NMR study of C-A-S-H structures

Walker, C.*

NIMS Bisai Kozo Kaiseki Purattofuomu Riyo Hokokusho (Internet), 2 Pages, 2021/09

High content fly ash silica fume cement (HFSC) has been considering a candidate low alkali cements for the geological disposal of radioactive waste in Japan. JAEA has been currently performing many experiments and modeling studies relevant to validation for the long-term stability of the C-A-S-H gel which is a dominant component of the HFSC. For developing the C-A-S-H model of hydration and degradation, it is necessary to determine the composition of C-A-S-H gel and accompanied minerals when it reacts with water. In the present subject, the synthesized sample of C-A-S-H gels were analyzed by using the NMR spectra of Al and Si to determine the coordination of these element in the C-A-S-H gel.

Long-term immersion experiments of low alkaline cementitious materials

Seno, Yasuhiro*; Noguchi, Akira*; Nakayama, Masashi; Sugita, Yutaka; Suto, Shunkichi; Tanai, Kenji; Fujita, Tomoo; Sato, Haruo*

JAEA-Technology 2016-011, 20 Pages, 2016/07

JAEA-Technology-2016-011.pdf:7.56MB

Cementitious materials are expected to be used for the construction of an underground repository for the geological disposal of radioactive wastes. Ordinary Portland Cement(OPC) would conventionally be used in the fields of civil engineering and architecture, however, OPC has the potential to generate a highly alkaline plume (pH12.5), which will likely degrade the performance of other barriers in the repository such as the bentonite buffer and/or host rock. Low alkaline cementitious materials are therefore being developed that will mitigate the generation of a highly alkaline plume. JAEA has developed a High-volume Fly ash Silica fume Cement (HFSC) as a candidate low alkaline cementitious material. The workability of the HFSC shotcrete was confirmed by conducting In-situ full scale construction tests in the Horonobe underground research laboratory. This report summarizes the results of immersion tests to assess the long-term pH behavior of hardened HFSC cement pastes made with mix designs that are expected to be able to be used in the construction of an underground repository in Japan.

A study on long term stability of bentonite; The preliminary study on the bentonite stability in the groundwater influenced by cementitious material

*; Mihara, Morihiro;

JNC TN8430 2001-007, 56 Pages, 2002/01

JNC-TN8430-2001-007.pdf:13.13MB

In the geological disposal concept of radioactive wastes, a kind of clay with sorption ability and low permeability, called bentonite, is envisaged as an engineered barrier system in the geological repository. Also, the cemetitious material is envisaged as the backfill material in the vaults and the structure material of the vaults. The groundwater in contact with the cementitious material will promote hyperalkaline conditions in the repository environment and these conditions will affect the performance of the bentonite. Therefore, it is necessary to investigate the interaction between the cementitious material and the bentonite for the evaluation of long term stability of the disposal system. In this study, for the identification and the investigation of the secondary minerals, the batch immersion experiments of the powder bentonite were carried out using synthetic cement leachates (pH=7, 12.5, 14) at 200C. As the results, it was confirmed that Na as exchangeable cations in the bentonite can exchange relatively easily with Ca in the solution from the experiment results. And the ratio of cation exchange was estimated to be about 25% based on the amount of exchangeable cations Ca between layers. Furthermore, it was concretely shown that the generation of analcime might be affected by the Na concentration from results of the solution analyses and a stability analysis of analcime using the chemical equilibrium model, in addition to the pH in the solution.

Degradation studies on granite in alkaline solution

Owada, Hitoshi*; Mihara, Morihiro; *; *

JNC TN8400 2000-027, 19 Pages, 2000/08

JNC-TN8400-2000-027.pdf:1.8MB

Bactch leaching experiments of granite with the artifitial cement leachate and the leachate of low-alkalinity-cement (LW) were carried out to evaluate the effect of the hiperalkaline plume on the environment of the high-level and TRU radioactive waste repository. Dissolution of Si and Al from feldspar included in the granite and precipitation of C-S-H were confirmed from the results of the leaching experiments with artifitial cement leachate. From this result it was found that the composition of sorrounding rock changed. It also suggested that the retardation factor of migration of radionuclides would change. On the contrary, only decrease of concentrations in Si, Al and Ca in the leachate was observed in the experiment with LW. This result might indicate that C-S-H and/or C-A-S-H precipitated as secondary minerals in the LW case. From these results, it was considered that the hiperalkaline plume from the cementitious leachate might caused the change of disposal conditions such as the change in distribution coefficients of rock by precipitation of the secondary mineral and the increase in hydraulic conductivity by the dissolution of rock. On the other hand, the influences of the LW would be comparatively small, because LW and granite might equilibrate in short time.

Effect of leachate of cementitious materials on the geological media; Experimental study of the influence of high pH plume on rock

Kato, Hiroshige*; Sato, Mitsuyoshi*; Owada, Hitoshi*; Mihara, Morihiro;

JNC TN8430 2000-008, 53 Pages, 2000/05

JNC-TN8430-2000-008.pdf:4.8MB

Cementitious materials will be used in TRU waste disposal repository. In such cases, it is considered that the migration of alkaline leachates from cementitious materials, so called high pH plume, will cause dissolution of rock and precipitation of secondary minerals. In addition, the high pH plume will move along the flow of groundwater, so it is predicted that rock formation and components of high pH groundwater vary with time and space. However, time and spatial dependence of the variations of secondary minerals and groundwater components has not been clarified. In order to acquire the data of variations of secondary minerals and groundwater components, we carried out the rock alteration experiments with column method. The crushed granodiorite was filled into 4 meters length column (3.7 cm) and artificial cement leachate (pH=13.3; Na=0,1 mol/l, K=0.1 mol/l, Ca=0.002 mol/l) was streamed at flow rates of 0.1 ml/min for 7 months at 80C. As the result, secondary minerals confirmed on the rock were calcite and C-S-H at upstream of column and C-S-H at mid-downstream. The pH value of the fluid dominated by Na and K did not be decreased by reaction with the rock. In this study, the data relating to the effect of high pH plume on rock over the long term was acquired.

Modelling of the interaction of bentonite with hyperalkaline fluids

Muroi, Masayuki*

JNC TJ8400 2000-042, 142 Pages, 2000/02

JNC-TJ8400-2000-042.pdf:14.6MB

Hyperalkaline pore water of cementitious material used in TRU waste repository would react with bentonite and cause the increased porosity and the loss of the swelling and sorption ability. This work is a modelling study on bentonite-cement pore water. The possible extent of reaction between bentonite and cement pore water was simulated using the PRECIP reaction-transport code. Three cement pore fluid compositions (leachates 1,2 and 3) were reacted with a 1-D, 1m flowpath of bentonite (+ sand) at 25 and 70C. Key minerals were allowed to dissolve and precipitate using kinetic reaction mechanism. Leachate 1 was the most aggressive fluid (highest pH, Na and K), and leachate 3 (1owest pH, Na and Ca) the least aggressive. Simulation with leachate 1 showed total removal of primary bentonite minerals up to 60 cm from the contact with cement after 1000 years. The maximum porosity increase observed was in leachate 1(up to 80-90%) over a narrow zone 1-2 cm. Simulations with all fluids showed total filling of pore with CSH minerals in a zone very close to the interface with the cement, whereas zeolites and sheet silicates formed far away. For a given leachate composition, there was little difference in the profiles at the two temperatures studied. It was suggested that bentonite alteration was not sensitive to the kinetic parameters over the conditions studied. The conceptual model chosen for the modelling study assumed that there was an unlimited amount of cement pore fluid available for reaction with bentonite so that the results of the simulations represent a conservative (pessimistic) estimate. There were a number of uncertainties associated with the modelling which relate to assumptions concerning: the kinetic mechanisms for dissolution and growth of minerals at elevated pH; evolving surface areas of minerals with time; thermodynamic data for CSH minerals, zeolites and aqueous species at high pH; the synergy between changing porosity and fluid ...

The Study on degradation of engineered barrier in ratioactive waste repositories effect of nitrate and leaching solutions

Iriya, Keishiro*; *; Kubo, Hiroshi*; Fujita, Hideki*

JNC TJ8400 2000-033, 95 Pages, 2000/02

JNC-TJ8400-2000-033.pdf:11.11MB

Cementious materials and highly compacted bentnite are expectable candidates as materials of TRU waste repositories. It was pointed out that Bentonite might be changed to Zeolite and surrounding rock might be altered by high alkalinity water flow, since cement hydrate leached to pore water of cement and it was changed to alkaline. Transportation of radio-nuclides might be accelerated by organic materials, such as super plasticizer, and nitrate which is contained in nuclear wastes. It was concluded by previous studies that rock and bentonite is stable in alkaline water which pH is less than 10.5. The new type of low alkalinity cement with high silica fume and fly ash content which could keep pH below 11.0 was developed and its performance has been assessed. However since Zeolitation and ilitation were reported upon deterioration of bentonite bated in certain condition, it should be assessed by long term experiment. Since Capacity of keeping integrity of bentonite hasn't been directly checked by experiments upon the developed new type of low alkalinity cement it should be done. Although amount of leaching organic was quantitatively and experimentally assessed at an early age, effect of changing of amount and shape hasn't assessed in leaching of radio nuclides. Although it is pointed out that deterioration of cementitious materials isn't accelerated by condensed nitrate solution at early period after closure, it is considered that it might be accelerated corresponding to chemical composition in case of decrement of concentration of nitrate. In this study, deterioration of materials will be assessed in detail in order to feed back the results to assessment of transportation of radio nuclides. Long term deterioration of bentonite by leaching water of cement will be experimentally assessed, and deteriorating test of bentonite will be carried out by leaching water of low alkalinity cement. Amount of organic and component of it will be measured. Furthermore ...

Models of Cement-Water Interaction and a Compilation of a Associated Thermodynamic Data

Savage, D.*; Lemke, K.*; Sasamoto, Hiroshi; Shibata, Masahiro; Arthur, R. C,*; Yui, Mikazu

JNC TN8400 2000-004, 30 Pages, 2000/01

JNC-TN8400-2000-004.pdf:1.26MB

Modeling approaches that have been proposed for cement-water system are reviewed in this report, and relevant supporting thsrmodynamic data are compiled. The thermodynamic data include standard molal thermodynamic properties of minerals and related compounds comprising cements, and equilibrium constants for associated hydrolysis reactions. Similar data for minerals that are stable in hyperalkaline geologic environments (e.g., zeolites) are also included because these minerals could be formed as hyperalkaline fluids emanating from cementitious matelials in a repository for radioactive wastes interact with the surrounding host rock. Standard molal properties (i.e., standard molal Gibbs free energies and enthalpies of formation and standard molal entropies), and/or equilibrium constants for associated hydrolysis reactions, are included for. (1)cement minerals and related compounds (Reardon, 1992; Glasser et al., 1999) (2)calcium-silicate hydrate minerals (Sarkar et al., 1982), and (3)zeolites (calorimetric and estimated values from various sources) All these data are accepted at face value, and it is therefore cautioned that the data, considered as a whole, may not be internally consistent. It is also important to note that the accuracy of these data have not been evaluated in the present study. Several models appropriate for cement-water systems have been proposed in recent years. Most are similar in the sense that they represent empirical fits to laboratory data for the CSH gel-water system, and therefore not thermodynamically defensible. An alternative modeling approach based on thermodynamic principles of solid-solution behavior appropriate for CSH gel has recently been proposed, however. It is reviewed in the present study, and evaluated in relation to experimental results obtained by JNC on cement-water interactions. The solid-solution model is based upon a thermodynamically- and structually-justifiable description of CSH gel in terms of a non-ideal ...

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PNC TJ1150 98-003, 99 Pages, 1998/03

PNC-TJ1150-98-003.pdf:4.39MB

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PNC TJ1150 97-004, 92 Pages, 1997/03

PNC-TJ1150-97-004.pdf:7.46MB

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