching conditions. Comparison between the leaching rate and the thickness of the layer showed that layers did not work as effective diffusion barriers until a threshold thickness was reached, which depended on the layer structures.

1982 ◽  
Vol 15 ◽  
Author(s):  
Werner Lutze ◽  
GÜnter Malow ◽  
Harald Rabe ◽  
Thomas J. Headley

Surface layers are a common feature of leached surfaces of borosilicate waste glasses. Layers are also observed upon weathering of volcanic glasses[l] and of silicate minerals[2]. The question of whether these layers can protect the glass against further attack by decreasing the leach rate is stïll a subject of controversy[3]. Both in geochemical work[4] and in work on waste forms [5,6], surface layers are attributed a protective function, and the stability of leached, million years old volcanic glasses[1] may be due to the presence of palagonite, a thin (≤100 μm) alteration layer, which forms in a few years but does not seem to increase in thickness after this time. The present study investigates the effects of layer formation on leaching kinetics of a borosilicate waste glass containing 20 wt.% LWR-type simulated waste oxides.


1995 ◽  
Vol 412 ◽  
Author(s):  
Shi-Ben Xing ◽  
Yijing Lin ◽  
Robert K. Mohr ◽  
Ian L. Pegg

AbstractIn many vitrification processes, refractory materials are used to contain the waste glass melt. The corrosive nature of the high-temperature melt consumes the waste feed materials but also limits refractory life. As vitrification is applied to more diverse waste streams, and particularly in higher-temperature applications, increasingly severe demands are placed on the refractory materials. A variety of potential refractory materials including Fused-cast AZS, Monofrax K3, Monofrax E, and the Corhart refractories ER1195, ER2161, C1215, C1215Z, Rechrome, and TI 186, were subjected to corrosion testing at 1450°C using the ASTM C-621 procedure. A series of simulated waste glasses was used which included F, Cl, S, Cu, Zn, Pb; these minor components were found to cause significant, and in some cases drastic, increases in corrosion rates. The corrosion tests were conducted over a range of time intervals extending to 144 hrs in order to investigate the kinetics of the corrosion processes. The change of the concentrations of constituents in the glass was monitored by compositional analysis of glass samples and correlated to the observed extent of corrosion; typically, components of the material under test increase with time while key minor components, such as Cu and Pb, decrease. The rate of corrosion of high-zirconia refractories was slowed considerably by adding zirconia to the waste glass composition; this has the added benefit of improving the aqueous leach resistance of the waste form that is produced.


1995 ◽  
Vol 412 ◽  
Author(s):  
W. L. Gong ◽  
R. C. Ewing ◽  
L. M. Wang ◽  
E. Vernaz ◽  
J. K. Bates ◽  
...  

AbstractThe SON68 inactive “R7T7” composition is the French reference glass for the LWR nuclear waste glass. Vapor phase alteration was used to accelerate the reaction progress of glass corrosion and to develop the characteristic suite of secondary, alteration phases. Extensive solid-state characterization (AEM/SEM/HRTEM) was completed on six inactive R7T7 waste glasses which were altered in the presence of saturated water vapor (200 °C) for 91, 241, 908, 1000, 1013, and 1021 days. The AEM samples were examined in cross-section (lattice-fringe imaging, microdiffraction, and quantitative thin-film EDS analysis). The glass monoliths were invariably covered with a thin altered rind. The layer became thicker with time: 0.5μm for 22 days; 4 μm for 91 days; 6 μm for 241 days; 10 μm for 908 days; 26 μm for 1013 days; and <35μm for 1021 days. The composite alteration layer of the SON68 samples is at least four time less thick than that of the SRL 131 glass composition.Six distinctive zones, based on phase chemistry and microstructure, were distinguished within the well-developed surface layers. Numerous crystalline phases such as analcime, tobermorite, apatite, and weeksite were identified on the surfaces of the reacted glasses as precipitates. Two crystalline phases, Ag2TeO3 and (Ca,Sr)Mo3O9(OH)2, were found within the inner zones of surface layers, and they must have nucleated in situ, indicating that Ag, Te, Sr, and Mo can be retained within the surface layer. The majority of the surface layer volume is composed of two morphologically and chemically different structures: one consists of well-crystallized fibrous smectite aggregates occurring along with cavities, the A-domain; and the other consists of poorlycrystallized regions containing needle-like smectite (montmorillonite) crystallites, a silica-rich amorphous matrix, and possibly ZrO2 particles, the B-domain. The retention of rare-earths and Zr mostly occurred within B-domains and that of transition elements, such as Zn, Cr, Ni, and Mn, in A-domains. The recrystallization of poorly-crystallized B-domains into well-crystallized Adomains may influence the long-term behavior of rare-earths, Zr, and transition elements. The mechanism of surface layer formation during vapor phase alteration is discussed based on the cross-sectional AEM studies of surface layers of the SON68 waste glasses.


1982 ◽  
Vol 49 (1-3) ◽  
pp. 413-428 ◽  
Author(s):  
George G Wicks ◽  
W.C Mosley ◽  
Peter G Whitkop ◽  
Kathy A Saturday

2018 ◽  
Vol 69 (5) ◽  
pp. 1139-1144
Author(s):  
Iosif Lingvay ◽  
Adriana Mariana Bors ◽  
Livia Carmen Ungureanu ◽  
Valerica Stanoi ◽  
Traian Rus

For the purpose of using three different types of painting materials for the inner protection of the transformer vats, their behavior was studied under actual conditions of operation in the transformer (thermal stress in electro-insulating fluid based on the natural ester in contact with copper for electro-technical use and electro-insulating paper). By comparing determination of the content in furans products (HPLC technique) and gases formed (by gas-chromatography) in the electro-insulating fluid (natural ester with high oleic content) thermally aged at 130 �C to 1000 hours in closed glass vessels, it have been found that the presence the investigated painting materials lead to a change in the mechanism and kinetics of the thermo-oxidation processes. These changes are supported by oxygen dissolved in oil, what leads to decrease both to gases formation CO2, CO, H2, CH4, C2H4 and C2H6) and furans products (5-HMF, 2-FOL, 2 -FAL and 2-ACF). The painting materials investigated during the heat treatment applied did not suffer any remarkable structural changes affecting their functionality in the electro-insulating fluid based on vegetable esters.


1987 ◽  
Vol 52 (3) ◽  
pp. 663-671 ◽  
Author(s):  
Jiří Hanika ◽  
Vladimír Janoušek ◽  
Karel Sporka

Adsorption data for the impregnation of alumina with an aqueous solution of cobalt dichloride and ammonium molybdate were treated in terms of the Langmuir adsorption isotherm and compared with a mathematical model set up to describe the kinetics of simultaneous impregnation of a support by two components. The effective diffusion coefficients of the two components at 25 °C in a cylindrical particle of alumina were obtained. The validity of the model used was verified qualitatively by comparing the numerical results with the experimental time dependent concentration profiles of the active components in a catalyst particle, measured by electron microanalysis technique.


2011 ◽  
Vol 324 ◽  
pp. 166-169 ◽  
Author(s):  
Farah Zeitouni ◽  
Gehan El-Subruiti ◽  
Ghassan Younes ◽  
Mohammad Amira

The rate of aquation of bromopentaammine cobalt(III) ion in the presence of different types of dicarboxylate solutions containing tert-butanol (40% V/V) have been measured spectrophotometrically at different temperatures (30-600°C) in the light of the effects of ion-pairing on reaction rates and mechanism. The thermodynamic and extrathermodynamic parameters of activation have been calculated and discussed in terms of solvent effect on the ion-pair aquation reaction. The free energy of activation ∆Gip* is more or less linearly varied among the studied dicarboxylate ion-pairing ligands indicating the presence of compensation effect between ∆Hip* and ∆Sip*. Comparing the kip values with respect of different buffers at 40% of ter-butanol is introduced.


1937 ◽  
Vol 20 (5) ◽  
pp. 737-766 ◽  
Author(s):  
A. G. Jacques

When 0.1 M NaI is added to the sea water surrounding Valonia iodide appears in the sap, presumably entering as NaI, KI, and HI. As the rate of entrance is not affected by changes in the external pH we conclude that the rate of entrance of HI is negligible in comparison with that of NaI, whose concentration is about 107 times that of HI (the entrance of KI may be neglected for reasons stated). This is in marked contrast with the behavior of sulfide which enters chiefly as H2S. It would seem that permeability to H2S is enormously greater than to Na2S. Similar considerations apply to CO2. In this respect the situation differs greatly from that found with iodide. NaI enters because its activity is greater outside than inside so that no energy need be supplied by the cell. The rate of entrance (i.e. the amount of iodide entering the sap in a given time) is proportional to the external concentration of iodide, or to the external product [N+]o [I-lo, after a certain external concentration of iodide has been reached. At lower concentrations the rate is relatively rapid. The reasons for this are discussed. The rate of passage of NaI through protoplasm is about a million times slower than through water. As the protoplasm is mostly water we may suppose that the delay is due chiefly to the non-aqueous protoplasmic surface layers. It would seem that these must be more than one molecule thick to bring this about. There is no great difference between the rate of entrance in the dark and in the light.


1979 ◽  
Vol 57 (4) ◽  
pp. 400-403 ◽  
Author(s):  
Anne Le Narvor ◽  
Pierre Saumagne

The ir spectra of mixtures of methyl propionate/water and methyl propionate/Ba2+ in dimethylsulfoxide and in acetonitrile have been recorded in the region of the νCO mode of the ester. Evidence is presented to indicate the presence of different types of complexes; their concentration was determined as a function of the composition of the medium. The spectroscopic results are compared to those from the kinetics of the alkaline hydrolysis in the same conditions. It is demonstrated that the orbital control explains the experimental results better than does the charge density on the carbon of the carbonyl group. [Journal translation]


Sign in / Sign up

Export Citation Format

Share Document