Glass Ceramic Waste Forms for Combined CS+LN+TM Fission Products Waste Streams
DOE Office of Scientific and Technical Information (OSTI.GOV)
Crum, Jarrod V.; Turo, Laura A.; Riley, Brian J.
2010-09-23
In this study, glass ceramics were explored as an alternative waste form for glass, the current baseline, to be used for immobilizing alkaline/alkaline earth + lanthanide (CS+LN) or CS+LN+transition metal (TM) fission-product waste streams generated by a uranium extraction (UREX+) aqueous separations type process. Results from past work on a glass waste form for the combined CS+LN waste streams showed that as waste loading increased, large fractions of crystalline phases precipitated upon slow cooling.[1] The crystalline phases had no noticeable impact on the waste form performance by the 7-day product consistency test (PCT). These results point towards the development ofmore » a glass ceramic waste form for treating CS+LN or CS+LN+TM combined waste streams. Three main benefits for exploring glass ceramics are: (1) Glass ceramics offer increased solubility of troublesome components in crystalline phases as compared to glass, leading to increased waste loading; (2) The crystalline network formed in the glass ceramic results in higher heat tolerance than glass; and (3) These glass ceramics are designed to be processed by the same melter technology as the current baseline glass waste form. It will only require adding controlled canister cooling for crystallization into a glass ceramic waste form. Highly annealed waste form (essentially crack free) with up to 50X lower surface area than a typical High-Level Waste (HLW) glass canister. Lower surface area translates directly into increased durability. This was the first full year of exploring glass ceramics for the Option 1 and 2 combined waste stream options. This work has shown that dramatic increases in waste loading are achievable by designing a glass ceramic waste form as an alternative to glass. Table S1 shows the upper limits for heat, waste loading (based on solubility), and the decay time needed before treatment can occur for glass and glass ceramic waste forms. The improvements are significant for both combined waste stream options in terms of waste loading and/or decay time required before treatment. For Option 1, glass ceramics show an increase in waste loading of 15 mass % and reduction in decay time of 24 years. Decay times of {approx}50 years or longer are close to the expected age of the fuel that will be reprocessed when the modified open or closed fuel cycle is expected to be put into action. Option 2 shows a 2x to 2.5x increase in waste loading with decay times of only 45 years. Note that for Option 2 glass, the required decay time before treatment is only 35 years because of the waste loading limits related to the solubility of MoO{sub 3} in glass. If glass was evaluated for similar waste loadings as those achieved in Option 2 glass ceramics, the decay time would be significantly longer than 45 years. These glass ceramics are not optimized, but already they show the potential to dramatically reduce the amount of waste generated while still utilizing the proven processing technology used for glass production.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Amoroso, J. W.; Marra, J. C.
2015-08-26
A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics)more » over geologic timescales of interest for nuclear waste immobilization [1]. A durable multi-phase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing. This report summarizes results from three years of work on the IAEA Coordinated Research Project on “Processing technologies for high level waste, formulation of matrices and characterization of waste forms” (T21027), and specific task “Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles” (17208).« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Amoroso, J. W.; Marra, J. C.
2015-08-26
A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics)more » over geologic timescales of interest for nuclear waste immobilization [1]. A durable multi-phase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing. This report summarizes results from three years of work on the IAEA Coordinated Research Project on “Processing technologies for high level waste, formulation of matrices and characterization of waste forms” (T21027), and specific task “Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles” (17208).« less
Process for immobilizing plutonium into vitreous ceramic waste forms
Feng, Xiangdong; Einziger, Robert E.
1997-01-01
Disclosed is a method for converting spent nuclear fuel and surplus plutonium into a vitreous ceramic final waste form wherein spent nuclear fuel is bound in a crystalline matrix which is in turn bound within glass.
Process for immobilizing plutonium into vitreous ceramic waste forms
Feng, X.; Einziger, R.E.
1997-08-12
Disclosed is a method for converting spent nuclear fuel and surplus plutonium into a vitreous ceramic final waste form wherein spent nuclear fuel is bound in a crystalline matrix which is in turn bound within glass.
Process for immobilizing plutonium into vitreous ceramic waste forms
Feng, X.; Einziger, R.E.
1997-01-28
Disclosed is a method for converting spent nuclear fuel and surplus plutonium into a vitreous ceramic final waste form wherein spent nuclear fuel is bound in a crystalline matrix which is in turn bound within glass.
Method for solidification of radioactive and other hazardous waste
Anshits, Alexander G.; Vereshchagina, Tatiana A.; Voskresenskaya, Elena N.; Kostin, Eduard M.; Pavlov, Vyacheslav F.; Revenko, Yurii A.; Tretyakov, Alexander A.; Sharonova, Olga M.; Aloy, Albert S.; Sapozhnikova, Natalia V.; Knecht, Dieter A.; Tranter, Troy J.; Macheret, Yevgeny
2002-01-01
Solidification of liquid radioactive waste, and other hazardous wastes, is accomplished by the method of the invention by incorporating the waste into a porous glass crystalline molded block. The porous block is first loaded with the liquid waste and then dehydrated and exposed to thermal treatment at 50-1,000.degree. C. The porous glass crystalline molded block consists of glass crystalline hollow microspheres separated from fly ash (cenospheres), resulting from incineration of fossil plant coals. In a preferred embodiment, the porous glass crystalline blocks are formed from perforated cenospheres of grain size -400+50, wherein the selected cenospheres are consolidated into the porous molded block with a binder, such as liquid silicate glass. The porous blocks are then subjected to repeated cycles of saturating with liquid waste, and drying, and after the last cycle the blocks are subjected to calcination to transform the dried salts to more stable oxides. Radioactive liquid waste can be further stabilized in the porous blocks by coating the internal surface of the block with metal oxides prior to adding the liquid waste, and by coating the outside of the block with a low-melting glass or a ceramic after the waste is loaded into the block.
Method of waste stabilization via chemically bonded phosphate ceramics
Wagh, Arun S.; Singh, Dileep; Jeong, Seung-Young
1998-01-01
A method for regulating the reaction temperature of a ceramic formulation process is provided comprising supplying a solution containing a monovalent alkali metal; mixing said solution with an oxide powder to create a binder; contacting said binder with bulk material to form a slurry; and allowing the slurry to cure. A highly crystalline waste form is also provided consisting of a binder containing potassium and waste substrate encapsulated by the binder.
Method of waste stabilization via chemically bonded phosphate ceramics
Wagh, A.S.; Singh, D.; Jeong, S.Y.
1998-11-03
A method for regulating the reaction temperature of a ceramic formulation process is provided comprising supplying a solution containing a monovalent alkali metal; mixing said solution with an oxide powder to create a binder; contacting said binder with bulk material to form a slurry; and allowing the slurry to cure. A highly crystalline waste form is also provided consisting of a binder containing potassium and waste substrate encapsulated by the binder. 3 figs.
NASA Astrophysics Data System (ADS)
Huang, J. C.; Wright, W. V.
1982-04-01
The Defense Waste Processing Facility (DWPF) for immobilizing nuclear high level waste (HLW) is scheduled to be built. High level waste is produced when reactor components are subjected to chemical separation operations. Two candidates for immobilizing this HLW are borosilicate glass and crystalline ceramic, either being contained in weld sealed stainless steel canisters. A number of technical analyses are being conducted to support a selection between these two waste forms. The risks associated with the manufacture and interim storage of these two forms in the DWPF are compared. Process information used in the risk analysis was taken primarily from a DWPF processibility analysis. The DWPF environmental analysis provided much of the necessary environmental information.
Performance and modeling of cesium ion exchange by ENGI neered form crystalline silicotitanates
DOE Office of Scientific and Technical Information (OSTI.GOV)
Anthony, R.G.; Gu, D.; Huckman, M.
1996-10-01
TAM-5, a hydrous crystalline silicotitanate (CST) powder developed by Sandia National Laboratories and Texas A&M University, and commercialized by UOP as IONSIV{reg_sign} Ion Exchanger Type IE-910, is a highly selective material for removing cesium and strontium from aqueous radioactive wastes such as those found at the Hanford site in Washington. An engineered form of the material suitable for column ion exchange type operations has been developed and tested. Data relevant to processing radioactive tank wastes including equilibrium distribution coefficients and column testing will be presented. The impact of exposure of the engineered form to chemically aggressive environments such as itmore » might experience during waste processing, and to the less aggressive environments it might experience during post processing storage has been assessed. The thermal stability of the material has also been evaluated. The experimental results have been integrated with an effort to model the material`s equilibrium and kinetic behavior.« less
Amoroso, Jake W.; Marra, James; Dandeneau, Christopher S.; ...
2017-01-18
The first scaled proof-of-principle cold crucible induction melter (CCIM) test to process a multiphase ceramic waste form from a simulated combined (Cs/Sr, lanthanide and transition metal fission products) commercial used nuclear fuel waste stream was recently conducted in the United States. X-ray diffraction, 2-D X-ray absorption near edge structure (XANES), electron microscopy, inductively coupled plasma-atomic emission spectroscopy (and inductively coupled plasma-mass spectroscopy for Cs), and product consistency tests were used to characterize the fabricated CCIM material. Characterization analyses confirmed that a crystalline ceramic with a desirable phase assemblage was produced from a melt using a CCIM. We identified primary hollandite,more » pyrochlore/zirconolite, and perovskite phases in addition to minor phases rich in Fe, Al, or Cs. The material produced in the CCIM was chemically homogeneous and displayed a uniform phase assemblage with acceptable aqueous chemical durability.« less
Letter report on PCT/Monolith glass ceramic corrosion tests
DOE Office of Scientific and Technical Information (OSTI.GOV)
Crawford, Charles L.
2015-09-24
The Savannah River National Laboratory (SRNL) is collaborating with personnel from Pacific Northwest National Laboratory (PNNL) to study advanced waste form glass ceramics for immobilization of waste from Used Nuclear Fuel (UNF) separations processes. The glass ceramic waste forms take advantage of both crystalline and glassy phases where ‘troublesome’ elements (e.g., low solubility in glass or very long-lived) partition to highly durable ceramic phases with the remainder of elements residing in the glassy phase. The ceramic phases are tailored to create certain minerals or unique crystalline structures that can host the radionuclides by binding them in their specific crystalline networkmore » while not adversely impacting the residual glass network (Crum et al., 2011). Glass ceramics have been demonstrated using a scaled melter test performed in a pilot scale (1/4 scale) cold crucible induction melter (CCIM) (Crum et al., 2014; Maio et al., 2015). This report summarizes recent results from both Phase I and Phase II bench scale tests involving crucible fabrication and corrosion testing of glass ceramics using the Product Consistency Test (PCT). Preliminary results from both Phase I and Phase II bench scale tests involving statistically designed matrices have previously been reported (Crawford, 2013; Crawford, 2014).« less
Mineral assemblage transformation of a metakaolin-based waste form after geopolymer encapsulation
NASA Astrophysics Data System (ADS)
Williams, Benjamin D.; Neeway, James J.; Snyder, Michelle M. V.; Bowden, Mark E.; Amonette, James E.; Arey, Bruce W.; Pierce, Eric M.; Brown, Christopher F.; Qafoku, Nikolla P.
2016-05-01
Mitigation of hazardous and radioactive waste can be improved through conversion of existing waste to a more chemically stable and physically robust waste form. One option for waste conversion is the fluidized bed steam reforming (FBSR) process. The resulting FBSR granular material was encapsulated in a geopolymer matrix referred to here as Geo-7. This provides mechanical strength for ease in transport and disposal. However, it is necessary to understand the phase assemblage evolution as a result of geopolymer encapsulation. In this study, we examine the mineral assemblages formed during the synthesis of the multiphase ceramic waste form. The FBSR granular samples were created from waste simulant that was chemically adjusted to resemble Hanford tank waste. Another set of samples was created using Savannah River Site Tank 50 waste simulant in order to mimic a blend of waste collected from 68 Hanford tank. Waste form performance tests were conducted using the product consistency test (PCT), the Toxicity Characteristic Leaching Procedure (TCLP), and the single-pass flow-through (SPFT) test. X-ray diffraction analyses revealed the structure of a previously unreported NAS phase and indicate that monolith creation may lead to a reduction in crystallinity as compared to the primary FBSR granular product.
Three-dimensional mapping of crystalline ceramic waste form materials
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cocco, Alex P.; DeGostin, Matthew B.; Wrubel, Jacob A.
Here, we demonstrate the use of synchrotron-based, transmission X-ray microscopy (TXM) and scanning electron microscopy to image the 3-D morphologies and spatial distributions of Ga-doped phases within model, single- and two-phase waste form material systems. Gallium doping levels consistent with those commonly used for nuclear waste immobilization (e.g., Ba 1.04Cs 0.24Ga 2.32Ti 5.68O 16) could be readily imaged. This analysis suggests that a minority phase with different stoichiometry/composition from the primary hollandite phase can be formed by the solid-state ceramic processing route with varying morphology (globular vs. cylindrical) as a function of Cs content. Our results represent a crucial stepmore » in developing the tools necessary to gain an improved understanding of the microstructural and chemical properties of waste form materials that influence their resistance to aqueous corrosion. This understanding will aid in the future design of higher durability waste form materials.« less
Three-dimensional mapping of crystalline ceramic waste form materials
Cocco, Alex P.; DeGostin, Matthew B.; Wrubel, Jacob A.; ...
2017-04-21
Here, we demonstrate the use of synchrotron-based, transmission X-ray microscopy (TXM) and scanning electron microscopy to image the 3-D morphologies and spatial distributions of Ga-doped phases within model, single- and two-phase waste form material systems. Gallium doping levels consistent with those commonly used for nuclear waste immobilization (e.g., Ba 1.04Cs 0.24Ga 2.32Ti 5.68O 16) could be readily imaged. This analysis suggests that a minority phase with different stoichiometry/composition from the primary hollandite phase can be formed by the solid-state ceramic processing route with varying morphology (globular vs. cylindrical) as a function of Cs content. Our results represent a crucial stepmore » in developing the tools necessary to gain an improved understanding of the microstructural and chemical properties of waste form materials that influence their resistance to aqueous corrosion. This understanding will aid in the future design of higher durability waste form materials.« less
Mineral assemblage transformation of a metakaolin-based waste form after geopolymer encapsulation
Williams, Benjamin D.; Neeway, James J.; Snyder, Michelle M. V.; ...
2015-12-23
We can improve mitigation of hazardous and radioactive waste through conversion of existing waste to a more chemically stable and physically robust waste form. One option for waste conversion is the fluidized bed steam reforming (FBSR) process. The resulting FBSR granular material was encapsulated in a geopolymer matrix referred to here as Geo-7. This provides mechanical strength for ease in transport and disposal. But, it is necessary to understand the phase assemblage evolution as a result of geopolymer encapsulation. In this study, we examine the mineral assemblages formed during the synthesis of the multiphase ceramic waste form. The FBSR granularmore » samples were created from waste simulant that was chemically adjusted to resemble Hanford tank waste. Another set of samples was created using Savannah River Site Tank 50 waste simulant in order to mimic a blend of waste collected from 68 Hanford tank. Waste form performance tests were conducted using the product consistency test (PCT), the Toxicity Characteristic Leaching Procedure (TCLP), and the single-pass flow-through (SPFT) test. Finally, X-ray diffraction analyses revealed the structure of a previously unreported NAS phase and indicate that monolith creation may lead to a reduction in crystallinity as compared to the primary FBSR granular product.« less
Radioactive Demonstrations Of Fluidized Bed Steam Reforming (FBSR) With Hanford Low Activity Wastes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jantzen, C. M.; Crawford, C. L.; Burket, P. R.
Several supplemental technologies for treating and immobilizing Hanford low activity waste (LAW) are being evaluated. One immobilization technology being considered is Fluidized Bed Steam Reforming (FBSR) which offers a low temperature (700-750?C) continuous method by which wastes high in organics, nitrates, sulfates/sulfides, or other aqueous components may be processed into a crystalline ceramic (mineral) waste form. The granular waste form produced by co-processing the waste with kaolin clay has been shown to be as durable as LAW glass. The FBSR granular product will be monolithed into a final waste form. The granular component is composed of insoluble sodium aluminosilicate (NAS)more » feldspathoid minerals such as sodalite. Production of the FBSR mineral product has been demonstrated both at the industrial, engineering, pilot, and laboratory scales on simulants. Radioactive testing at SRNL commenced in late 2010 to demonstrate the technology on radioactive LAW streams which is the focus of this study.« less
The Effect of Carbonate, Oxalate and Peroxide on the Cesium Loading of Ionsiv IE-910 and IE-911
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fondeur, F.F.
2000-12-19
The Savannah River Site (SRS) continues to examine three processes for the removal of radiocesium from high-level waste. One option involves the use of crystalline silicotitanate (CST) as a non-elutable ion exchange medium. The process uses CST in its engineered form - IONSIV IE-911 made by UOP, LLC. - in a column to contact the liquid waste. Cesium exchanges with sodium ions residing inside the CST particles. The design disposes of the cesium-loaded CST by vitrification within the Defense Waste Processing Facility.
Ceramics: Durability and radiation effects
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ewing, R.C.; Lutze, W.; Weber, W.J.
1996-05-01
At present, there are three seriously considered options for the disposition of excess weapons plutonium: (1) incorporation, partial burn-up and direct disposal of MOX-fuel; (2) vitrification with defense waste and disposal as glass {open_quotes}logs{close_quotes}; (3) deep borehole disposal. The first two options provide a safeguard due to the high activity of fission products in the irradiated fuel and the defense waste. The latter option has only been examined in a preliminary manner, and the exact form of the plutonium has not been identified. In this paper, we review the potential for the immobilization of plutonium in highly durable crystalline ceramicsmore » apatite, pyrochlore, zirconolite, monazite and zircon. Based on available data, we propose zircon as the preferred crystalline ceramic for the permanent disposition of excess weapons plutonium.« less
Corrosion Behavior and Microstructure Influence of Glass-Ceramic Nuclear Waste Forms
DOE Office of Scientific and Technical Information (OSTI.GOV)
Matthew Asmussen, R.; Neeway, James J.; Kaspar, Tiffany C.
Glass ceramic waste forms present a potentially viable technology for the long term immobilization and disposal of liquid nuclear wastes. Through control of chemistry during fabrication, such waste forms can have designed secondary crystalline phases within a borosilicate glass matrix. In this work, a glass ceramic containing powellite and oxyapatite secondary phases was tested for its corrosion properties in dilute conditions using single pass flow through testing (SPFT). Three glass ceramic samples were prepared using different cooling rates to produce samples with varying microstructure sizes. In testing at 90 °C in buffered pH 7 and pH 9 solutions, it wasmore » found that increasing pH and decreasing microstructure size (resulting from rapid cooling during fabrication) both led to a reduction in overall corrosion rate. The phases of the glass ceramic were found, using a combination of solutions analysis, SEM and AFM, to corrode preferably in the order of powellite > bulk glass matrix > oxyapatite.« less
Method for converting asbestos to non-carcinogenic compounds
Selby, Thomas W.
1996-01-01
Hazardous and carcinogenic asbestos waste characterized by a crystalline fibrous structure is transformed into non-carcinogenic, relatively nonhazardous, and non-crystalline solid compounds and gaseous compounds which have commercial utilization. The asbestos waste is so transformed by the complete fluorination of the crystalline fibrous silicate mineral defining the asbestos.
Method for converting asbestos to non-carcinogenic compounds
Selby, T.W.
1996-08-06
Hazardous and carcinogenic asbestos waste characterized by a crystalline fibrous structure is transformed into non-carcinogenic, relatively nonhazardous, and non-crystalline solid compounds and gaseous compounds which have commercial utilization. The asbestos waste is so transformed by the complete fluorination of the crystalline fibrous silicate mineral defining the asbestos. 7 figs.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kaminski, Michael D.; Mertz, Carol J.
2016-01-01
The physical properties of a surrogate waste form containing cesium, strontium, rubidium, and barium sintered into bentonite clay were evaluated for several simulant feed streams: chlorinated cobalt dicarbollide/polyethylene glycol (CCD-PEG) strip solution, nitrate salt, and chloride salt feeds. We sintered bentonite clay samples with a loading of 30 mass% of cesium, strontium, rubidium, and barium to a density of approximately 3 g/cm 3. Sintering temperatures of up to 1000°C did not result in volatility of cesium. Instead, there was an increase in crystallinity of the waste form upon sintering to 1000ºC for chloride- and nitrate-salt loaded clays. The nitrate saltmore » feed produced various cesium pollucite phases, while the chloride salt feed did not produce these familiar phases. In fact, many of the x-ray diffraction peaks could not be matched to known phases. Assemblages of silicates were formed that incorporated the Sr, Rb, and Ba ions. Gas evolution during sintering to 1000°C was significant (35% weight loss for the CCD-PEG waste-loaded clay), with significant water being evolved at approximately 600°C.« less
Docking 90Sr radionuclide in cement: An atomistic modeling study
NASA Astrophysics Data System (ADS)
Youssef, Mostafa; Pellenq, Roland J.-M.; Yildiz, Bilge
Cementitious materials are considered to be a waste form for the ultimate disposal of radioactive materials in geological repositories. We investigated by means of atomistic simulations the encapsulation of strontium-90, an important radionuclide, in calcium-silicate-hydrate (C-S-H) and its crystalline analog, the 9 Å-tobermorite. C-S-H is the major binding phase of cement. Strontium was shown to energetically favor substituting calcium in the interlayer sites in C-S-H and 9 Å-tobermorite with the trend more pronounced in the latter. The integrity of the silicate chains in both cementitious waste forms were not affected by strontium substitution within the time span of molecular dynamics simulation. Finally, we observed a limited degradation of the mechanical properties in the strontium-containing cementitious waste form with the increasing strontium concentration. These results suggest the cement hydrate as a good candidate for immobilizing radioactive strontium.
Feasible Recycling of Industrial Waste Coal Gangue for Preparation of Mullite Based Ceramic Proppant
NASA Astrophysics Data System (ADS)
Li, Guomin; Ma, Haiqiang; Tian, Yuming; Wang, Kaiyue; Zhou, Yi; Wu, Yaqiao; Zou, Xinwei; Hao, Jianying; Bai, Pinbo
2017-09-01
Industrial waste coal gangue was successfully utilized to prepare the mullite-based ceramic proppants. The experiments involved the pelletizing technology of proppant through intensive mixer and following the sintering process under different temperatures. The crystalline phase, microstructure, density and breakage ratio of the proppants were investigated. The results showed that with the increasing of sintering temperature, the crystalline phases were transformed to rod-like mullite, which formed the cross-linked structure, improving the densification of proppants. Consequently, the breakage ratio under the closure pressure of 35 MPa exhibited declining trend and reached the minimum value of 6.8% at 1450 °C. Owing to the easy preparation, feasible design, low cost and moderate breakage ratio, the mullite-based ceramic proppant prepared by coal gangue and bauxite is promising candidate for fracturing proppants in future applications.
Secondary Waste Form Down Selection Data Package – Ceramicrete
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cantrell, Kirk J.; Westsik, Joseph H.
2011-08-31
As part of high-level waste pretreatment and immobilized low activity waste processing, liquid secondary wastes will be generated that will be transferred to the Effluent Treatment Facility on the Hanford Site for further treatment. These liquid secondary wastes will be converted to stable solid waste forms that will be disposed in the Integrated Disposal Facility. Currently, four waste forms are being considered for stabilization and solidification of the liquid secondary wastes. These waste forms are Cast Stone, Ceramicrete, DuraLith, and Fluidized Bed Steam Reformer. The preferred alternative will be down selected from these four waste forms. Pacific Northwest National Laboratorymore » is developing data packages to support the down selection process. The objective of the data packages is to identify, evaluate, and summarize the existing information on the four waste forms being considered for stabilization and solidification of the liquid secondary wastes. The information included will be based on information available in the open literature and from data obtained from testing currently underway. This data package is for the Ceramicrete waste form. Ceramicrete is a relatively new engineering material developed at Argonne National Laboratory to treat radioactive and hazardous waste streams (e.g., Wagh 2004; Wagh et al. 1999a, 2003; Singh et al. 2000). This cement-like waste form can be used to treat solids, liquids, and sludges by chemical immobilization, microencapsulation, and/or macroencapsulation. The Ceramicrete technology is based on chemical reaction between phosphate anions and metal cations to form a strong, dense, durable, low porosity matrix that immobilizes hazardous and radioactive contaminants as insoluble phosphates and microencapsulates insoluble radioactive components and other constituents that do not form phosphates. Ceramicrete is a type of phosphate-bonded ceramic, which are also known as chemically bonded phosphate ceramics. The Ceramicrete binder is formed through an acid-base reaction between calcined magnesium oxide (MgO; a base) and potassium hydrogen phosphate (KH{sub 2}PO{sub 4}; an acid) in aqueous solution. The reaction product sets at room temperature to form a highly crystalline material. During the reaction, the hazardous and radioactive contaminants also react with KH{sub 2}PO{sub 4} to form highly insoluble phosphates. In this data package, physical property and waste acceptance data for Ceramicrete waste forms fabricated with wastes having compositions that were similar to those expected for secondary waste effluents, as well as secondary waste effluent simulants from the Hanford Tank Waste Treatment and Immobilization Plant were reviewed. With the exception of one secondary waste form formulation (25FA+25 W+1B.A. fabricated with the mixed simulant did not meet the compressive strength requirement), all the Ceramicrete waste forms that were reviewed met or exceeded Integrated Disposal Facility waste acceptance criteria.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fondeur, F.; Pennebaker, F.; Fink, S.
2010-11-11
The use of crystalline silicotitanate (CST) is proposed for an at-tank process to treat High Level Waste at the Savannah River Site. The proposed configuration includes deployment of ion exchange columns suspended in the risers of existing tanks to process salt waste without building a new facility. The CST is available in an engineered form, designated as IE-911-CW, from UOP. Prior data indicates CST has a proclivity to agglomerate from deposits of silica rich compounds present in the alkaline waste solutions. This report documents the prior literature and provides guidance for the design and operations that include CST to mitigatemore » that risk. The proposed operation will also add monosodium titanate (MST) to the supernate of the tank prior to the ion exchange operation to remove strontium and select alpha-emitting actinides. The cesium loaded CST is ground and then passed forward to the sludge washing tank as feed to the Defense Waste Processing Facility (DWPF). Similarly, the MST will be transferred to the sludge washing tank. Sludge processing includes the potential to leach aluminum from the solids at elevated temperature (e.g., 65 C) using concentrated (3M) sodium hydroxide solutions. Prior literature indicates that both CST and MST will agglomerate and form higher yield stress slurries with exposure to elevated temperatures. This report assessed that data and provides guidance on minimizing the impact of CST and MST on sludge transfer and aluminum leaching sludge.« less
Ion exchange of several radionuclides on the hydrous crystalline silicotitanate, UOP IONSIV IE-911
DOE Office of Scientific and Technical Information (OSTI.GOV)
Huckman, M.E.; Latheef, I.M.; Anthony, R.G.
1999-04-01
The crystalline silicotitanate, UOP IONSIV IE-911, is a proven material for removing radionuclides from a wide variety of waste streams. It is superior for removing several radionuclides from the highly alkaline solutions typical of DOE wastes. This laboratory previously developed an equilibrium model applicable to complex solutions for IE-910 (the power form of the granular IE-911), and more recently, the authors have developed several single component ion-exchange kinetic models for predicting column breakthrough curves and batch reactor concentration histories. In this paper, the authors model ion-exchange column performance using effective diffusivities determined from batch kinetic experiments. This technique is preferablemore » because the batch experiments are easier, faster, and cheaper to perform than column experiments. They also extend these ideas to multicomponent systems. Finally, they evaluate the ability of the equilibrium model to predict data for IE-911.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fox, K. M.; Johnson, F. C.
Increased loading of high level waste in glass can lead to crystallization within the glass. Some crystalline species, such as spinel, have no practical impact on the chemical durability of the glass, and therefore may be acceptable from both a processing and a product performance standpoint. In order to operate a melter with a controlled amount of crystallization, options must be developed for remediating an unacceptable accumulation of crystals. This report describes preliminary experiments designed to evaluate the ability to dissolve spinel crystals in simulated waste glass melts via the addition of glass forming chemicals (GFCs).
Vitrified metal finishing wastes I. Composition, density and chemical durability.
Bingham, P A; Hand, R J
2005-03-17
Durable phosphate glasses were formed by vitrifying waste filter cakes from two metal finishing operations. Some melts formed crystalline components during cooling. Compositional analysis of dried, heat treated and vitrified samples was made using energy-dispersive X-ray spectroscopy, X-ray fluorescence spectroscopy, inductively-coupled plasma spectroscopy and Leco induction furnace combustion analysis. Hydrolytic dissolution, measured by an adapted product consistency test, was reduced by up to 3 orders of magnitude upon heat treatment or vitrification, surpassing the performance of borosilicate glass in some cases. This was attributed to the high levels of iron and zinc in the wastes, which greatly improve the durability of phosphate glasses. One of the wastes arose from a metal phosphating process and was particularly suitable for vitrification due to its high P2O5 content and favourable melting behaviour. The other waste, which arose from a number of processes, was less suitable as it had a low P2O5 content and during heating it emitted harmful corrosive gases and underwent violent reactions. Substantial volume reductions were obtained by heat treatment and vitrification of both wastes. Compositions and performances of some vitrified wastes were comparable with those of glasses which are under consideration for the immobilisation of toxic and nuclear wastes.
Evaluation of final waste forms and recommendations for baseline alternatives to group and glass
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bleier, A.
1997-09-01
An assessment of final waste forms was made as part of the Federal Facilities Compliance Agreement/Development, Demonstration, Testing, and Evaluation (FFCA/DDT&E) Program because supplemental waste-form technologies are needed for the hazardous, radioactive, and mixed wastes of concern to the Department of Energy and the problematic wastes on the Oak Ridge Reservation. The principal objective was to identify a primary waste-form candidate as an alternative to grout (cement) and glass. The effort principally comprised a literature search, the goal of which was to establish a knowledge base regarding four areas: (1) the waste-form technologies based on grout and glass, (2) candidatemore » alternatives, (3) the wastes that need to be immobilized, and (4) the technical and regulatory constraints on the waste-from technologies. This report serves, in part, to meet this goal. Six families of materials emerged as relevant; inorganic, organic, vitrified, devitrified, ceramic, and metallic matrices. Multiple members of each family were assessed, emphasizing the materials-oriented factors and accounting for the fact that the two most prevalent types of wastes for the FFCA/DDT&E Program are aqueous liquids and inorganic sludges and solids. Presently, no individual matrix is sufficiently developed to permit its immediate implementation as a baseline alternative. Three thermoplastic materials, sulfur-polymer cement (inorganic), bitumen (organic), and polyethylene (organic), are the most technologically developed candidates. Each warrants further study, emphasizing the engineering and economic factors, but each also has limitations that regulate it to a status of short-term alternative. The crystallinity and flexible processing of sulfur provide sulfur-polymer cement with the highest potential for short-term success via encapsulation. Long-term immobilization demands chemical stabilization, which the thermoplastic matrices do not offer. Among the properties of the remaining candidates, those of glass-ceramics (devitrified matrices) represent the best compromise for meeting the probable stricter disposal requirements in the future.« less
Piatak, N.M.; Seal, R.R.; Sanzolone, R.F.; Lamothe, P.J.; Brown, Z.A.; Adams, M.
2007-01-01
We report results from sequential extraction experiments and the quantitative mineralogy for samples of stream sediments and mine wastes collected from metal mines. Samples were from the Elizabeth, Ely Copper, and Pike Hill Copper mines in Vermont, the Callahan Mine in Maine, and the Martha Mine in New Zealand. The extraction technique targeted the following operationally defined fractions and solid-phase forms: (1) soluble, adsorbed, and exchangeable fractions; (2) carbonates; (3) organic material; (4) amorphous iron- and aluminum-hydroxides and crystalline manganese-oxides; (5) crystalline iron-oxides; (6) sulfides and selenides; and (7) residual material. For most elements, the sum of an element from all extractions steps correlated well with the original unleached concentration. Also, the quantitative mineralogy of the original material compared to that of the residues from two extraction steps gave insight into the effectiveness of reagents at dissolving targeted phases. The data are presented here with minimal interpretation or discussion and further analyses and interpretation will be presented elsewhere.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Callow, R.A.; Weidner, J.R.; Loehr, C.A.
This report describes two in situ vitrification field tests conducted on simulated buried waste pits during June and July 1990 at the Idaho National Engineering Laboratory. In situ vitrification, an emerging technology for in place conversion of contaminated soils into a durable glass and crystalline waste form, is being investigated as a potential remediation technology for buried waste. The overall objective of the two tests was to access the general suitability of the process to remediate waste structures representative of buried waste found at Idaho National Engineering Laboratory. In particular, these tests, as part of a treatability study, were designedmore » to provide essential information on the field performance of the process under conditions of significant combustible and metal wastes and to test a newly developed electrode feed technology. The tests were successfully completed, and the electrode feed technology successfully processed the high metal content waste. Test results indicate the process is a feasible technology for application to buried waste. 33 refs., 109 figs., 39 tabs.« less
Alpha-decay-induced fracturing in zircon - The transition from the crystalline to the metamict state
NASA Technical Reports Server (NTRS)
Chakoumakos, Bryan C.; Murakami, Takashi; Lumpkin, Gregory R.; Ewing, Rodney C.
1987-01-01
Zonation due to alpha-decay damage in a natural single crystal of zircon from Sri Lanka is discussed. The zones vary in thickness on a scale from one to hundreds of microns. The uranium and thorium concentrations vary from zone to zone such that the alpha decay dose is between 0.2 x 10 to the 16th and 0.8 x 10 to the 16th alpha-events per milligram. The transition from the crystalline to the aperiodic metamict state occurs over this dose range. At doses greater than 0.8 x 10 to the 16th alpha events/mg there is no evidence for long-range order. This type of damage will accumulate in actinide-bearing, ceramic nuclear waste forms. The systematic pattern of fractures would occur in crystalline phases that are zoned with respect to actinide radionuclides.
Melter Feed Reactions at T ≤ 700°C for Nuclear Waste Vitrification
DOE Office of Scientific and Technical Information (OSTI.GOV)
Xu, Kai; Hrma, Pavel R.; Rice, Jarrett A.
2015-07-23
Batch reactions and phase transitions in a nuclear waste feed heated at 5 K min-1 up to 600°C were investigated by optical microscopy, scanning electron microscopy with energy dispersive X-ray spectrometer, and X-ray diffraction. Quenched samples were leached in deionized water at room temperature and 80°C to extract soluble salts and early glass-forming melt, respectively. To determine the content and composition of leachable phases, the leachates were analyzed by the inductively-coupled plasma spectroscopy. By ~400°C, gibbsite and borax lost water and converted to amorphous and intermediate crystalline phases. Between 400°C and 600°C, the sodium borate early glass-forming melt reacted withmore » amorphous aluminum oxide and calcium oxide to form intermediate products containing Al and Ca. At ~600°C, half Na and B converted to the early glass-forming melt, and quartz began to dissolve in the melt.« less
Groundwork for Universal Canister System Development
DOE Office of Scientific and Technical Information (OSTI.GOV)
Price, Laura L.; Gross, Mike; Prouty, Jeralyn L.
2015-09-01
The mission of the United States Department of Energy's Office of Environmental Management is to complete the safe cleanup of the environmental legacy brought about from five decades of nuclear weapons development and go vernment - sponsored nuclear energy re search. S ome of the waste s that that must be managed have be en identified as good candidates for disposal in a deep borehole in crystalline rock (SNL 2014 a). In particular, wastes that can be disposed of in a small package are good candidates for this disposal concept. A canister - based system that can be used formore » handling these wastes during the disposition process (i.e., storage, transfers, transportation, and disposal) could facilitate the eventual disposal of these wastes. This report provides information for a program plan for developing specifications regarding a canister - based system that facilitates small waste form packaging and disposal and that is integrated with the overall efforts of the DOE's Office of Nuclear Energy Used Fuel Dis position Camp aign's Deep Borehole Field Test . Groundwork for Universal Ca nister System Development September 2015 ii W astes to be considered as candidates for the universal canister system include capsules containing cesium and strontium currently stored in pools at the Hanford Site, cesium to be processed using elutable or nonelutable resins at the Hanford Site, and calcine waste from Idaho National Laboratory. The initial emphasis will be on disposal of the cesium and strontium capsules in a deep borehole that has been drilled into crystalline rock. Specifications for a universal canister system are derived from operational, performance, and regulatory requirements for storage, transfers, transportation, and disposal of radioactive waste. Agreements between the Department of Energy and the States of Washington and Idaho, as well as the Deep Borehole Field Test plan provide schedule requirements for development of the universal canister system . Future work includes collaboration with the Hanford Site to move the cesium and strontium capsules into dry storage, collaboration with the Deep Borehole Field Tes t to develop surface handling and emplacement techniques and to develop the waste package design requirements, developing universal canister system design options and concepts of operations, and developing system analysis tools. Areas in which f urther research and development are needed include material properties and structural integrity, in - package sorbents and fillers, waste form tolerance to heat and postweld stress relief, waste package impact limiters, sensors, cesium mobility under downhol e conditions, and the impact of high pressure and high temperature environment on seals design.« less
Effective Recovery of Vanadium from Oil Refinery Waste into Vanadium-Based Metal-Organic Frameworks.
Zhan, Guowu; Ng, Wei Cheng; Lin, Wenlin Yvonne; Koh, Shin Nuo; Wang, Chi-Hwa
2018-03-06
Carbon black waste, an oil refinery waste, contains a high concentration of vanadium(V) leftover from the processing of crude oil. For the sake of environmental sustainability, it is therefore of interest to recover the vanadium as useful products instead of disposing of it. In this work, V was recovered in the form of vanadium-based metal-organic frameworks (V-MOFs) via a novel pathway by using the leaching solution of carbon black waste instead of commercially available vanadium chemicals. Two different types of V-MOFs with high levels of crystallinity and phase purity were fabricated in very high yields (>98%) based on a coordination modulation method. The V-MOFs exhibited well-defined and controlled shapes such as nanofibers (length: > 10 μm) and nanorods (length: ∼270 nm). Furthermore, the V-MOFs showed high catalytic activities for the oxidation of benzyl alcohol to benzaldehyde, indicating the strong potential of the waste-derived V-MOFs in catalysis applications. Overall, our work offers a green synthesis pathway for the preparation of V-MOFs by using heavy metals of industrial waste as the metal source.
Proceedings of the scientific visit on crystalline rock repository development.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mariner, Paul E.; Hardin, Ernest L.; Miksova, Jitka
2013-02-01
A scientific visit on Crystalline Rock Repository Development was held in the Czech Republic on September 24-27, 2012. The visit was hosted by the Czech Radioactive Waste Repository Authority (RAWRA), co-hosted by Sandia National Laboratories (SNL), and supported by the International Atomic Energy Agency (IAEA). The purpose of the visit was to promote technical information exchange between participants from countries engaged in the investigation and exploration of crystalline rock for the eventual construction of nuclear waste repositories. The visit was designed especially for participants of countries that have recently commenced (or recommenced) national repository programmes in crystalline host rock formations.more » Discussion topics included repository programme development, site screening and selection, site characterization, disposal concepts in crystalline host rock, regulatory frameworks, and safety assessment methodology. Interest was surveyed in establishing a %E2%80%9Cclub,%E2%80%9D the mission of which would be to identify and address the various technical challenges that confront the disposal of radioactive waste in crystalline rock environments. The idea of a second scientific visit to be held one year later in another host country received popular support. The visit concluded with a trip to the countryside south of Prague where participants were treated to a tour of the laboratory and underground facilities of the Josef Regional Underground Research Centre.« less
NASA Astrophysics Data System (ADS)
Ewing, Rodney C.; Weber, William J.; Lian, Jie
2004-06-01
During the past half-century, the nuclear fuel cycle has generated approximately 1400 metric tons of plutonium and substantial quantities of the "minor" actinides, such as Np, Am, and Cm. The successful disposition of these actinides has an important impact on the strategy for developing advanced nuclear fuel cycles, weapons proliferation, and the geologic disposal of high-level radioactive waste. During the last decade, there has been substantial interest in the use of the isometric pyrochlore structure-type, A2B2O7, for the immobilization of actinides. Most of the interest has focused on titanate-pyrochlore because of its chemical durability; however, these compositions experience a radiation-induced transition from the crystalline-to-aperiodic state due to radiation damage from the alpha-decay of actinides. Depending on the actinide concentration, the titanate pyrochlore will become amorphous in less than 1000 years of storage. Recently, systematic ion beam irradiations of a variety of pyrochlore compositions has revealed that many zirconate pyrochlores do not become amorphous, but remain crystalline as a defect fluorite structure-type due to disordering of the A- and B-site cations. The zirconate pyrochlores will remain crystalline even to very high doses, greater than 100 displacements per atom. Systematic experimental studies of actinide-doped and ion beam-irradiated pyrochlore, analyses of natural U- and Th-bearing pyrochlore, and simulations of the energetics of the disordering process now provide a rather detailed understanding of the structural and chemical controls on the response of pyrochlore to radiation. These results provide a solid basis for predicting the behavior and durability of pyrochlore used to immobilize plutonium.
NASA Astrophysics Data System (ADS)
Setiawan, D.; Subhan, A.; Saptari, S. A.
2017-07-01
The necessity of high charge-discharge capacity lithium-ion battery becomes very urgent due to its applications demand. Several researches have been done to meet the demand including Ca doping on Li4Ti5O12 for anode material of lithium-ion batteries. Ca-doped Li4Ti5O12 (LTO) in the form of Li4-xCaxTi5O12 (x = 0, 0.05, 0.075, and 0.1) have been synthesized using simple solid state reaction. The materials preparation involved waste eggshells in the form of CaCO3 as Ca source. The structure and capacity of as-prepared samples were characterized using X-Ray Diffractometer and Cyclic Voltametry. X-Ray Diffractometer characterization revealed that all amount of dopant had entered the lattice structure of LTO successfully. The crystalline sizes were obtained by using Scherrer equation. No significant differences are detected in lattice parameters (˜8.35 Å) and crystalline sizes (˜27 nm) between all samples. Cyclic Voltametry characterization shows that Li4-xCaxTi5O12 (x = 0.05) has highest charge-discharge capacity of 177.14 mAh/g and 181.92 mAh/g, respectively. Redox-potentials of samples show no significant differences with the average of 1.589 V.
Waste separation and pretreatment using crystalline silicotitanate ion exchangers
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tadros, M.E.; Miller, J.E.; Anthony, R.G.
1997-10-01
A new class of inorganic ion exchangers called crystalline silicotitanates (CSTs) has been developed jointly by Sandia National Laboratories and Texas A&M University to selectively remove Cs and other radionuclides from a wide spectrum of radioactive defense wastes. The CST exhibits high selectivity and affinity for Cs and Sr under a wide range of conditions. Tests show it can remove part-per-million concentrations of Cs{sup +} from highly alkaline, high-sodium simulated radioactive waste solutions modeled after those at Hanford, Oak Ridge, and Savannah River. The materials exhibit ion exchange properties based on ionic size selectivity. Specifically, crystalline lattice spacing is controlledmore » to be highly selective for Cs ions even in waste streams containing very high (5 to 10 M) concentrations of sodium. The CST technology is being demonstrated with actual waste at several DOE facilities. The use of inorganic ion exchangers. The inorganics are more resistant to chemical, thermal, and radiation degradation. Their high selectivities result in more efficient operations offering the possibility of a simple single-pass operation. In contrast, regenerable organic ion exchangers require additional processing equipment to handle the regeneration liquids and the eluant with the dissolved Cs.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Maio, Vince
This plan covers test BFY14CCIM-C which will be a first–of–its-kind demonstration for the complete non-radioactive surrogate production of multi-phase ceramic (SYNROC) High Level Waste Forms (HLW) using Cold Crucible Induction Melting (CCIM) Technology. The test will occur in the Idaho National Laboratory’s (INL) CCIM Pilot Plant and is tentatively scheduled for the week of September 15, 2014. The purpose of the test is to begin collecting qualitative data for validating the ceramic HLW form processability advantages using CCIM technology- as opposed to existing ceramic–lined Joule Heated Melters (JHM) currently producing BSG HLW forms. The major objectives of BFY14CCIM-C are tomore » complete crystalline melt initiation with a new joule-heated resistive starter ring, sustain inductive melting at temperatures between 1600 to 1700°C for two different relatively high conductive materials representative of the SYNROC ceramic formation inclusive of a HLW surrogate, complete melter tapping and pouring of molten ceramic material in to a preheated 4 inch graphite canister and a similar canister at room temperature. Other goals include assessing the performance of a new crucible specially designed to accommodate the tapping and pouring of pure crystalline forms in contrast to less recalcitrant amorphous glass, assessing the overall operational effectiveness of melt initiation using a resistive starter ring with a dedicated power source, and observing the tapped molten flow and subsequent relatively quick crystallization behavior in pans with areas identical to standard HLW disposal canisters. Surrogate waste compositions with ceramic SYNROC forming additives and their measured properties for inductive melting, testing parameters, pre-test conditions and modifications, data collection requirements, and sampling/post-demonstration analysis requirements for the produced forms are provided and defined.« less
Wu, Angjian; Li, Xiaodong; Yang, Jian; Du, Changming; Shen, Wangjun; Yan, Jianhua
2017-10-12
Vertical graphene (VG) sheets were single-step synthesized via inductively coupled plasma (ICP)-enhanced chemical vapor deposition (PECVD) using waste lard oil as a sustainable and economical carbon source. Interweaved few-layer VG sheets, H₂, and other hydrocarbon gases were obtained after the decomposition of waste lard oil. The influence of parameters such as temperature, gas proportion, ICP power was investigated to tune the nanostructures of obtained VG, which indicated that a proper temperature and H₂ concentration was indispensable for the synthesis of VG sheets. Rich defects of VG were formed with a high I D / I G ratio (1.29), consistent with the dense edges structure observed in electron microscopy. Additionally, the morphologies, crystalline degree, and wettability of nanostructure carbon induced by PECVD and ICP separately were comparatively analyzed. The present work demonstrated the potential of our PECVD recipe to synthesize VG from abundant natural waste oil, which paved the way to upgrade the low-value hydrocarbons into advanced carbon material.
NASA Astrophysics Data System (ADS)
Wu, Lang; Xiao, Jizong; Wang, Xin; Teng, Yuancheng; Li, Yuxiang; Liao, Qilong
2018-01-01
The crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics with different content (0-30 wt %) of simulated sulfate bearing high-level liquid waste (HLLW) were evaluated. The sulfate phase segregation in vitrification process was also investigated. The results show that the glass-ceramics with 0-20 wt% of HLLW possess mainly zirconolite phase along with a small amount baddeleyite phase. The amount of perovskite crystals increases while the amount of zirconolite crystals decreases when the HLLW content increases from 20 to 30 wt%. For the samples with 20-30 wt% HLLW, yellow phase was observed during the vitrification process and it disappeared after melting at 1150 °C for 2 h. The viscosity of the sample with 16 wt% HLLW (HLLW-16) is about 27 dPa·s at 1150 °C. The addition of a certain amount (≤20 wt %) of HLLW has no significant change on the aqueous stability of glass-ceramic waste forms. After 28 days, the 90 °C PCT-type normalized leaching rates of Na, B, Si, and La of the sample HLLW-16 are 7.23 × 10-3, 1.57 × 10-3, 8.06 × 10-4, and 1.23 × 10-4 g·m-2·d-1, respectively.
Lloyd, O.B.; Davis, R.W.
1989-01-01
Preliminary interpretation of available hydrogeologic data suggests that some areas underlying eastern Indiana, north-central Kentucky, and western Ohio might be worthy of further study regarding the disposal of high-level radioactive waste in Precambrian crystalline rocks buried beneath Paleozoic sedimentary rocks in the area. The data indicate that (1) largest areas of deepest potential burial and thickest sedimentary rock cover occur in eastern Indiana; (2) highest concentrations of dissolved solids in the basal sandstone aquifer, suggesting the most restricted circulation, are found in the southern part of the area near the Kentucky-Ohio State line and in southeastern Indiana; (3) largest areas of lowest porosity in the basal sandstone aquifer, low porosity taken as an indicator of the lowest groundwater flow velocity and contaminant migration, are found in northeastern Indiana and northwestern Ohio, central and southeastern Indiana, and central Kentucky; (4) the thickest confining units that directly overlie the basal sandstone aquifer are found in central Kentucky and eastern Indiana where their thickness exceeds 500 ft; (5) steeply dipping faults that form potential hydraulic connections between crystalline rock, the basal sandstone aquifer, and the freshwater circulation system occur on the boundaries of the study area mainly in central Kentucky and central Indiana. Collectively, these data indicate that the hydrogeology of the sedimentary rocks in the western part of the study area is more favorably suited than that in the remainder of the area for the application of the buried crystalline-rock concept. (USGS)
Zwetsloot, Marie J; Lehmann, Johannes; Solomon, Dawit
2015-01-01
Pyrolysis of slaughterhouse waste could promote more sustainable phosphorus (P) usage through the development of alternative P fertilizers. This study investigated how pyrolysis temperature (220, 350, 550 and 750 °C), rendering before pyrolysis, and wood or corn biomass additions affect P chemistry in bone char, plant availability, and its potential as P fertilizer. Linear combination fitting of synchrotron-based X-ray absorption near edge structure spectra demonstrated that higher pyrolysis temperatures decreased the fit with organic P references, but increased the fit with a hydroxyapatite (HA) reference, used as an indicator of high calcium phosphate (CaP) crystallinity. The fit to the HA reference increased from 0% to 69% in bone with meat residue and from 20% to 95% in rendered bone. Biomass additions to the bone with meat residue reduced the fit to the HA reference by 83% for wood and 95% for corn, and additions to rendered bone by 37% for wood. No detectable aromatic P forms were generated by pyrolysis. High CaP crystallinity was correlated with low water-extractable P, but high formic acid-extractable P indicative of high plant availability. Bone char supplied available P which was only 24% lower than Triple Superphosphate fertilizer and two- to five-fold higher than rock phosphate. Pyrolysis temperature and biomass additions can be used to design P fertilizer characteristics of bone char through changing CaP crystallinity that optimize P availability to plants. © 2014 Society of Chemical Industry.
Davis, R.W.
1984-01-01
Among the concepts suggested for the deep disposal of high-level radioactive wastes from nuclear power reactors is the excavation of a repository in suitable crystalline rocks overlain by a thick sequence of sedimentary strata in a hydrogeologic environment that would effectively impede waste transport. To determine the occurrence of such environments in the Eastern United States, a review was made of available sources of published or unpublished information, using the following hydrogeologic criteria:The top of the crystalline basement rock is 1,000 to 4,000 feet below land surface.The crystalline rock is overlain by sedimentary rock whose lowermost part, at least, contains ground water with a dissolved-solids concentration of 10,000 milligrams per liter or more.Shale or clay confining beds overlie the saline-water aquifer.The flow system in the saline-water aquifer is known or determinable from presently available data.All of these hydrogeologic conditions occur in two general areas: (1) parts of Indiana, Ohio, and Kentucky, underlain by part of the geologic structure known as the Cincinnati arch, and (2) parts of the Atlantic Coastal Plain from Georgia to New Jersey.
Granite disposal of U.S. high-level radioactive waste.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Freeze, Geoffrey A.; Mariner, Paul E.; Lee, Joon H.
This report evaluates the feasibility of disposing U.S. high-level radioactive waste in granite several hundred meters below the surface of the earth. The U.S. has many granite formations with positive attributes for permanent disposal. Similar crystalline formations have been extensively studied by international programs, two of which, in Sweden and Finland, are the host rocks of submitted or imminent repository license applications. This report is enabled by the advanced work of the international community to establish functional and operational requirements for disposal of a range of waste forms in granite media. In this report we develop scoping performance analyses, basedmore » on the applicable features, events, and processes (FEPs) identified by international investigators, to support generic conclusions regarding post-closure safety. Unlike the safety analyses for disposal in salt, shale/clay, or deep boreholes, the safety analysis for a mined granite repository depends largely on waste package preservation. In crystalline rock, waste packages are preserved by the high mechanical stability of the excavations, the diffusive barrier of the buffer, and favorable chemical conditions. The buffer is preserved by low groundwater fluxes, favorable chemical conditions, backfill, and the rigid confines of the host rock. An added advantage of a mined granite repository is that waste packages would be fairly easy to retrieve, should retrievability be an important objective. The results of the safety analyses performed in this study are consistent with the results of comprehensive safety assessments performed for sites in Sweden, Finland, and Canada. They indicate that a granite repository would satisfy established safety criteria and suggest that a small number of FEPs would largely control the release and transport of radionuclides. In the event the U.S. decides to pursue a potential repository in granite, a detailed evaluation of these FEPs would be needed to inform site selection and safety assessment.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Oji, L.; Martin, K.; Hobbs, D.
2012-01-03
Experimental results for the selective removal of strontium and cesium from simulated waste solutions with monosodium titanate and crystalline silicotitanate laden filter cartridges are presented. In these proof-of-principle tests, effective uptake of both strontium-85 and cesium-137 were observed using ion-exchangers in this filter cartridge configuration. At low salt simulant conditions, the instantaneous decontamination factor for strontium-85 with monosodium titanate impregnated filter membrane cartridges measured 26, representing 96% strontium-85 removal efficiency. On the other hand, the strontium-85 instantaneous decontamination factor with co-sintered active monosodium titanate cartridges measured 40 or 98% Sr-85 removal efficiency. Strontium-85 removal with the monosodium titanate impregnated membranemore » cartridges and crystalline silicotitanate impregnated membrane cartridges, placed in series arrangement, produced an instantaneous decontamination factor of 41 compared to an instantaneous decontamination factor of 368 for strontium-85 with co-sintered active monosodium titanate cartridges and co-sintered active crystalline silicotitanate cartridges placed in series. Overall, polyethylene co-sintered active titanates cartridges performed as well as titanate impregnated filter membrane cartridges in the uptake of strontium. At low ionic strength conditions, there was a significant uptake of cesium-137 with co-sintered crystalline silicotitanate cartridges. Tests results with crystalline silicotitanate impregnated membrane cartridges for cesium-137 decontamination are currently being re-evaluated. Based on these preliminary findings we conclude that incorporating monosodium titanate and crystalline silicotitanate sorbents into membranes represent a promising method for the semicontinuous removal of radioisotopes of strontium and cesium from nuclear waste solutions.« less
Digestion of Crystalline Silicotitanate (CST)
DOE Office of Scientific and Technical Information (OSTI.GOV)
DARREL, WALKER
2004-11-04
Researchers tested methods for chemically dissolving crystalline silicotitanate (CST) as a substitute for mechanical grinding to reduce particle size before vitrification. Testing used the commercially available form of CST, UOP IONSIV(R) IE-911. Reduction of the particle size to a range similar to that of the glass frit used by the Defense Waste Processing Facility (DWPF) could reduce problems with coupling cesium ion exchange to the vitrification process. This study found that IONSIV(R) IE-911 dissolves completely using a combination of acid, hydrogen peroxide, and fluoride ion. Neutralization of the resulting acidic solution precipitates components of the IONSIV(R) IE-911. Digestion requires extremelymore » corrosive conditions. Also, large particles may reform during neutralization, and the initiation and rate of gas generation are unpredictable. Therefore, the method is not recommended as a substitute for mechanical grinding.« less
CHEMICAL DIFFERENCES BETWEEN SLUDGE SOLIDS AT THE F AND H AREA TANK FARMS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Reboul, S.
2012-08-29
The primary source of waste solids received into the F Area Tank Farm (FTF) was from PUREX processing performed to recover uranium and plutonium from irradiated depleted uranium targets. In contrast, two primary sources of waste solids were received into the H Area Tank Farm (HTF): a) waste from PUREX processing; and b) waste from H-modified (HM) processing performed to recover uranium and neptunium from burned enriched uranium fuel. Due to the differences between the irradiated depleted uranium targets and the burned enriched uranium fuel, the average compositions of the F and H Area wastes are markedly different from onemore » another. Both F and H Area wastes contain significant amounts of iron and aluminum compounds. However, because the iron content of PUREX waste is higher than that of HM waste, and the aluminum content of PUREX waste is lower than that of HM waste, the iron to aluminum ratios of typical FTF waste solids are appreciably higher than those of typical HTF waste solids. Other constituents present at significantly higher concentrations in the typical FTF waste solids include uranium, nickel, ruthenium, zinc, silver, cobalt and copper. In contrast, constituents present at significantly higher concentrations in the typical HTF waste solids include mercury, thorium, oxalate, and radionuclides U-233, U-234, U-235, U-236, Pu-238, Pu-242, Cm-244, and Cm-245. Because of the higher concentrations of Pu-238 in HTF, the long-term concentrations of Th-230 and Ra-226 (from Pu-238 decay) will also be higher in HTF. The uranium and plutonium distributions of the average FTF waste were found to be consistent with depleted uranium and weapons grade plutonium, respectively (U-235 comprised 0.3 wt% of the FTF uranium, and Pu-240 comprised 6 wt% of the FTF plutonium). In contrast, at HTF, U-235 comprised 5 wt% of the uranium, and Pu-240 comprised 17 wt% of the plutonium, consistent with enriched uranium and high burn-up plutonium. X-ray diffraction analyses of various FTF and HTF samples indicated that the primary crystalline compounds of iron in sludge solids are Fe{sub 2}O{sub 3}, Fe{sub 3}O{sub 4}, and FeO(OH), and the primary crystalline compounds of aluminum are Al(OH){sub 3} and AlO(OH). Also identified were carbonate compounds of calcium, magnesium, and sodium; a nitrated sodium aluminosilicate; and various uranium compounds. Consistent with expectations, oxalate compounds were identified in solids associated with oxalic acid cleaning operations. The most likely oxidation states and chemical forms of technetium are assessed in the context of solubility, since technetium-99 is a key risk driver from an environmental fate and transport perspective. The primary oxidation state of technetium in SRS sludge solids is expected to be Tc(IV). In salt waste, the primary oxidation state is expected to be Tc(VII). The primary form of technetium in sludge is expected to be a hydrated technetium dioxide, TcO{sub 2} {center_dot} xH{sub 2}O, which is relatively insoluble and likely co-precipitated with iron. In salt waste solutions, the primary form of technetium is expected to be the very soluble pertechnetate anion, TcO{sub 4}{sup -}. The relative differences between the F and H Tank Farm waste provide a basis for anticipating differences that will occur as constituents of FTF and HTF waste residue enter the environment over the long-term future. If a constituent is significantly more dominant in one of the Tank Farms, its long-term environmental contribution will likely be commensurately higher, assuming the environmental transport conditions of the two Tank Farms share some commonality. It is in this vein that the information cited in this document is provided - for use during the generation, assessment, and validation of Performance Assessment modeling results.« less
Novel Crystalline SiO2 Nanoparticles via Annelids Bioprocessing of Agro-Industrial Wastes
2010-01-01
The synthesis of nanoparticles silica oxide from rice husk, sugar cane bagasse and coffee husk, by employing vermicompost with annelids (Eisenia foetida) is reported. The product (humus) is calcinated and extracted to recover the crystalline nanoparticles. X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and dynamic light scattering (DLS) show that the biotransformation allows creating specific crystalline phases, since equivalent particles synthesized without biotransformation are bigger and with different crystalline structure. PMID:20802789
NASA Astrophysics Data System (ADS)
Arbel Haddad, M.; Ofer-Rozovsky, E.; Bar-Nes, G.; Borojovich, E. J. C.; Nikolski, A.; Mogiliansky, D.; Katz, A.
2017-09-01
Alkali-activated aluminisilicate materials, also known as geopolymers, have been considered as attractive candidates for nuclear waste immobilization, due to their ability to incorporate cations, combined with high chemical resistance and suitable mechanical and thermal properties. The goal of the present research was to study the incorporation and immobilization of Cs in low-Si geopolymers (SiO2:Al2O3 molar ratio ≤ 2) which are known to have a relatively high crystalline phase content. A series of low-Si geopolymers was prepared from metakaolin using activating solutions containing CsOH and NaOH at different proportions. The structural evolution of the resulting products was followed using X-ray diffraction, the incorporation of Cs in the geopolymer was followed by pore water analysis, and its immobilization efficiency was determined from leaching tests following the ANSI/ANS-16.1 standard procedure. Like low-Si NaOH-based geopolymers, the mixed CsOH-NaOH geopolymers contain a significant amount of crystalline material which is imbedded within an amorphous matrix. Formulations with 1%Cs yielded the crystalline phases zeolite A and zeolite X. At 50%Cs the Cs-bearing zeolite F was formed. All three phases were observed at an intermediate Cs content (7%Cs). Pore water analysis indicated a preference for Cs uptake from the activating solution, while leaching experiments indicated selectivity for Cs immobilization in the mixed CsOH-NaOH geopolymers. Correlation of the apparent diffusion constants for both Na and Cs, as obtained from the leaching experiments, with the structural data lead to the conclusion that Cs is more efficiently bound by zeolite F, whereas Na binding is preferred by zeolites A and X. Nevertheless, the leachability indices for both Cs and Na were well above 6, indicating that such matrices may be considered as waste forms for 137Cs.
Guo, Xiaofeng; Kukkadapu, Ravi K.; Lanzirotti, Antonio; ...
2015-04-20
The garnet structure has been proposed as a potential crystalline nuclear waste form for accommodation of actinide elements, especially uranium (U). In this study, yttrium iron garnet (YIG) as a model garnet host was studied for the incorporation of U analogs, cerium (Ce) and thorium (Th), incorporated by a charge-coupled substitution with calcium (Ca) for yttrium (Y) in YIG, namely, 2Y³⁺ = Ca²⁺ + M⁴⁺, where M⁴⁺ = Ce⁴⁺ or Th⁴⁺. Single-phase garnets Y 3–xCa 0.5xM 0.5xFe₅O₁₂ (x = 0.1–0.7) were synthesized by the citrate–nitrate combustion method. Ce was confirmed to be tetravalent by X-ray absorption spectroscopy and X-ray photoelectronmore » spectroscopy. X-ray diffraction and ⁵⁷Fe–Mössbauer spectroscopy indicated that M⁴⁺ and Ca²⁺ cations are restricted to the c site, and the local environments of both the tetrahedral and the octahedral Fe³⁺ are systematically affected by the extent of substitution. The charge-coupled substitution has advantages in incorporating Ce/Th and in stabilizing the substituted phases compared to a single substitution strategy. Enthalpies of formation of garnets were obtained by high-temperature oxide melt solution calorimetry, and the enthalpies of substitution of Ce and Th were determined. The thermodynamic analysis demonstrates that the substituted garnets are entropically rather than energetically stabilized. This suggests that such garnets may form and persist in repositories at high temperature but might decompose near room temperature.« less
Crystalline matrices for the immobilization of plutonium and actinides
DOE Office of Scientific and Technical Information (OSTI.GOV)
Anderson, E.B.; Burakov, E.E.; Galkin, Ya.B.
1996-05-01
The management of weapon plutonium, disengaged as a result of conversion, is considered together with the problem of the actinide fraction of long-lived high level radioactive wastes. It is proposed to use polymineral ceramics based on crystalline host-phases: zircon ZrSiO{sub 4} and zirconium dioxide ZrO{sub 2}, for various variants of the management of plutonium and actinides (including the purposes of long-term safe storage or final disposal from the human activity sphere). It is shown that plutonium and actinides are able to form with these phases on ZrSiO{sub 4} and ZrO{sub 2} was done on laboratory level by the hot pressingmore » method, using the plasmochemical calcination technology. To incorporate simulators of plutonium into the structure of ZrSiO{sub 4} and ZrO{sub 2} in the course of synthesis, an original method developed by the authors as a result of studying the high-uranium zircon (Zr,U) SiO{sub 4} form Chernobyl {open_quotes}lavas{close_quotes} was used.« less
Experimental study on cesium immobilization in struvite structures.
Wagh, Arun S; Sayenko, S Y; Shkuropatenko, V A; Tarasov, R V; Dykiy, M P; Svitlychniy, Y O; Virych, V D; Ulybkina, Е А
2016-01-25
Ceramicrete, a chemically bonded phosphate ceramic, was developed for nuclear waste immobilization and nuclear radiation shielding. Ceramicrete products are fabricated by an acid-base reaction between magnesium oxide and mono potassium phosphate that has a struvite-K mineral structure. In this study, we demonstrate that this crystalline structure is ideal for incorporating radioactive Cs into a Ceramicrete matrix. This is accomplished by partially replacing K by Cs in the struvite-K structure, thus forming struvite-(K, Cs) mineral. X-ray diffraction and thermo-gravimetric analyses are used to confirm such a replacement. The resulting product is non-leachable and stable at high temperatures, and hence it is an ideal matrix for immobilizing Cs found in high-activity nuclear waste streams. The product can also be used for immobilizing secondary waste streams generated during glass vitrification of spent fuel, or the method described in this article can be used as a pretreatment method during glass vitrification of high level radioactive waste streams. Furthermore, it suggests a method of producing safe commercial radioactive Cs sources. Copyright © 2015 Elsevier B.V. All rights reserved.
Recycling of hazardous waste from tertiary aluminium industry in a value-added material.
Gonzalo-Delgado, Laura; López-Delgado, Aurora; López, Félix Antonio; Alguacil, Francisco José; López-Andrés, Sol
2011-02-01
The recent European Directive on waste, 2008/98/EC seeks to reduce the exploitation of natural resources through the use of secondary resource management. Thus the main objective of this study was to explore how a waste could cease to be considered as waste and could be utilized for a specific purpose. In this way, a hazardous waste from the tertiary aluminium industry was studied for its use as a raw material in the synthesis of an added-value product, boehmite. This waste is classified as a hazardous residue, principally because in the presence of water or humidity, it releases toxic gases such as hydrogen, ammonia, methane and hydrogen sulfide. The low temperature hydrothermal method developed permits the recovery of 90% of the aluminium content in the residue in the form of a high purity (96%) AlOOH (boehmite). The method of synthesis consists of an initial HCl digestion followed by a gel precipitation. In the first stage a 10% HCl solution is used to yield a 12.63 g L(-1) Al( 3+) solution. In the second stage boehmite is precipitated in the form of a gel by increasing the pH of the acid Al(3+) solution by adding 1 mol L(-1) NaOH solution. Several pH values were tested and boehmite was obtained as the only crystalline phase at pH 8. Boehmite was completely characterized by X-ray diffraction, Fourier transform infrared and scanning electron microscopy. A study of its thermal behaviour was also carried out by thermogravimetric/differential thermal analysis.
Generation of 3-D surface maps in waste storage silos using a structured light source
NASA Technical Reports Server (NTRS)
Burks, B. L.; Rowe, J. C.; Dinkins, M. A.; Christensen, B.; Selleck, C.; Jacoboski, D.; Markus, R.
1992-01-01
Surface contours inside the large waste storage tanks typical of the Department of Energy (DOE) complex are, in general, highly irregular. In addition to pipes and other pieces of equipment in the tanks, the surfaces may have features such as mounds, fissures, crystalline structures, and mixed solid and liquid forms. Prior to remediation activities, it will be necessary to characterize the waste to determine the most effective remediation approaches. Surface contour data will be required both prior to and during remediation. The use is described of a structured light source to generate 3-D surface contour maps of the interior of waste storage silos at the Feed Materials Production Center at Fernald, OH. The landscape inside these large waste storage tanks bears a strong resemblance to some of the landscapes that might be encountered during lunar or planetary exploration. Hence, these terrestrial 3-D mapping techniques may be directly applicable to extraterrestrial exploration. In further development, it will be demonstrated that these 3-D data can be used for robotic task planning just as 3-D surface contour data of a satellite could be used to plan maintenance tasks for a space-based servicing robot.
NASA Astrophysics Data System (ADS)
Chen, Yong; Hu, Liangbin; Qiu, Changjun; He, Bin; Wang, Zhongchang
2017-08-01
The Al2O3-TiO2 crystalline and amorphous multiphase ceramic coatings were prepared on a martensitic steel by laser in situ reaction technique and impose irradiation with 200 keV He ions at different doses. The helium ion irradiation goes 1.55 μm deep from the surface of coating, and the displacement per atom (dpa) for the Al2O3-TiO2 coating is 20.0. When the irradiation fluency is 5 × 1017 ions/cm2, defects are identified in crystalline areas and there form interfacial areas in the coating. These crystal defects tend to migrate and converge at the interfaces. Moreover, helium ion irradiation is found to exert no effect on surface chemical composition and phase constitution of the coatings, while surface mechanical properties for the coatings after irradiation differ from those before irradiation. Further nano-indentation experiments reveal that surface nano-hardness of the Al2O3-TiO2 multiphase coatings decreases as the helium ions irradiation flux increases. Such Al2O3-TiO2 crystalline and amorphous multiphase ceramic coatings exhibit the strongest resistance against helium ion irradiation which shall be applied as candidate structural materials for accelerator-driven sub-critical system to handle the nuclear waste under extreme conditions.
Geopolymerisation of silt generated from construction and demolition waste washing plants.
Lampris, C; Lupo, R; Cheeseman, C R
2009-01-01
Recycling plants that size, sort and wash construction and demolition waste can produce high quality aggregate. However, they also produce up to 80ton per hour of filter cake waste containing fine (<63mum) silt particles that is classified as inert waste and normally landfilled. This research investigated the potential to form geopolymers containing silt, which would allow this problematic waste to be beneficially reused as aggregate. This would significantly improve the economic viability of recycling plants that wash wastes. Silt filter cakes have been collected from a number of aggregate washing plants operating in the UK. These were found to contain similar aluminosilicate crystalline phases. Geopolymer samples were produced using silt and silt mixed with either metakaolin or pulverised fuel ash (PFA). Silt geopolymers cured at room temperature had average 7-day compressive strengths of 18.7MPa, while partial substitution of silt by metakaolin or PFA increased average compressive strengths to 30.5 and 21.9MPa, respectively. Curing specimens for 24h at 105 degrees C resulted in a compressive strength of 39.7MPa and microstructural analysis confirmed the formation of dense materials. These strengths are in excess of those required for materials to be used as aggregate, particularly in unbound applications. The implications of this research for the management of waste silt at construction and demolition waste washing plants are discussed.
Microwave-specific heating of crystalline species in nuclear waste glass
Christian, Jonathan H.; Fox, Kevin M.; Washington, Aaron L.
2016-08-03
Here, the microwave heating of a crystal-free and a partially trevorite-crystallized nuclear waste glass simulant was evaluated. Our results show that a 500-mg monolith of partially crystallized waste glass can be heated from room temperature to above 1600°C within 2 min using a single-mode, highly focused, 2.45 GHz microwave, operating at 300 W. Using X-ray diffraction measurements, we show that trevorite is no longer detectable after irradiation and thermal quenching. When a crystal-free analog of the same waste glass simulant composition was exposed to the same microwave radiation, it could not be heated above 450°C regardless of the heating time.more » The reduction in crystalline content achieved by selectively heating spinels in the presence of glass suggests that microwave-specific heating should be further explored as a technique for remediating crystal accumulation in a glass melt.« less
Alternative High-Performance Ceramic Waste Forms
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sundaram, S. K.
This final report (M5NU-12-NY-AU # 0202-0410) summarizes the results of the project titled “Alternative High-Performance Ceramic Waste Forms,” funded in FY12 by the Nuclear Energy University Program (NEUP Project # 12-3809) being led by Alfred University in collaboration with Savannah River National Laboratory (SRNL). The overall focus of the project is to advance fundamental understanding of crystalline ceramic waste forms and to demonstrate their viability as alternative waste forms to borosilicate glasses. We processed single- and multiphase hollandite waste forms based on simulated waste streams compositions provided by SRNL based on the advanced fuel cycle initiative (AFCI) aqueous separation process developed in the Fuel Cycle Research and Development (FCR&D). For multiphase simulated waste forms, oxide and carbonate precursors were mixed together via ball milling with deionized water using zirconia media in a polyethylene jar for 2 h. The slurry was dried overnight and then separated from the media. The blended powders were then subjected to melting or spark plasma sintering (SPS) processes. Microstructural evolution and phase assemblages of these samples were studied using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersion analysis of x-rays (EDAX), wavelength dispersive spectrometry (WDS), transmission electron spectroscopy (TEM), selective area x-ray diffraction (SAXD), and electron backscatter diffraction (EBSD). These results showed that the processing methods have significant effect on the microstructure and thus the performance of these waste forms. The Ce substitution into zirconolite and pyrochlore materials was investigated using a combination of experimental (in situ XRD and x-ray absorption near edge structure (XANES)) and modeling techniques to study these single phases independently. In zirconolite materials, a transition from the 2M to the 4M polymorph was observed with increasing Ce content. The resulting powders were consolidated via SPS. Ce was reduced to the trivalent oxidation state and the zirconolite was converted into undesirable perovskite. The zirconolite polymorphs found in the synthesized powders were recovered after a post-SPS heat treatment in air. These results demonstrated the potential of processing in controlling the phase assemblage in these waste forms. Hollandites with Cr 3+ trivalent cations were identified as potential hosts for Cs immobilization and are being investigated for Cs retention properties. Series of compositions Ba 1.15-xCs 2xCr 2.3Ti 5.7O 16, with increasing Cs loadings, were prepared by sol-gel process and characterized for structural parameters. Structural characterization was performed by a combination of powder XRD and neutron powder diffraction. Phase pure hollandite adapting monoclinic symmetry (I2/m) was observed for 0 ≤ x ≤ 0.55. These results were used to develop a new structural model to interpret Cs immobilization in these hollandites. Performance of these waste forms were evaluated for chemical durability and radiation resistance. Product consistency testing (PCT) and vapor hydration testing (VHT) were used for testing of chemical durability. Radiation resistance was tested using He + ions to simulatemore » $$\\alpha$$ particles and heavy ions such as Au 3+ to simulate a recoil. These results showed that these waste forms were chemically durable. The waste forms also amorphized to various degrees on exposure to simulated radiation.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kruger, Albert A.; Pegg, I. L.; Chaudhuri, M.
2013-11-13
The principal objective of the work reported here was to develop and identify HLW glass compositions that maximize waste processing rates for the aluminum limted waste composition specified by ORP while maintaining high waste loadings and acceptable glass properties. This was accomplished through a combination of crucible-scale tests, confirmation tests on the DM100 melter system, and demonstration at pilot scale (DM1200). The DM100-BL unit was selected for these tests since it was used previously with the HLW waste streams evaluated in this study, was used for tests on HLW glass compositions to support subsequent tests on the HLW Pilot Melter,more » conduct tests to determine the effect of various glass properties (viscosity and conductivity) and oxide concentrations on glass production rates with HLW feed streams, and to assess the volatility of cesium and technetium during the vitrification of an HLW AZ-102 composition. The same melter was selected for the present tests in order to maintain comparisons between the previously collected data. These tests provide information on melter processing characteristics and off-gas data, including formation of secondary phases and partitioning. Once DM100 tests were completed, one of the compositions was selected for further testing on the DM1200; the DM1200 system has been used for processing a variety of simulated Hanford waste streams. Tests on the larger melter provide processing data at one third of the scale of the actual WTP HLW melter and, therefore, provide a more accurate and reliable assessment of production rates and potential processing issues. The work focused on maximizing waste processing rates for high aluminum HLW compositions. In view of the diversity of forms of aluminum in the Hanford tanks, tests were also conducted on the DM100 to determine the effect of changes in the form of aluminum on feed properties and production rate. In addition, the work evaluated the effect on production rate of modest increases in melter operating temperature. Glass composition development was based on one of the HLW waste compositions specified by ORP that has a high concentration of aluminum. Small-scale tests were used to provide an initial screening of various glass formulations with respect to melt rates; more definitive screening was provided by the subsequent DM100 tests. Glass properties evaluated included: viscosity, electrical conductivity, crystallinity, gross glass phase separation and the 7- day Product Consistency Test (ASTM-1285). Glass property limits were based upon the reference properties for the WTP HLW melter. However, the WTP crystallinity limit (< 1 vol% at 950oC) was relaxed slightly as a waste loading constraint for the crucible melts.« less
Chu, J P; Chen, Y T; Mahalingam, T; Tzeng, C C; Cheng, T W
2006-12-01
Fiber reinforced plastic (FRP) composite material has widespread use in general tank, special chemical tank and body of yacht, etc. The purpose of this study is directed towards the volume reduction of non-combustible FRP by thermal plasma and recycling of vitrified slag with specific procedures. In this study, we have employed three main wastes such as, FRP, gill net and waste glass. The thermal molten process was applied to treat vitrified slag at high temperatures whereas in the post-heat treatment vitrified slags were mixed with specific additive and ground into powder form and then heat treated at high temperatures. With a two-stage heat treatment, the treated sample was generated into four crystalline phases, cristobalite, albite, anorthite and wollastonite. Fine and relatively high dense structures with desirable properties were obtained for samples treated by the two-stage heating treatment. Good physical and mechanical properties were achieved after heat treatment, and this study reveals that our results could be comparable with the commercial products.
Crystalline Silicotitanate Ion Exchange Support for Salt-Alternatives
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fondeur, F.F.
2001-02-23
The current version of crystalline silicotitanate (TAM5) is commercially available from UOP under the trade name IONSIV IE-911. TAM5 was extensively tested by several researchers and was determined as the best currently available material for removing radioisotopes from various types of nuclear wastes salt solutions stored at various DOE sites. The studies at Savannah River Technology Center (SRTC) indicated that the CST granules tend to leach into the nuclear waste simulants as it is processed by the ion exchange columns that is packed with CST granules from UOP. We, at Texas A and M University, agreed to conduct research tomore » compliment the efforts at SRTC so that IONSIV IE-911 could be used for the treatment of nuclear waste stored at the DOE Savannah River facility. After consultation, we developed a Task Plan in January 2000. According to the agreement between Westinghouse Savannah River Company, Savannah River Technology Center, Aiken SC 29808 and, College Station, TX 77843, synthesis and the performance evaluations of crystalline silicotitanates (CST) were performed the during period of April 1 - September 30, 2000. Our main goals were delivery of a kilogram of CST (TAM5-4) synthesized at Texas A and M University in July to SRTC, performance evaluation of CST in nuclear waste simulants, and consultation mainly by telephone.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zheng, Z.; Anthony, R.G.; Miller, J.E.
1997-06-01
An equilibrium multicomponent ion exchange model is presented for the ion exchange of group I metals by TAM-5, a hydrous crystalline silicotitanate. On the basis of the data from ion exchange and structure studies, the solid phase is represented as Na{sub 3}X instead of the usual form of NaX. By using this solid phase representation, the solid can be considered as an ideal phase. A set of model ion exchange reactions is proposed for ion exchange between H{sup +}, Na{sup +}, K{sup +}, Rb{sup +}, and Cs{sup +}. The equilibrium constants for these reactions were estimated from experiments with simplemore » ion exchange systems. Bromley`s model for activity coefficients of electrolytic solutions was used to account for liquid phase nonideality. Bromley`s model parameters for CsOH at high ionic strength and for NO{sub 2}{sup {minus}} and Al(OH){sub 4}{sup {minus}} were estimated in order to apply the model for complex waste simulants. The equilibrium compositions and distribution coefficients of counterions were calculated for complex simulants typical of DOE wastes by solving the equilibrium equations for the model reactions and material balance equations. The predictions match the experimental results within 10% for all of these solutions.« less
Brown, D A; Kamineni, D C; Sawicki, J A; Beveridge, T J
1994-09-01
The concept of disposal of nuclear fuel waste in crystalline rock requires the effects of microbial action to be investigated. The Underground Research Laboratory excavated in a pluton of the Canadian Shield provides a unique opportunity to study these effects. Three biofilms kept moist by seepage through fractures in granitic rock faces of the Underground Research Laboratory have been examined. The biofilms contained a variety of gram-negative and gram-positive morphotypes held together by an organic extracellular matrix. Nutrient levels in the groundwater were low, but energy-dispersive X-ray spectroscopy has shown biogeochemical immobilization of several elements in the biofilms; some of these elements were concentrated from extremely dilute environmental concentrations, and all elements were chemically complexed together to form amorphous or crystalline fine-grained minerals. These were seen by transmission electron microscopy to be both associated with the surfaces of the bacteria and scattered throughout the extracellular matrix, suggesting their de novo development through bacterial surface-mediated nucleation. The biofilm consortia are thought to concentrate elements both by passive sorption and by energy metabolism. By Mössbauer spectroscopy and X-ray diffraction, one of the biofilms showed that iron was both oxidized and precipitated as ferrihydrite or hematite aerobically and reduced and precipitated as siderite anaerobically. We believe that some Archean banded-iron formations could have been formed in a manner similar to this, as it would explain the deposition of hematite and siderite in close proximity. This biogeochemical development of minerals may also affect the transport of material in waste disposal sites.
Brown, D. Ann; Kamineni, D. Choudari; Sawicki, Jerzy A.; Beveridge, Terry J.
1994-01-01
The concept of disposal of nuclear fuel waste in crystalline rock requires the effects of microbial action to be investigated. The Underground Research Laboratory excavated in a pluton of the Canadian Shield provides a unique opportunity to study these effects. Three biofilms kept moist by seepage through fractures in granitic rock faces of the Underground Research Laboratory have been examined. The biofilms contained a variety of gram-negative and gram-positive morphotypes held together by an organic extracellular matrix. Nutrient levels in the groundwater were low, but energy-dispersive X-ray spectroscopy has shown biogeochemical immobilization of several elements in the biofilms; some of these elements were concentrated from extremely dilute environmental concentrations, and all elements were chemically complexed together to form amorphous or crystalline fine-grained minerals. These were seen by transmission electron microscopy to be both associated with the surfaces of the bacteria and scattered throughout the extracellular matrix, suggesting their de novo development through bacterial surface-mediated nucleation. The biofilm consortia are thought to concentrate elements both by passive sorption and by energy metabolism. By Mössbauer spectroscopy and X-ray diffraction, one of the biofilms showed that iron was both oxidized and precipitated as ferrihydrite or hematite aerobically and reduced and precipitated as siderite anaerobically. We believe that some Archean banded-iron formations could have been formed in a manner similar to this, as it would explain the deposition of hematite and siderite in close proximity. This biogeochemical development of minerals may also affect the transport of material in waste disposal sites. Images PMID:16349374
NASA Astrophysics Data System (ADS)
Mao, Xianhe; Qin, Zhigui; Yuan, Xiaoning; Wang, Chunming; Cai, Xinan; Zhao, Weixia; Zhao, Kang; Yang, Ping; Fan, Xiaoling
2013-11-01
A simulated radioactive soil waste containing cerium as an imitator element has been immobilized by a thermite self-propagating high-temperature synthesis (SHS) process. The compositions, structures, and element leaching rates of products with different cerium contents have been characterized. To investigate the influence of iron on the chemical stability of the immobilized products, leaching tests of samples with different iron contents with different leaching solutions were carried out. The results showed that the imitator element cerium mainly forms the crystalline phases CeAl11O18 and Ce2SiO5. The leaching rate of cerium over a period of 28 days was 10-5-10-6 g/(m2 day). Iron in the reactants, the reaction products, and the environment has no significant effect on the chemical stability of the immobilized SHS products.
Handling and Emplacement Options for Deep Borehole Disposal Conceptual Design.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cochran, John R.; Hardin, Ernest
2015-07-01
This report presents conceptual design information for a system to handle and emplace packages containing radioactive waste, in boreholes 16,400 ft deep or possibly deeper. Its intended use is for a design selection study that compares the costs and risks associated with two emplacement methods: drill-string and wireline emplacement. The deep borehole disposal (DBD) concept calls for siting a borehole (or array of boreholes) that penetrate crystalline basement rock to a depth below surface of about 16,400 ft (5 km). Waste packages would be emplaced in the lower 6,560 ft (2 km) of the borehole, with sealing of appropriate portionsmore » of the upper 9,840 ft (3 km). A deep borehole field test (DBFT) is planned to test and refine the DBD concept. The DBFT is a scientific and engineering experiment, conducted at full-scale, in-situ, without radioactive waste. Waste handling operations are conceptualized to begin with the onsite receipt of a purpose-built Type B shipping cask, that contains a waste package. Emplacement operations begin when the cask is upended over the borehole, locked to a receiving flange or collar. The scope of emplacement includes activities to lower waste packages to total depth, and to retrieve them back to the surface when necessary for any reason. This report describes three concepts for the handling and emplacement of the waste packages: 1) a concept proposed by Woodward-Clyde Consultants in 1983; 2) an updated version of the 1983 concept developed for the DBFT; and 3) a new concept in which individual waste packages would be lowered to depth using a wireline. The systems described here could be adapted to different waste forms, but for design of waste packaging, handling, and emplacement systems the reference waste forms are DOE-owned high- level waste including Cs/Sr capsules and bulk granular HLW from fuel processing. Handling and Emplacement Options for Deep Borehole Disposal Conceptual Design July 23, 2015 iv ACKNOWLEDGEMENTS This report has benefited greatly from review principally by Steve Pye, and also by Paul Eslinger, Dave Sevougian and Jiann Su.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
T.J. Tranter; R.D. Tillotson; T.A. Todd
2005-04-01
Bench-scale column tests were performed using a commercial form of crystalline silicotitanate (CST) for removing radio-cesium from a surrogate acidic tank solution representative of liquid waste stored at the Idaho National Engineering and Environmental Laboratory (INEEL). An engineered form of CST ion exchanger, known as IONSIVtm IE-911 (UOP, Mt Laurel, NJ, USA), was tested in 15 cm3 columns at a flow rate of 5 bed volumes per hour. These experiments showed the ion exchange material to have reasonable selectivity and capacity for removing cesium from the complex chemical matrix of the solution. However, previous testing indicated that partial neutralization ofmore » the feed stream was necessary to increase the stability of the ion exchange media. Thus, in these studies, CST degradation was determined as a function of throughput in order to better assess the stability characteristics of the exchanger for potential future waste treatment applications. Results of these tests indicate that the degradation of the CST reaches a maximum very soon after the acidic feed is introduced to the column and then rapidly declines. Total dissolution of bed material did not exceed 3% under the experimental regime used.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yang, Pin; Wang, Yifeng; Rodriguez, Mark A.
The concept of deep borehole nuclear waste disposal has recently been proposed. Effective sealing of a borehole after waste emplacement is generally required. In a high temperature disposal mode, the sealing function will be fulfilled by melting the ambient granitic rock with waste decay heat or an external heating source, creating a melt that will encapsulate waste containers or plug a portion of the borehole above a stack of the containers. However, there are certain drawbacks associated with natural materials, such as high melting temperatures, slow crystallization kinetics, the resulting sealing materials generally being porous with low mechanical strength, insufficientmore » adhesion to waste container surface, and lack of flexibility for engineering controls. Here we show that natural granitic materials can be purposefully engineered through chemical modifications to enhance the sealing capability of the materials for deep borehole disposal. This work systematically explores the effect of chemical modification and crystallinity (amorphous vs. crystalline) on the melting and crystallization processes of a granitic rock system. A number of engineered granitic materials have been obtained that have decreased melting points, enhanced viscous densification, and accelerated recrystallization rates without compromising the mechanical integrity of the materials.« less
Enhanced materials from nature: nanocellulose from citrus waste.
Mariño, Mayra; Lopes da Silva, Lucimara; Durán, Nelson; Tasic, Ljubica
2015-04-03
Nanocellulose is a relatively inexpensive, highly versatile bio-based renewable material with advantageous properties, including biodegradability and nontoxicity. Numerous potential applications of nanocellulose, such as its use for the preparation of high-performance composites, have attracted much attention from industry. Owing to the low energy consumption and the addition of significant value, nanocellulose extraction from agricultural waste is one of the best alternatives for waste treatment. Different techniques for the isolation and purification of nanocellulose have been reported, and combining these techniques influences the morphology of the resultant fibers. Herein, some of the extraction routes for obtaining nanocellulose from citrus waste are addressed. The morphology of nanocellulose was determined by Scanning Electron Microscopy (SEM) and Field Emission Scanning Electron Microscopy (FESEM), while cellulose crystallinity indexes (CI) from lyophilized samples were determined using solid-state Nuclear Magnetic Resonance (NMR) and X-Ray Diffraction (XRD) measurements. The resultant nanofibers had 55% crystallinity, an average diameter of 10 nm and a length of 458 nm.
Li, Zheng; Wang, Lifen; Hua, Jiachuan; Jia, Shiru; Zhang, Jianfei; Liu, Hao
2015-04-20
The work is aimed to investigate the suitability of waste water of candied jujube-processing industry for the production of bacterial cellulose (BC) by Gluconacetobacter xylinum CGMCC No.2955 and to study the structure properties of bacterial cellulose membranes. After acid pretreatment, the glucose of hydrolysate was higher than that of waste water of candied jujube. The volumetric yield of bacterial cellulose in hydrolysate was 2.25 g/L, which was 1.5-folds of that in waste water of candied jujube. The structures indicated that the fiber size distribution was 3-14 nm in those media with an average diameter being around 5.9 nm. The crystallinity index of BC from pretreatment medium was lower than that of without pretreatment medium and BCs from various media had similar chemical binding. Ammonium citrate was a key factor for improving production yield and the crystallinity index of BC. Copyright © 2014 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hang, T.
2003-07-16
The U.S. Department of Energy (DOE) and the Nuclear Energy Commission of Argentina (CNEA) have a collaborative project to separate cesium/strontium from waste resulting from the production of Mo-99. The Pacific Northwest National Laboratory (PNNL) is assisting DOE on this joint project by providing technical guidance to CNEA scientists. As part of the collaboration, PNNL staff works with staff at the Savannah River Technology Center (SRTC) to run the VERSE-LC model for removal of cesium from the Mo-99 waste using the crystalline silicotitanate (CST) material (IONSIV(R) IE-911, UOP LLC, DesPlaines, IL) based on technical data provided by CNEA. This reportmore » discusses the VERSE-LC ion-exchange-column model and the predicted results of CNEA test cases.« less
Electrorheological crystallization of proteins and other molecules
Craig, G.D.; Rupp, B.
1996-06-11
An electrorheological crystalline mass of a molecule is formed by dispersing the molecule in a dispersion fluid and subjecting the molecule dispersion to a uniform electrical field for a period of time during which time an electrorheological crystalline mass is formed. Molecules that may be used to form an electrorheological crystalline mass include any organic or inorganic molecule which has a permanent dipole and/or which is capable of becoming an induced dipole in the presence of an electric field. The molecules used to form the electrorheological crystalline mass are preferably macromolecules, such as biomolecules, such as proteins, nucleic acids, carbohydrates, lipoproteins and viruses. Molecules are crystallized by a method in which an electric field is maintained for a period of time after the electrorheological crystalline mass has formed during which time at least some of the molecules making up the electrorheological crystalline mass form a crystal lattice. The three dimensional structure of a molecule is determined by a method in which an electrorheological crystalline mass of the molecule is formed, an X-ray diffraction pattern of the electrorheological crystalline mass is obtained and the three dimensional structure of the molecule is calculated from the X-ray diffraction pattern. 4 figs.
Electrorheological crystallization of proteins and other molecules
Craig, George D.; Rupp, Bernhard
1996-01-01
An electrorheological crystalline mass of a molecule is formed by dispersing the molecule in a dispersion fluid and subjecting the molecule dispersion to a uniform electrical field for a period of time during which time an electrorheological crystalline mass is formed. Molecules that may be used to form an electrorheological crystalline mass include any organic or inorganic molecule which has a permanent dipole and/or which is capable of becoming an induced dipole in the presence of an electric field. The molecules used to form the electrorheological crystalline mass are preferably macromolecules, such as biomolecules, such as proteins, nucleic acids, carbohydrates, lipoproteins and viruses. Molecules are crystallized by a method in which an electric field is maintained for a period of time after the electrorheological crystalline mass has formed during which time at least some of the molecules making up the electrorheological crystalline mass form a crystal lattice. The three dimensional structure of a molecule is determined by a method in which an electrorheological crystalline mass of the molecule is formed, an x-ray diffraction pattern of the electrorheological crystalline mass is obtained and the three dimensional structure of the molecule is calculated from the x-ray diffraction pattern.
Xu, Yun; Wen, Yi; Grote, Rob; Amoroso, Jake; Shuller Nickles, Lindsay; Brinkman, Kyle S.
2016-01-01
The hollandite structure is a promising crystalline host for Cs immobilization. A series of Ga-doped hollandite BaxCsyGa2x+yTi8−2x−yO16 (x = 0, 0.667, 1.04, 1.33; y = 1.33, 0.667, 0.24, 0) was synthesized through a solid oxide reaction method resulting in a tetragonal hollandite structure (space group I4/m). The lattice parameter associated with the tunnel dimension was found to increases as Cs substitution in the tunnel increased. A direct investigation of cation mobility in tunnels using electrochemical impedance spectroscopy was conducted to evaluate the ability of the hollandite structure to immobilize cations over a wide compositional range. Hollandite with the largest tunnel size and highest aspect ratio grain morphology resulting in rod-like microstructural features exhibited the highest ionic conductivity. The results indicate that grain size and optimized Cs stoichiometry control cation motion and by extension, the propensity for Cs release from hollandite. PMID:27273791
Jantzen, Carol M.; Trivelpiece, Cory L.; Crawford, Charles L.; ...
2017-02-18
The durability of high level nuclear waste glasses must be predicted on geological time scales. Waste glass surfaces form hydrogels when in contact with water for varying test durations. As the glass hydrogels age, some exhibit an undesirable resumption of dissolution at long times while others exhibit near steady-state dissolution, that is, nonresumption of dissolution. Resumption of dissolution is associated with the formation of zeolitic phases while nonresumption of dissolution is associated with the formation of clay minerals. Hydrogels with a stoichiometry close to that of imogolite, (Al 2O 3·Si(OH) 4), with ferrihydrite (Fe 2O 3·0.5H 2O), have been shownmore » to be associated with waste glasses that resume dissolution. Aluminosilicate hydrogels with a stoichiometry of allophane-hisingerite ((Al,Fe) 2O 3·1.3-2Si(OH) 4) have been shown to be associated with waste glasses that exhibit near steady-state dissolution at long times. These phases are all amorphous and poorly crystalline and are also found on natural weathered basalt glasses. Interaction of these hydrogels with excess alkali and OH – (strong base) in the leachates, causes the Al 2O 3· nSiO 2 (where n=1-2) hydrogels to mineralize to zeolites. Excess alkali in the leachate is generated by alkali in the glass. As a result, preliminary rate-determining leach layer forming exchange reactions are hypothesized based on these findings.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jantzen, Carol M.; Trivelpiece, Cory L.; Crawford, Charles L.
The durability of high level nuclear waste glasses must be predicted on geological time scales. Waste glass surfaces form hydrogels when in contact with water for varying test durations. As the glass hydrogels age, some exhibit an undesirable resumption of dissolution at long times while others exhibit near steady-state dissolution, that is, nonresumption of dissolution. Resumption of dissolution is associated with the formation of zeolitic phases while nonresumption of dissolution is associated with the formation of clay minerals. Hydrogels with a stoichiometry close to that of imogolite, (Al 2O 3·Si(OH) 4), with ferrihydrite (Fe 2O 3·0.5H 2O), have been shownmore » to be associated with waste glasses that resume dissolution. Aluminosilicate hydrogels with a stoichiometry of allophane-hisingerite ((Al,Fe) 2O 3·1.3-2Si(OH) 4) have been shown to be associated with waste glasses that exhibit near steady-state dissolution at long times. These phases are all amorphous and poorly crystalline and are also found on natural weathered basalt glasses. Interaction of these hydrogels with excess alkali and OH – (strong base) in the leachates, causes the Al 2O 3· nSiO 2 (where n=1-2) hydrogels to mineralize to zeolites. Excess alkali in the leachate is generated by alkali in the glass. As a result, preliminary rate-determining leach layer forming exchange reactions are hypothesized based on these findings.« less
NASA Astrophysics Data System (ADS)
Loiseau, P.; Caurant, D.
2010-07-01
Glass-ceramic materials containing zirconolite (nominally CaZrTi 2O 7) crystals in their bulk can be envisaged as potential waste forms for minor actinides (Np, Am, Cm) and Pu immobilization. In this study such matrices are synthesized by crystallization of SiO 2-Al 2O 3-CaO-ZrO 2-TiO 2 glasses containing lanthanides (Ce, Nd, Eu, Gd, Yb) and actinides (Th) as surrogates. A thin partially crystallized layer containing titanite and anorthite (nominally CaTiSiO 5 and CaAl 2Si 2O 8, respectively) growing from glass surface is also observed. The effect of the nature and concentration of surrogates on the structure, the microstructure and the composition of the crystals formed in the surface layer is presented in this paper. Titanite is the only crystalline phase able to significantly incorporate trivalent lanthanides whereas ThO 2 precipitates in the layer. The crystal growth thermal treatment duration (2-300 h) at high temperature (1050-1200 °C) is shown to strongly affect glass-ceramics microstructure. For the system studied in this paper, it appears that zirconolite is not thermodynamically stable in comparison with titanite growing form glass surface. Nevertheless, for kinetic reasons, such transformation (i.e. zirconolite disappearance to the benefit of titanite) is not expected to occur during interim storage and disposal of the glass-ceramic waste forms because their temperature will never exceed a few hundred degrees.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vienna, John D.; Schweiger, Michael J.; Bonham, Charles C.
Roughly half of the projected Hanford high-level waste batches will have waste loadings limited by relatively high concentration of Al2O3. Individual glasses have been formulated and tested to demonstrate that it is possible to increase the loading of these high-Al2O3 wastes in glass by as much as 50%. To implement such increases in waste loading in the Hanford Tank Waste Treatment and Immobilization Plant, the impact of composition on the properties of high-Al2O3 waste glasses must be quantified in the form of validated glass property-composition models. To collect the data necessary for glass property-composition models, a multi-phase experimental approach wasmore » developed. In the first phase of the study, a set of 46 glass compositions were statistically designed to most efficiently backfill existing data in the composition region for high-Al2O3 (15 to 30 wt%) waste glasses. The glasses were fabricated and key glass properties were tested: •Product Consistency Test (PCT) on quench (Q) and canister centerline cooled (CCC) samples •Toxicity Characteristic Leaching Procedure (TCLP) on Q and CCC samples •Crystallinity as a function of temperature (T) at equilibrium and of CCC samples •Viscosity and electrical conductivity as a function of T The measured properties of these glasses were compared to predictions from previously existing models developed over lower Al2O3 concentration ranges. Areas requiring additional testing and modeling were highlighted.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Guo, Xiaofeng; Kukkadapu, Ravi K.; Lanzirotti, Anthony
2015-04-20
The garnet structure has been proposed as a potential crystalline nuclear waste form for accommodation of actinide elements, especially uranium (U). In this study, yttrium iron garnet (YIG) as a model garnet host was studied for the incorporation of U analogs, cerium (Ce), and thorium (Th), incorporated by a charge-coupled substitution with calci-um (Ca) for yttrium (Y) in YIG, namely 2Y3+ = Ca2+ + M4+, where M4+ = Ce4+ or Th4+. Single phase garnets Y3-xCa0.5xM0.5xFe5O12, synthesized by the citrate-nitrate combustion method, were obtained up to x = 0.7. Ce was confirmed to be tetravalent by X-ray absorption spectroscopy and X-raymore » photoelectron spectroscopy. X-ray diffraction and 57Fe-Mössbauer spectroscopy indicated that the samples are single phase, M4+ and Ca2+ cations are restricted to the c-site, the nature of M4+ has only a minor effect on the structure, and the local environments of both the tetrahedral and octahedral Fe3+ are systematically affected by the extent of substitution, especially on the tetrahedral sublattice. The charge coupled substitution has advantages in incorporating Ce/Th and in stabilizing the substituted phases, compared to a single substitution strategy. Enthalpies of formation of garnets were obtained by high temperature oxide melt solution calorimetry, and the enthalpies of substitution of Ce and Th were determined. The thermodynamic analysis demonstrates that the substituted garnets are entropically rather than energetically stabilized. This suggests that such garnets may form and persist in repositories at high temperature but might decompose near room temperature. These structural and thermodynamic findings shed light on possible incorporation of U in this garnet system.« less
Synthesis of nano-crystalline hydroxyapatite and ammonium sulfate from phosphogypsum waste
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mousa, Sahar, E-mail: dollyriri@yahoo.com; King Abdulaziz University, Science and Art College, Chemistry Department, Rabigh Campus, P.O. Box:344, Postal code: 21911 Rabigh; Hanna, Adly
2013-02-15
Graphical abstract: TEM micrograph of dried HAP at 800 °C. -- Abstract: Phosphogypsum (PG) waste which is derived from phosphoric acid manufacture by using wet method was converted into hydroxyapatite (HAP) and ammonium sulfate. Very simple method was applied by reacting PG with phosphoric acid in alkaline medium with adjusting pH using ammonia solution. The obtained nano-HAP was dried at 80 °C and calcined at 600 °C and 900 °C for 2 h. Both of HAP and ammonium sulfate were characterized by X-ray diffraction (XRD) and infrared spectroscopy (IR) to study the structural evolution. The thermal behavior of nano-HAP wasmore » studied; the particle size and morphology were estimated by using transmission electron microscopy (TEM) and scanning electron microscopy (SEM). All the results showed that HAP nano-crystalline and ammonium sulfate can successfully be produced from phosphogypsum waste.« less
New Metal Niobate and Silicotitanate Ion Exchangers: Development and Characterization
DOE Office of Scientific and Technical Information (OSTI.GOV)
Alexandra Navrotsky; Mary Lou Balmer; Tina M. Nenoff
2003-12-05
This renewal proposal outlines our current progress and future research plans for ion exchangers: novel metal niobate and silicotitanate ion exchangers and their ultimate deployment in the DOE complex. In our original study several forms (including Cs exchanged) of the heat treated Crystalline Silicotitanates (CSTs) were fully characterized by a combination of high temperature synthesis and phase identification, low temperature synthesis and phase identification, and thermodynamics. This renewal proposal is predicated on work completed in our current EMSP program: we have shown preliminary data of a novel class of niobate-based molecular sieves (Na/Nb/M/O, M = transition metals), which show exceptionallymore » high selectivity for divalent cations under extreme conditions (acid solutions, competing cations), in addition to novel silicotitanate phases which are also selective for divalent cations. Furthermore, these materials are easily converted by a high temperature in-situ heat treatment into a refractory ceramic waste form with low cation leachability. The new waste form is a perovskite phase, which is also a major component of Synroc, a titanate ceramic waste form used for sequestration of HLW wastes from reprocessed, spent nuclear fuel. These new niobate ion exchangers also shown orders of magnitude better selectivity for Sr2+ under acid conditions than any other material. The goal of the program is to reduce the costs associated with divalent cation waste removal and disposal, to minimize the risk of contamination to the environment during ion exchanger processing, and to provide DOE with materials for near-term lab-bench stimulant testing, and eventual deployment. The proposed work will provide information on the structure/property relationship between ion exchanger frameworks and selectivity for specific ions, allowing for the eventual ''tuning'' of framework for specific ion exchange needs. To date, DOE sites have become interested in on-site testing of these materials; ongoing discussions and initial experiments are occurring with Dr. Dean Peterman, Idaho National Engineering and Environmental Laboratory (INEEL) (location of the DOE/EM Waste Treatment Focus Area), and Dr. John Harbour, Savannah River Site (SRS). Yet the materials have not been optimized, and further research and development of the novel ion exchangers and testing conditions with simulants are needed. In addition, studies of the ion exchanger composition versus ion selectivity, ion exchange capacity and durability of final waste form are needed. This program will bring together three key institutions to address scientific hurdles of the separation process associated with metal niobate and silicotitanate ion exchangers, in particular for divalent cations (e.g., Sr2+). The program involves a joint effort between researchers at Pacific Northwest National Laboratory, who are leaders in structure/property relations in silicotitanates and in waste form development and performance assessment, Sandia National Laboratories, who discovered and developed crystalline silicotitanate ion exchangers (with Texas A&M and UOP) and also the novel class of divalent metal niobate ion exchangers, and the Thermochemistry Facility at UC Davis, who are world renowned experts in calorimetry and have already performed extensive thermodynamic studies on silicotitanate materials. In addition, Dr. Rodney Ewing of University of Michigan, an expert in radiation effects on materials, and Dr. Robert Roth of the National Institute of Standards and Technology and The Viper Group, a leader in phase equilibria development, will be consultants for radiation and phase studies. The research team will focus on three tasks that will provide both the basic research necessary for the development of highly selective ion exchange materials and also materials for short-term deployment within the DOE complex: (1) Structure/property relationships of a novel class of niobate-based molecular sieves (Na/Nb/M/O, M = transition metals), which show exceptionally high selectivity for divalent cations under extreme conditions (acid solutions, competing cations), (2) the role of ion exchanger structure change (both niobates and silicotitanates) on the exchange capacity (for elements such as Sr and actinide-surrogates) which results from exposure to DOE complex waste simulants, (3) thermodynamic stability of metal niobates and silicotitanate ion exchangers.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jantzen, C.; Crawford, C.; Cozzi, A.
The U.S. Department of Energy's Office of River Protection (ORP) is responsible for the retrieval, treatment, immobilization, and disposal of Hanford's tank waste. Currently there are approximately 56 million gallons of highly radioactive mixed wastes awaiting treatment. A key aspect of the River Protection Project (RPP) cleanup mission is to construct and operate the Waste Treatment and Immobilization Plant (WTP). The WTP will separate the tank waste into high-level and low-activity waste (LAW) fractions, both of which will subsequently be vitrified. The projected throughput capacity of the WTP LAW Vitrification Facility is insufficient to complete the RPP mission in themore » time frame required by the Hanford Federal Facility Agreement and Consent Order, also known as the Tri-Party Agreement (TPA), i.e. December 31, 2047. Therefore, Supplemental Treatment is required both to meet the TPA treatment requirements as well as to more cost effectively complete the tank waste treatment mission. The Supplemental Treatment chosen will immobilize that portion of the retrieved LAW that is not sent to the WTP's LAW Vitrification facility into a solidified waste form. The solidified waste will then be disposed on the Hanford site in the Integrated Disposal Facility (IDF). In addition, the WTP LAW vitrification facility off-gas condensate known as WTP Secondary Waste (WTP-SW) will be generated and enriched in volatile components such as Cs-137, I-129, Tc-99, Cl, F, and SO4 that volatilize at the vitrification temperature of 1150 C in the absence of a continuous cold cap. The current waste disposal path for the WTP-SW is to recycle it to the supplemental LAW treatment to avoid a large steady state accumulation in the pretreatment-vitrification loop. Fluidized Bed Steam Reforming (FBSR) offers a moderate temperature (700-750 C) continuous method by which LAW and/or WTP-SW wastes can be processed irrespective of whether they contain organics, nitrates, sulfates/sulfides, chlorides, fluorides, volatile radionuclides or other aqueous components. The FBSR technology can process these wastes into a crystalline ceramic (mineral) waste form. The mineral waste form that is produced by co-processing waste with kaolin clay in an FBSR process has been shown to be as durable as LAW glass. Monolithing of the granular FBSR product is being investigated to prevent dispersion during transport or burial/storage but is not necessary for performance. A Benchscale Steam Reformer (BSR) was designed and constructed at the Savannah River National Laboratory (SRNL) to treat actual radioactive wastes to confirm the findings of the non-radioactive FBSR pilot scale tests and to qualify the waste form for applications at Hanford. Radioactive testing commenced in 2010 with a demonstration of Hanford's WTP-SW where Savannah River Site (SRS) High Level Waste (HLW) secondary waste from the Defense Waste Processing Facility (DWPF) was shimmed with a mixture of I-125/129 and Tc-99 to chemically resemble WTP-SW. Ninety six grams of radioactive product were made for testing. The second campaign commenced using SRS LAW chemically trimmed to look like Hanford's LAW. Six hundred grams of radioactive product were made for extensive testing and comparison to the non-radioactive pilot scale tests. The same mineral phases were found in the radioactive and non-radioactive testing.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Crawford, C.; Burket, P.; Cozzi, A.
2012-02-02
The U.S. Department of Energy's Office of River Protection (ORP) is responsible for the retrieval, treatment, immobilization, and disposal of Hanford's tank waste. Currently there are approximately 56 million gallons of highly radioactive mixed wastes awaiting treatment. A key aspect of the River Protection Project (RPP) cleanup mission is to construct and operate the Waste Treatment and Immobilization Plant (WTP). The WTP will separate the tank waste into high-level and low-activity waste (LAW) fractions, both of which will subsequently be vitrified. The projected throughput capacity of the WTP LAW Vitrification Facility is insufficient to complete the RPP mission in themore » time frame required by the Hanford Federal Facility Agreement and Consent Order, also known as the Tri-Party Agreement (TPA), i.e. December 31, 2047. Therefore, Supplemental Treatment is required both to meet the TPA treatment requirements as well as to more cost effectively complete the tank waste treatment mission. In addition, the WTP LAW vitrification facility off-gas condensate known as WTP Secondary Waste (WTP-SW) will be generated and enriched in volatile components such as {sup 137}Cs, {sup 129}I, {sup 99}Tc, Cl, F, and SO{sub 4} that volatilize at the vitrification temperature of 1150 C in the absence of a continuous cold cap (that could minimize volatilization). The current waste disposal path for the WTP-SW is to process it through the Effluent Treatment Facility (ETF). Fluidized Bed Steam Reforming (FBSR) is being considered for immobilization of the ETF concentrate that would be generated by processing the WTP-SW. The focus of this current report is the WTP-SW. FBSR offers a moderate temperature (700-750 C) continuous method by which WTP-SW wastes can be processed irrespective of whether they contain organics, nitrates, sulfates/sulfides, chlorides, fluorides, volatile radionuclides or other aqueous components. The FBSR technology can process these wastes into a crystalline ceramic (mineral) waste form. The mineral waste form that is produced by co-processing waste with kaolin clay in an FBSR process has been shown to be as durable as LAW glass. Monolithing of the granular FBSR product is being investigated to prevent dispersion during transport or burial/storage, but is not necessary for performance. A Benchscale Steam Reformer (BSR) was designed and constructed at the SRNL to treat actual radioactive wastes to confirm the findings of the non-radioactive FBSR pilot scale tests and to qualify the waste form for applications at Hanford. BSR testing with WTP SW waste surrogates and associated analytical analyses and tests of granular products (GP) and monoliths began in the Fall of 2009, and then was continued from the Fall of 2010 through the Spring of 2011. Radioactive testing commenced in 2010 with a demonstration of Hanford's WTP-SW where Savannah River Site (SRS) High Level Waste (HLW) secondary waste from the Defense Waste Processing Facility (DWPF) was shimmed with a mixture of {sup 125/129}I and {sup 99}Tc to chemically resemble WTP-SW. Prior to these radioactive feed tests, non-radioactive simulants were also processed. Ninety six grams of radioactive granular product were made for testing and comparison to the non-radioactive pilot scale tests. The same mineral phases were found in the radioactive and non-radioactive testing.« less
Used fuel disposition in crystalline rocks
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Y.; Hadgu, Teklu; Kalinina, Elena Arkadievna
The U.S. Department of Energy Office of Nuclear Energy, Office of Fuel Cycle Technology established the Used Fuel Disposition Campaign (UFDC) in fiscal year 2010 (FY10) to conduct the research and development (R&D) activities related to storage, transportation and disposal of used nuclear fuel and high level nuclear waste. The objective of the Crystalline Disposal R&D Work Package is to advance our understanding of long-term disposal of used fuel in crystalline rocks and to develop necessary experimental and computational capabilities to evaluate various disposal concepts in such media.
DOE Office of Scientific and Technical Information (OSTI.GOV)
T.J. Tranter; R.D. Tillotson; T.A. Todd
2005-04-01
A semi-scale column test was performed using a commercial form of crystalline silicotitanate (CST) for removing radio-cesium from a surrogate acidic tank solution, which represents liquid waste stored at the Idaho National Engineering and Environmental Laboratory (INEEL). The engineered form of CST ion exchanger, known as IONSIVtmIE-911 (UOP, Mt. Laurel,NJ, USA), was tested in a 500-cm3 column to obtain a cesium breakthrough curve. The cesium exchange capacity of this column matched that obtained from previous testing with a 15-mc3 column. A numerical algorithm using implicit finite difference approximations was developed to solve the governing mass transport equations for the CSTmore » columns. An effective mass transfer coefficient was derived from solving these equations for previously reported 15 cm3 tests. The effective mass transfer coefficient was then used to predict the cesium breakthrough curve for the 500-cm3 column and compared to the experimental data reported in this paper. The calculated breakthrough curve showed excellent agreement with the data from the 500-cm3 column even though the interstitial velocity was a factor of two greater. Thus, this approach should provide a reasonable method for scale up to larger columns for treating actual tank waste.« less
Silicotitanate molecular sieve and condensed phases
Nenoff, Tina M.; Nyman, May D.
2002-01-01
A new microporous crystalline molecular sieve material having the formula Cs.sub.3 TiSi.sub.3 O.sub.95.cndot.3H.sub.2 O and its hydrothermally condensed phase, Cs.sub.2 TiSi.sub.6 O.sub.15, are disclosed. The microporous material can adsorb divalent ions of radionuclides or other industrial metals such as chromium, nickel, lead, copper, cobalt, zinc, cadmium, barium, and mercury, from aqueous or hydrocarbon solutions. The adsorbed metal ions can be leached out for recovery purposes or the microporous material can be hydrothermally condensed to a radiation resistant, structurally and chemically stable phase which can serve as a storage waste form for radionuclides.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bostick, D.T.; Steele, W.V.
1999-08-01
This document describes physical and thermophysical property determinations that were made in order to resolve questions associated with the decontamination of Savannah River Site (SRS) waste streams using ion exchange on crystalline silicotitanate (CST). The research will aid in the understanding of potential issues associated with cooling of feed streams within SRS waste treatment processes. Toward this end, the thermophysical properties of engineered CST, manufactured under the trade name, Ionsive{reg_sign} IE-911 by UOP, Mobile, AL, were determined. The heating profiles of CST samples from several manufacturers' production runs were observed using differential scanning calorimetric (DSC) measurements. DSC data were obtainedmore » over the region of 10 to 215 C to check for the possibility of a phase transition or any other enthalpic event in that temperature region. Finally, the heat capacity, thermal conductivity, density, viscosity, and salting-out point were determined for SRS waste simulants designated as Average, High NO{sub 3}{sup {minus}} and High OH{sup {minus}} simulants.« less
Ageing of a phosphate ceramic used to immobilize chloride-contaminated actinide waste
DOE Office of Scientific and Technical Information (OSTI.GOV)
Metcalfe, Brian; Donald, Ian W.; Fong, Shirley K.
2009-03-31
At AWE, we have developed a process for the immobilization of ILW waste containing a significant quantity of chloride with Ca 3(PO 4) 2 as the host material. Waste ions are incorporated into two phosphate-based phases, chlorapatite [Ca 5(PO 4) 3Cl] and spodiosite [Ca 2(PO 4)Cl]. Non-active trials performed at AWE with Sm as the actinide surrogate demonstrated the durability of these phases in aqueous solution. Trials of the process, in which actinide-doped materials were used, wer performed at PNNL where the waste form was found to be resistant to aqueous leaching. Initial leach trials conducted on 239Pu / 241Ammore » loaded ceramic at 40°C/28 days gave normalized mass losses of 1.2 x 10 -5 g.m -2 and 2.7 x 10 -3 g.m -2 for Pu and Cl respectively. In order to assess the response of the phases to radiation-induced damage, accelerated ageing trials were performed on samples in which the 239Pu was replaced with 238Pu. No changes to the crystalline structure of the waste were detected in the XRD patterns after the samples had experienced an α radiation dose of 4 x 10 18 g -1. Leach trials showed that there was an increase in the P and Ca release rates but no change in the Pu release rate.« less
Solar cell contact formation using laser ablation
Harley, Gabriel; Smith, David D.; Cousins, Peter John
2015-07-21
The formation of solar cell contacts using a laser is described. A method of fabricating a back-contact solar cell includes forming a poly-crystalline material layer above a single-crystalline substrate. The method also includes forming a dielectric material stack above the poly-crystalline material layer. The method also includes forming, by laser ablation, a plurality of contacts holes in the dielectric material stack, each of the contact holes exposing a portion of the poly-crystalline material layer; and forming conductive contacts in the plurality of contact holes.
Solar cell contact formation using laser ablation
Harley, Gabriel; Smith, David; Cousins, Peter
2012-12-04
The formation of solar cell contacts using a laser is described. A method of fabricating a back-contact solar cell includes forming a poly-crystalline material layer above a single-crystalline substrate. The method also includes forming a dielectric material stack above the poly-crystalline material layer. The method also includes forming, by laser ablation, a plurality of contacts holes in the dielectric material stack, each of the contact holes exposing a portion of the poly-crystalline material layer; and forming conductive contacts in the plurality of contact holes.
Solar cell contact formation using laser ablation
Harley, Gabriel; Smith, David D.; Cousins, Peter John
2014-07-22
The formation of solar cell contacts using a laser is described. A method of fabricating a back-contact solar cell includes forming a poly-crystalline material layer above a single-crystalline substrate. The method also includes forming a dielectric material stack above the poly-crystalline material layer. The method also includes forming, by laser ablation, a plurality of contacts holes in the dielectric material stack, each of the contact holes exposing a portion of the poly-crystalline materiat layer; and forming conductive contacts in the plurality of contact holes.
McCloy, John S; Riley, Brian J; Goel, Ashutosh; Liezers, Martin; Schweiger, Michael J; Rodriguez, Carmen P; Hrma, Pavel; Kim, Dong-Sang; Lukens, Wayne W; Kruger, Albert A
2012-11-20
The immobilization of technetium-99 ((99)Tc) in a suitable host matrix has proven to be a challenging task for researchers in the nuclear waste community around the world. In this context, the present work reports on the solubility and retention of rhenium, a nonradioactive surrogate for (99)Tc, in a sodium borosilicate glass. Glasses containing target Re concentrations from 0 to 10,000 ppm [by mass, added as KReO(4) (Re(7+))] were synthesized in vacuum-sealed quartz ampules to minimize the loss of Re from volatilization during melting at 1000 °C. The rhenium was found as Re(7+) in all of the glasses as observed by X-ray absorption near-edge structure. The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) using inductively coupled plasma optical emission spectroscopy. At higher rhenium concentrations, additional rhenium was retained in the glasses as crystalline inclusions of alkali perrhenates detected with X-ray diffraction. Since (99)Tc concentrations in a glass waste form are predicted to be <10 ppm (by mass), these Re results implied that the solubility should not be a limiting factor in processing radioactive wastes, assuming Tc as Tc(7+) and similarities between Re(7+) and Tc(7+) behavior in this glass system.
Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site ...
DOE Office of Scientific and Technical Information (OSTI.GOV)
Martin, K.B.
1999-12-08
This study examined the ion exchange capacity of crystalline silicotitanate in a simulated waste solution. The focus areas included the effect of temperature and radiation on cesium sorption capacity. The cesium is expected to be removed from high-level radioactive wastes using these ion exchange materials.
Generic repository design concepts and thermal analysis (FY11).
DOE Office of Scientific and Technical Information (OSTI.GOV)
Howard, Robert; Dupont, Mark; Blink, James A.
2011-08-01
Reference concepts for geologic disposal of used nuclear fuel and high-level radioactive waste in the U.S. are developed, including geologic settings and engineered barriers. Repository thermal analysis is demonstrated for a range of waste types from projected future, advanced nuclear fuel cycles. The results show significant differences among geologic media considered (clay/shale, crystalline rock, salt), and also that waste package size and waste loading must be limited to meet targeted maximum temperature values. In this study, the UFD R&D Campaign has developed a set of reference geologic disposal concepts for a range of waste types that could potentially be generatedmore » in advanced nuclear FCs. A disposal concept consists of three components: waste inventory, geologic setting, and concept of operations. Mature repository concepts have been developed in other countries for disposal of spent LWR fuel and HLW from reprocessing UNF, and these serve as starting points for developing this set. Additional design details and EBS concepts will be considered as the reference disposal concepts evolve. The waste inventory considered in this study includes: (1) direct disposal of SNF from the LWR fleet, including Gen III+ advanced LWRs being developed through the Nuclear Power 2010 Program, operating in a once-through cycle; (2) waste generated from reprocessing of LWR UOX UNF to recover U and Pu, and subsequent direct disposal of used Pu-MOX fuel (also used in LWRs) in a modified-open cycle; and (3) waste generated by continuous recycling of metal fuel from fast reactors operating in a TRU burner configuration, with additional TRU material input supplied from reprocessing of LWR UOX fuel. The geologic setting provides the natural barriers, and establishes the boundary conditions for performance of engineered barriers. The composition and physical properties of the host medium dictate design and construction approaches, and determine hydrologic and thermal responses of the disposal system. Clay/shale, salt, and crystalline rock media are selected as the basis for reference mined geologic disposal concepts in this study, consistent with advanced international repository programs, and previous investigations in the U.S. The U.S. pursued deep geologic disposal programs in crystalline rock, shale, salt, and volcanic rock in the years leading up to the Nuclear Waste Policy Act, or NWPA (Rechard et al. 2011). The 1987 NWPA amendment act focused the U.S. program on unsaturated, volcanic rock at the Yucca Mountain site, culminating in the 2008 license application. Additional work on unsaturated, crystalline rock settings (e.g., volcanic tuff) is not required to support this generic study. Reference disposal concepts are selected for the media listed above and for deep borehole disposal, drawing from recent work in the U.S. and internationally. The main features of the repository concepts are discussed in Section 4.5 and summarized in Table ES-1. Temperature histories at the waste package surface and a specified distance into the host rock are calculated for combinations of waste types and reference disposal concepts, specifying waste package emplacement modes. Target maximum waste package surface temperatures are identified, enabling a sensitivity study to inform the tradeoff between the quantity of waste per disposal package, and decay storage duration, with respect to peak temperature at the waste package surface. For surface storage duration on the order of 100 years or less, waste package sizes for direct disposal of SNF are effectively limited to 4-PWR configurations (or equivalent size and output). Thermal results are summarized, along with recommendations for follow-on work including adding additional reference concepts, verification and uncertainty analysis for thermal calculations, developing descriptions of surface facilities and other system details, and cost estimation to support system-level evaluations.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ma, Dongyang; Wang, Zhendong; Guo, Min
2014-11-15
Highlights: • Concept to convert waste to valuable product is carried out in this study. • An industrially feasible and cost-effective approach was developed and optimized. • Highly crystalline and well-defined zeolite was produced under moderate conditions. • The zeolite derived from the bauxite tailings displayed high ion exchange capacity. • Bauxite tailings have potential application in heavy metal ions adsorbent. - Abstract: Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceivedmore » and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO{sub 3}/g, comparable to commercially-available zeolite (310 mg CaCO{sub 3}/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena
2014-09-24
The thermotropic and lyotropic liquid crystalline phase behaviour of a series of diethanolamide amphiphiles with isoprenoid-type hydrocarbon chains (geranoyl, H-farnesoyl, and phytanoyl) has been investigated. When neat, both H-farnesoyl and phytanoyl diethanolamide form a smectic liquid crystalline structure at sub-zero temperatures. In addition, all three diethanolamides exhibit a glass transition temperature at around -73 C. Geranoyl diethanolamide forms a lamellar crystalline phase with a lattice parameter of 17.4 {angstrom} following long term storage accompanied by the loss of the glass transition. In the presence of water, H-farnesoyl and phytanoyl diethanolamide form lyotropic liquid crystalline phases, whilst geranoyl diethanolamide forms anmore » L{sub 2} phase. H-farnesoyl diethanolamide forms a fluid lamellar phase (L{sub {alpha}}) at room temperature and up to {approx} 40 C. Phytanoyl diethanolamide displays a rich mesomorphism forming the inverse diamond (Q{sub II}{sup D}) and gyroid (Q{sub II}{sup G}) bicontinuous cubic phases in addition to an L{sub {alpha}} phase.« less
Reconditioning perovskite films in vapor environments through repeated cation doping
NASA Astrophysics Data System (ADS)
Boonthum, Chirapa; Pinsuwan, Kusuma; Ponchai, Jitprabhat; Srikhirin, Toemsak; Kanjanaboos, Pongsakorn
2018-06-01
Perovskites have attracted considerable attention for application as high-efficiency photovoltaic devices owing to their low-cost and low-temperature fabrication. A good surface and high crystallinity are necessary for high-performance devices. We examine the negative effects of chemical ambiences on the perovskite crystal formation and morphology. The repeated cation doping (RCD) technique was developed to remedy these issues by gradually dropping methylammonium ions on top of about-to-form perovskite surfaces to cause recrystallization. RCD promotes pinhole-free, compact, and polygonal-like surfaces under various vapor conditions. Furthermore, it enhances the electronic properties and crystallization. The benefits of RCD extend beyond perovskites under vapor ambiences, as it can improve regular and wasted perovskites.
Kim, Miae; Corkhill, Claire L; Hyatt, Neil C; Heo, Jong
2018-03-28
Calcium-aluminoborate (CAB) glasses were developed to sequester new waste compositions made of several rare-earth oxides generated from the pyrochemical reprocessing of spent nuclear fuel. Several important wasteform properties such as waste loading, processability and chemical durability were evaluated. The maximum waste loading of the CAB compositions was determined to be ~56.8 wt%. Viscosity and the electrical conductivity of the CAB melt at 1300 °C were 7.817 Pa·s and 0.4603 S/cm, respectively, which satisfies the conditions for commercial cold-crucible induction melting (CCIM) process. Addition of rare-earth oxides to CAB glasses resulted in dramatic decreases in the elemental releases of B and Ca in aqueous dissolution experiments. Normalized elemental releases from product consistency standard chemical durability test were <3.62·10 -5 g·m -2 for Nd, 0.009 g·m -2 for Al, 0.067 g·m -2 for B and 0.073 g·m -2 for Ca (at 90, after 7 days, for SA/V = 2000m -1 ); all meet European and US regulation limits. After 20 d of dissolution, a hydrated alteration layer of ~ 200-nm-thick, Ca-depleted and Nd-rich, was formed at the surface of CAB glasses with 20 mol% Nd 2 O 3 whereas boehmite [AlO(OH)] secondary crystalline phases were formed in pure CAB glass that contained no Nd 2 O 3 .
Residual waste from Hanford tanks 241-C-203 and 241-C-204. 1. Solids characterization.
Krupka, Kenneth M; Schaef, Herbert T; Arey, Bruce W; Heald, Steve M; Deutsch, William I; Lindberg, Michael J; Cantrell, Kirk J
2006-06-15
Bulk X-ray diffraction (XRD), synchrotron X-ray microdiffraction (microXRD), and scanning electron microscopy/ energy-dispersive X-ray spectroscopy (SEM/EDS) were used to characterize solids in residual sludge from single-shell underground waste tanks C-203 and C-204 at the U.S. Department of Energy's Hanford Site in southeastern Washington state. Cejkaite [Na4(UO2)(CO3)3] was the dominant crystalline phase in the C-203 and C-204 sludges. This is one of the few occurrences of cejkaite reported in the literature and may be the first documented occurrence of this phase in radioactive wastes from DOE sites. Characterization of residual solids from water leach and selective extraction tests indicates that cejkaite has a high solubility and a rapid rate of dissolution in water at ambient temperature and that these sludges may also contain poorly crystalline Na2U207 [or clarkeite Na[(UO2)O(OH)](H2O)0-1] as well as nitratine (soda niter, NaNO3), goethite [alpha-FeO(OH)], and maghemite (gamma-Fe2O3). Results of the SEM/EDS analyses indicate that the C-204 sludge also contains a solid that lacks crystalline form and is composed of Na, Al, P, O, and possibly C. Other identified solids include Fe oxides that often also contain Cr and Ni and occur as individual particles, coatings on particles, and botryoidal aggregates; a porous-looking material (or an aggregate of submicrometer particles) that typically contain Al, Cr, Fe, Na, Ni, Si, U, P, O, and C; Si oxide (probably quartz); and Na-Al silicate(s). The latter two solids probably represent minerals from the Hanford sediment, which were introduced into the tank during prior sampling campaigns or other tank operation activities. The surfaces of some Fe-oxide particles in residual solids from the water leach and selective extraction tests appear to have preferential dissolution cavities. If these Fe oxides contain contaminants of concern, then the release of these contaminants into infiltrating water would be limited by the dissolution rates of these Fe oxides, which in general have lowto very low solubilities and slow dissolution rates at near neutral to basic pH values under oxic conditions.
Deep Borehole Disposal Concept: Development of Universal Canister Concept of Operations
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rigali, Mark J.; Price, Laura L.
This report documents key elements of the conceptual design for deep borehole disposal of radioactive waste to support the development of a universal canister concept of operations. A universal canister is a canister that is designed to be able to store, transport, and dispose of radioactive waste without the canister having to be reopened to treat or repackage the waste. This report focuses on the conceptual design for disposal of radioactive waste contained in a universal canister in a deep borehole. The general deep borehole disposal concept consists of drilling a borehole into crystalline basement rock to a depth ofmore » about 5 km, emplacing WPs in the lower 2 km of the borehole, and sealing and plugging the upper 3 km. Research and development programs for deep borehole disposal have been ongoing for several years in the United States and the United Kingdom; these studies have shown that deep borehole disposal of radioactive waste could be safe, cost effective, and technically feasible. The design concepts described in this report are workable solutions based on expert judgment, and are intended to guide follow-on design activities. Both preclosure and postclosure safety were considered in the development of the reference design concept. The requirements and assumptions that form the basis for the deep borehole disposal concept include WP performance requirements, radiological protection requirements, surface handling and transport requirements, and emplacement requirements. The key features of the reference disposal concept include borehole drilling and construction concepts, WP designs, and waste handling and emplacement concepts. These features are supported by engineering analyses.« less
Thermodynamics of rock forming crystalline solutions
NASA Technical Reports Server (NTRS)
Saxena, S. K.
1971-01-01
Analysis of phase diagrams and cation distributions within crystalline solutions as means of obtaining thermodynamic data on rock forming crystalline solutions is discussed along with some aspects of partitioning of elements in coexisting phases. Crystalline solutions, components in a silicate mineral, and chemical potentials of these components were defined. Examples were given for calculating thermodynamic mixing functions in the CaW04-SrW04, olivine-chloride solution, and orthopyroxene systems.
Nuclear Waste Disposal and Strategies for Predicting Long-Term Performance of Material
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wicks, G G
2001-03-28
Ceramics have been an important part of the nuclear community for many years. On December 2, 1942, an historic event occurred under the West Stands of Stagg Field, at the University of Chicago. Man initiated his first self-sustaining nuclear chain reaction and controlled it. The impact of this event on civilization is considered by many as monumental and compared by some to other significant events in history, such as the invention of the steam engine and the manufacturing of the first automobile. Making this event possible and the successful operation of this first man-made nuclear reactor, was the use ofmore » forty tons of UO2. The use of natural or enriched UO2 is still used today as a nuclear fuel in many nuclear power plants operating world-wide. Other ceramic materials, such as 238Pu, are used for other important purposes, such as ceramic fuels for space exploration to provide electrical power to operate instruments on board spacecrafts. Radioisotopic Thermoelectric Generators (RTGs) are used to supply electrical power and consist of a nuclear heat source and converter to transform heat energy from radioactive decay into electrical power, thus providing reliable and relatively uniform power over the very long lifetime of a mission. These sources have been used in the Galileo spacecraft orbiting Jupiter and for scientific investigations of Saturn with the Cassini spacecraft. Still another very important series of applications using the unique properties of ceramics in the nuclear field, are as immobilization matrices for management of some of the most hazardous wastes known to man. For example, in long-term management of radioactive and hazardous wastes, glass matrices are currently in production immobilizing high-level radioactive materials, and cementious forms have also been produced to incorporate low level wastes. Also, as part of nuclear disarmament activities, assemblages of crystalline phases are being developed for immobilizing weapons grade plutonium, to not only produce environmentally friendly products, but also forms that are proliferation resistant. All of these waste forms as well as others, are designed to take advantage of the unique properties of the ceramic systems.« less
Similar local order in disordered fluorite and aperiodic pyrochlore structures
Shamblin, Jacob; Tracy, Cameron; Palomares, Raul; ...
2017-10-01
A major challenge to understanding the response of materials to extreme environments (e.g., nuclear fuels/waste forms and fusion materials) is to unravel the processes by which a material can incorporate atomic-scale disorder, and at the same time, remain crystalline. While it has long been known that all condensed matter, even liquids and glasses, possess short-range order, the relation between fully-ordered, disordered, and aperiodic structures over multiple length scales is not well understood. For example, when defects are introduced (via pressure or irradiation) into materials adopting the pyrochlore structure, these complex oxides either disorder over specific crystallographic sites, remaining crystalline, ormore » become aperiodic. Here we present neutron total scattering results characterizing the irradiation response of two pyrochlores, one that is known to disorder (Er2Sn2O7) and the other to amorphize (Dy2Sn2O7) under ion irradiation. The results demonstrate that in both cases, the local pyrochlore structure is transformed into similar short range configurations that are best fit by the orthorhombic weberite structure, even though the two compositions have distinctly different structures, aperiodic vs. disordered-crystalline, at longer length scales. Thus, a material's resistance to amorphization may not depend primarily on local defect formation energies, but rather on the structure's compatibility with meso-scale modulations of the local order in a way that maintains long-range periodicity.« less
(Note: This entry is no longer valid; the paper was rewritten and submitted to a different journal.) This paper highlights some methods that can be used at a local scale to assess whether waste disposal activities are responsible for enhanced arsenic mobility through redox-contro...
Nanocrystallography measurements of early stage synthetic malaria pigment
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dilanian, Ruben A.; Streltsov, Victor; Coughlan, Hannah D.
The recent availability of extremely intense, femtosecond X-ray free-electron laser (XFEL) sources has spurred the development of serial femtosecond nanocrystallography (SFX). Here, SFX is used to analyze nanoscale crystals of β-hematin, the synthetic form of hemozoin which is a waste by-product of the malaria parasite. This analysis reveals significant differences in β-hematin data collected during SFX and synchrotron crystallography experiments. To interpret these differences two possibilities are considered: structural differences between the nanocrystal and larger crystalline forms of β-hematin, and radiation damage. Simulation studies show that structural inhomogeneity appears at present to provide a better fit to the experimental data.more » If confirmed, these observations will have implications for designing compounds that inhibit hemozoin formation and suggest that, for some systems at least, additional information may be gained by comparing structures obtained from nanocrystals and macroscopic crystals of the same molecule.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dilanian, Ruben A.; Streltsov, Victor; Coughlan, Hannah D.
The recent availability of extremely intense, femtosecond X-ray free-electron laser (XFEL) sources has spurred the development of serial femtosecond nanocrystallography (SFX). Here, SFX is used to analyze nanoscale crystals of β-hematin, the synthetic form of hemozoin which is a waste by-product of the malaria parasite. This analysis reveals significant differences in β-hematin data collected during SFX and synchrotron crystallography experiments. To interpret these differences two possibilities are considered: structural differences between the nanocrystal and larger crystalline forms of β-hematin, and radiation damage. Simulation studies show that structural inhomogeneity appears at present to provide a better fit to the experimental data.more » If confirmed, these observations will have implications for designing compounds that inhibit hemozoin formation and suggest that, for some systems at least, additional information may be gained by comparing structures obtained from nanocrystals and macroscopic crystals of the same molecule.« less
Nanocrystallography measurements of early stage synthetic malaria pigment
Dilanian, Ruben A.; Streltsov, Victor; Coughlan, Hannah D.; ...
2017-09-28
The recent availability of extremely intense, femtosecond X-ray free-electron laser (XFEL) sources has spurred the development of serial femtosecond nanocrystallography (SFX). Here, SFX is used to analyze nanoscale crystals of β-hematin, the synthetic form of hemozoin which is a waste by-product of the malaria parasite. This analysis reveals significant differences in β-hematin data collected during SFX and synchrotron crystallography experiments. To interpret these differences two possibilities are considered: structural differences between the nanocrystal and larger crystalline forms of β-hematin, and radiation damage. Simulation studies show that structural inhomogeneity appears at present to provide a better fit to the experimental data.more » If confirmed, these observations will have implications for designing compounds that inhibit hemozoin formation and suggest that, for some systems at least, additional information may be gained by comparing structures obtained from nanocrystals and macroscopic crystals of the same molecule.« less
Iuraş, Andreea; Scurr, David J; Boissier, Catherine; Nicholas, Mark L; Roberts, Clive J; Alexander, Morgan R
2016-04-05
The structure of a material, in particular the extremes of crystalline and amorphous forms, significantly impacts material performance in numerous sectors such as semiconductors, energy storage, and pharmaceutical products, which are investigated in this paper. To characterize the spatial distribution for crystalline-amorphous forms at the uppermost molecular surface layer, we performed time-of-flight secondary-ion mass spectroscopy (ToF-SIMS) measurements for quench-cooled amorphous and recrystallized samples of the drugs indomethacin, felodipine, and acetaminophen. Polarized light microscopy was used to localize crystallinity induced in the samples under controlled conditions. Principal component analysis was used to identify the subtle changes in the ToF-SIMS spectra indicative of the amorphous and crystalline forms for each drug. The indicators of amorphous and crystalline surfaces were common in type across the three drugs, and could be explained in general terms of crystal packing and intermolecular bonding, leading to intramolecular bond scission in the formation of secondary ions. Less intramolecular scission occurred in the amorphous form, resulting in a greater intensity of molecular and dimer secondary ions. To test the generality of amorphous-crystalline differentiation using ToF-SIMS, a different recrystallization method was investigated where acetaminophen single crystals were recrystallized from supersaturated solutions. The findings indicated that the ability to assign the crystalline/amorphous state of the sample using ToF-SIMS was insensitive to the recrystallization method. This demonstrates that ToF-SIMS is capable of detecting and mapping ordered crystalline and disordered amorphous molecular materials forms at micron spatial resolution in the uppermost surface of a material.
Uyama, Makoto; Araki, Hidefumi; Fukuhara, Tadao; Watanabe, Kei
2018-06-07
The α-form hydrated crystalline phase (often called as an α-gel) is one of the hydrated crystalline phases which can be exhibited by surfactants and lipids. In this study, a novel system of an α-form hydrated crystal was developed, composed of 3-(10-carboxydecyl)-1,1,1,3,5,5,5-heptamethyl trisiloxane (CDTS), polyoxyethylene (5 mol) glyceryl monostearate (GMS-5), higher alcohol. This is the first report to indicate that a silicone surfactant can form an α-form hydrated crystal. The physicochemical properties of this system were characterized by small and wide angle X-ray scattering (SWAXS), differential scanning calorimetry (DSC), and diffusion-ordered NMR spectroscopy (DOSY) experiments. SWAXS and DSC measurements revealed that a plurality of crystalline phases coexist in the CDTS/higher alcohol/water ternary system. By adding GMS-5 to the ternary system, however, a wide region of a single α-form hydrated crystalline phase was obtained. The self-diffusion coefficients (D sel ) from the NMR measurements suggested that all of the CDTS, GMS-5, and higher alcohol molecules were incorporated into the same α-form hydrated crystals.
Densified waste form and method for forming
Garino, Terry J.; Nenoff, Tina M.; Sava Gallis, Dorina Florentina
2015-08-25
Materials and methods of making densified waste forms for temperature sensitive waste material, such as nuclear waste, formed with low temperature processing using metallic powder that forms the matrix that encapsulates the temperature sensitive waste material. The densified waste form includes a temperature sensitive waste material in a physically densified matrix, the matrix is a compacted metallic powder. The method for forming the densified waste form includes mixing a metallic powder and a temperature sensitive waste material to form a waste form precursor. The waste form precursor is compacted with sufficient pressure to densify the waste precursor and encapsulate the temperature sensitive waste material in a physically densified matrix.
Methods of forming hardened surfaces
Branagan, Daniel J [Iona, ID
2004-07-27
The invention encompasses a method of forming a metallic coating. A metallic glass coating is formed over a metallic substrate. After formation of the coating, at least a portion of the metallic glass can be converted into a crystalline material having a nanocrystalline grain size. The invention also encompasses metallic coatings comprising metallic glass. Additionally, the invention encompasses metallic coatings comprising crystalline metallic material, with at least some of the crystalline metallic material having a nanocrystalline grain size.
Crystal forms of the hydrogen oxalate salt of o-desmethylvenlafaxine.
Dichiarante, Elena; Curzi, Marco; Giaffreda, Stefano L; Grepioni, Fabrizia; Maini, Lucia; Braga, Dario
2015-06-01
To prepare new crystalline forms of the antidepressant o-desmethylvenlafaxine salt as potential new commercial forms and evaluate their physicochemical properties, in particular the dissolution rate. A new hydrogen oxalate salt of o-desmethylvenlafaxine hydrogen oxalate (ODV-OX) was synthesized, and a polymorph screening was performed using different solvents and crystallization conditions. Crystalline forms were characterized by a combination of solid-state techniques: X-ray powder diffraction, differential scanning calorimetry, thermogravimetric analysis, FT-IR spectroscopy and single crystal X-ray diffraction. The stability of all crystalline phases was tested under International Conference on Harmonisation (ICH) conditions (40°C and 75% Relative Humidity (RH)) for 1 week. Dissolution tests were performed on the hydrogen oxalate salt ODV-OX Form 1 and compared with dissolution test on the commercial form of the succinate salt of o-desmethylvenlafaxine. Five crystalline forms of ODV-OX were isolated, namely three hydrated forms (Form 1, Form 2, Form 3) and two anhydrous forms (Form 4 and Form 5). Comparative solubility tests on ODV-OX Form 1 and o-desmethylvenlafaxine succinate evidenced a significant increase in solubility for the hydrogen oxalate salt (142 g/l) with respect to the succinate salt (70 g/l). © 2015 Royal Pharmaceutical Society.
NASA Astrophysics Data System (ADS)
Collins, Mary Kayla; Anctil, Annick
2017-07-01
The appropriateness of regulatory methods to characterise the toxicity of photovoltaic (PV) modules was investigated to quantify potential environmental impacts for modules disposed of in landfills. Because solar energy is perceived as a green technology, it is important to ensure that end-of-life issues will not be detrimental to solar energy's success. United States Environmental Protection Agency Method 1311, California waste extraction test, and modified versions of both were performed on a multi-crystalline silicon module and cells and a copper indium gallium diselenide (CIGS) module. Variations in metal leachate concentrations were found with changes in testing parameters. Lead concentrations from the multi-crystalline module ranged from 16.2 to 50.2 mg/L. Cadmium concentrations from the CIGS module ranged from 0.1 to 3.52 mg/L. This raises doubt that regulatory methods can adequately characterise PV modules. The results are useful for developing end-of-life procedures, which is a positive step towards avoiding an e-waste problem and continuing trends of increasing installation and cost reduction in the PV market.
Reuse of hazardous calcium fluoride sludge from the integrated circuit industry.
Zhu, Ping; Cao, Zhenbang; Ye, YiLi; Qian, Guangren; Lu, Bo; Zhou, Ming; Zhou, Jin
2013-11-01
The Chinese integrated circuit industry has been transformed from a small state-owned sector into a global competitor, but chip manufacturing produces large amounts of calcium fluoride sludges (CFS). In China, landfill is a current option for treating CFS. In order to solve the problem of unavailable landfill sites and prevent fluorine from dissolved CFS polluting water sources, CFS was tested as a component for a ceramic product made with sodium borate, sodium phosphate and waste alumina using a low-temperature sintering technology, and the effects of various factors on characteristics of the ceramic were investigated to optimize the process. The best sintering temperature was controlled at 700°C, and the optimal raw material ratio of the ceramic was 11% sodium borate, 54% sodium phosphate, 30% CFS and 5% waste alumina. The CFS ceramic was characterized by a morphological structure and X-ray diffraction. The results indicated that CFS was transformed into Na2Ca(PO4)F as an inert and a main crystalline phase in the ceramic, which was enclosed by the borophosphate glass. Toxicity characteristic leaching procedure, corrosion resistance and compressive strength tests verified CFS ceramic as a qualified construction ceramic material, and the fluorine from CFS was solidified in the inert crystalline phase, which would not be released to cause secondary pollution. This novel technology not only avoids the CFS hydrolyzing reaction forming harmful hydrofluoric acid gas at 800°C and above, but also produces high-performance ceramics as a construction material, in accordance with the concept of sustainable development.
Densified waste form and method for forming
DOE Office of Scientific and Technical Information (OSTI.GOV)
Garino, Terry J.; Nenoff, Tina M.; Sava Gallis, Dorina Florentina
Materials and methods of making densified waste forms for temperature sensitive waste material, such as nuclear waste, formed with low temperature processing using metallic powder that forms the matrix that encapsulates the temperature sensitive waste material. The densified waste form includes a temperature sensitive waste material in a physically densified matrix, the matrix is a compacted metallic powder. The method for forming the densified waste form includes mixing a metallic powder and a temperature sensitive waste material to form a waste form precursor. The waste form precursor is compacted with sufficient pressure to densify the waste precursor and encapsulate themore » temperature sensitive waste material in a physically densified matrix.« less
High Level Waste System Impacts from Small Column Ion Exchange Implementation
DOE Office of Scientific and Technical Information (OSTI.GOV)
McCabe, D. J.; Hamm, L. L.; Aleman, S. E.
2005-08-18
The objective of this task is to identify potential waste streams that could be treated with the Small Column Ion Exchange (SCIX) and perform an initial assessment of the impact of doing so on the High-Level Waste (HLW) system. Design of the SCIX system has been performed as a backup technology for decontamination of High-Level Waste (HLW) at the Savannah River Site (SRS). The SCIX consists of three modules which can be placed in risers inside underground HLW storage tanks. The pump and filter module and the ion exchange module are used to filter and decontaminate the aqueous tank wastesmore » for disposition in Saltstone. The ion exchange module contains Crystalline Silicotitanate (CST in its engineered granular form is referred to as IONSIV{reg_sign} IE-911), and is selective for removal of cesium ions. After the IE-911 is loaded with Cs-137, it is removed and the column is refilled with a fresh batch. The grinder module is used to size-reduce the cesium-loaded IE-911 to make it compatible with the sludge vitrification system in the Defense Waste Processing Facility (DWPF). If installed at the SRS, this SCIX would need to operate within the current constraints of the larger HLW storage, retrieval, treatment, and disposal system. Although the equipment has been physically designed to comply with system requirements, there is also a need to identify which waste streams could be treated, how it could be implemented in the tank farms, and when this system could be incorporated into the HLW flowsheet and planning. This document summarizes a preliminary examination of the tentative HLW retrieval plans, facility schedules, decontamination factor targets, and vitrified waste form compatibility, with recommendations for a more detailed study later. The examination was based upon four batches of salt solution from the currently planned disposition pathway to treatment in the SCIX. Because of differences in capabilities between the SRS baseline and SCIX, these four batches were combined into three batches for a total of about 3.2 million gallons of liquid waste. The chemical and radiological composition of these batches was estimated from the SpaceMan Plus{trademark} model using the same data set and assumptions as the baseline plans.« less
Method for forming a hardened surface on a substrate
Branagan, Daniel J [Iona, ID
2008-01-29
The invention encompasses a method of forming a metallic coating. A metallic glass coating is formed over a metallic substrate. After formation of the coating, at least a portion of the metallic glass can be converted into a crystalline material having a nanocrystalline grain size. The invention also encompasses metallic coatings comprising metallic glass. Additionally, the invention encompasses metallic coatings comprising crystalline metallic material, with at least some of the crystalline metallic material having a nanocrystalline grain size.
Synthesis of Zeolite-X from Bottom Ash for H2 Adsorption
NASA Astrophysics Data System (ADS)
Kurniawan, R. Y.; Romadiansyah, T. Q.; Tsamarah, A. D.; Widiastuti, N.
2018-01-01
Zeolite-X was synthesized from bottom ash power plant waste using fusion method on air atmosphere. The fused product dissolved in demineralized water and aluminate solution was added to adjust the SiO2/Al2O3 molar ratio gel prior hydrothermal process. The synthesis results were characterized using X-Ray Diffraction (XRD), Scanning Electron Microscope (SEM), and Fourier Transform Infrared (FTIR). The results showed that the zeolite-X has a high crystallinity with octahedral particle. The pure-form zeolite-X then was characterized and tested for H2 gas adsorption by gravimetric method to determine the H2 gas adsorption capacity of zeolite-X from bottom ash and it was compared to synthetic zeolite-X.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zheng, Z.; Gu, D.; Anthony, R.G.
1995-06-01
Polzer et al.`s method combined with Bromley`s method for estimating activity coefficients and a Langmuir isotherm for cesium in a simple simulated waste solution containing 5.1 M NaNO{sub 3} and 0.6 M NaOH was used to estimate distribution coefficients for cesium in a complex simulated waste solution characteristic of the radioactive tank wastes at Hanford and other US Department of energy sites. The ion exchange material was a hydrous sodium crystalline silicotitanate, labeled TAM-5, which is being developed by Texas A and M University, Sandia National Laboratories, and UOP Associates. Cesium distribution coefficients collected by Bray et al. on amore » NCAW simulated waste solution were predicted with deviations of less than 25% for solutions containing 1 M, 3 M, and 5 M Na{sup +} and Na:Cs ratios of 10{sup 3}--10{sup 8}. The deviations were less than 5% for the solutions with 1 M Na{sup +}. Cesium distribution coefficients were also predicted and compared with values measured by Egan et al. for TAM-5 and for a storage tank supernate and a newly generated waste solution. Excellent results were obtained for the newly generated waste simulated solution, which did not contain potassium or rubidium.The predictions for the other simulated waste solution were significantly greater than the measured values, because of the presence of large concentrations of potassium or rubidium. The effect of competitive ion exchange between Cs, Rb, and K was not included in the theory. However, the effect of competitive ion exchange between Cs, Rb, and K was not included in the theory. However, the effect of competitive exchange of Cs, Rb, and K appears to be greater for the Oak Ridge simulated waste solution than for the NCAW waste.« less
Lloyd, O.B.; Larson, J.D.; Davis, R.W.
1985-01-01
Interpretation of available hydrologic data suggests that some areas beneath the Coastal Plain in the States of Delaware, Maryland, New Jersey, North Carolina, and Virginia might have some potential for the disposal of nuclear waste in crystalline rock that is buried beneath the Coastal Plain sediments. The areas of major interest occur where the top of the basement rock lies between 1,000 and 4,000 feet below sea level, the aquifer(s) immediately above the basement rock are saturated with saline water, confining material overlies the saline water bearing aquifer(s), and groundwater flow in the saline water aquifer(s) can be established. Preliminary data on (1) the distribution and thickness of the lowermost aquifers and confining beds, (2) the distribution of hydraulic conductivity in the lowermost aquifers, (3) estimated hydraulic heads and inferred direction of lateral groundwater flow for 1980, and (4) the distribution of saline water and brine, indicate eastern parts of the study area relatively best meet most of the criteria proposed for sediments that would overlie any potential buried crystalline-rock disposal site.
Removal of Cesium From Acidic Radioactive Tank Waste Using IONSIV IE-911 (CST)
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mann, Nicholas Robert; Todd, Terry Allen
2004-10-01
IONSIV IE-911, or the engineered form of crystalline silicotitanate (CST), manufactured by UOP Molecular Sieves, has been evaluated for the removal of cesium from Idaho National Engineering and Environmental Laboratory (INEEL) acidic radioactive tank waste. A series of batch contacts and column tests were performed by using three separate batches of CST. Batch contacts were performed to evaluate the concentration effects of nitric acid, sodium, and potassium ions on cesium sorption. Additional batch tests were performed to determine if americium, mercury, and plutonium would sorb onto IONSIV IE-911. An equilibrium isotherm was generated by using a concentrated tank waste simulant.more » Column tests using a 1.5 cm 3 column and flow rates of 3, 5, 10, 20, and 30 bed volumes (BV)/hr were performed to elucidate dynamic cesium sorption capacities and sorption kinetics. Additional experiments investigated the effect of CST batch and pretreatment on cesium sorption. The thermal stability of IONSIV IE-911 was evaluated by performing thermal gravimetric analysis/differential thermal analysis. Overall, IONSIV IE-911 was shown to be effective for cesium sorption from complex, highly acidic solutions; however, sorbent stability in these solutions may have a deleterious effect on cesium sorption.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Anderson, K.K.; Collins, J.L.; Hunt, R.D.
1999-02-01
The Department of Energy (DOE) is required by law to treat and safely dispose of the radioactive wastes from its nuclear weapon production activities. The primary radionuclide in the DOE liquid wastes or supernatants is {sup 137}Cs. At the Savannah River Site (SRS), the In-Tank Precipitation (ITP) process was selected as the baseline technology to remove {sup 137}Cs from the supernatants, which are stored in underground storage tanks. In the ITP process, tetraphenylborate reacts with the water-soluble cesium to form a precipitant. The treated supernatant can then be immobilized in grout or saltstone and stored in vaults at the SRS.more » However, problems were encountered during the full-scale ITP processing. These difficulties have led to the evaluation of alternative technologies and/or concepts to the currently configured ITP process. The High-Level Waste Salt Disposition Team at the SRS is currently performing this assessment. After an initial screening of all potential alternatives, the Salt Disposition Team selected four primary options to evaluate further before the final down-selection. Crystalline silicotitanate (CST), an inorganic ion exchanger, was chosen as one of the leading alternatives. Since nearly all of the CST tests have been performed on supernatants from Hanford and Oak Ridge, the Salt Disposition Team has requested that personnel at the SRS and Oak Ridge National Laboratory (ORNL) determine the performance of the engineered form of CST, IONSIV{reg_sign} IE-911, with actual and simulated SRS supernatants.« less
Structure and thermodynamics of uranium-containing iron garnets
NASA Astrophysics Data System (ADS)
Guo, Xiaofeng; Navrotsky, Alexandra; Kukkadapu, Ravi K.; Engelhard, Mark H.; Lanzirotti, Antonio; Newville, Matthew; Ilton, Eugene S.; Sutton, Stephen R.; Xu, Hongwu
2016-09-01
Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca3UxZr2-xFe3O12 (x = 0.5-0.7), along with the endmember phase, Ca3(Zr2)SiFe3+2O12, for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in the phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe3+. U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca3UxZr2-xFe3O12 as viable waste form phases for U and other actinides.
Norman, Peter
2011-02-01
This patent application claims a novel crystalline form (Form A) of a tosylate salt of a previously disclosed neutrophil elastase inhibitor. It also claims oral compositions of the salt and a process for the preparation of the crystalline form. The novel form is indicated to show improved physical properties relative to the free base. The claimed compound is evidently one of the elastase inhibitors currently being developed by AstraZeneca.
Hybrid emitter all back contact solar cell
Loscutoff, Paul; Rim, Seung
2016-04-12
An all back contact solar cell has a hybrid emitter design. The solar cell has a thin dielectric layer formed on a backside surface of a single crystalline silicon substrate. One emitter of the solar cell is made of doped polycrystalline silicon that is formed on the thin dielectric layer. The other emitter of the solar cell is formed in the single crystalline silicon substrate and is made of doped single crystalline silicon. The solar cell includes contact holes that allow metal contacts to connect to corresponding emitters.
Lu, Ying-Yuan; Dai, Wen-Bing; Wang, Xin; Wang, Xiao-Wei; Liu, Jun-Yi; Li, Pu; Lou, Ya-Qing; Lu, Chuang; Zhang, Qiang; Zhang, Guo-Liang
2018-02-01
The objective of this study was to investigate the effect of crystalline state and a formulation of self-nanoemulsifying drug delivery system (SNEDDS) on oral bioavailability of 6-benzyl-1-benzyloxymethyl-5-iodouracil (W-1), a novel non-nucleoside reverse transcriptase inhibitor, in rats. The crystalline states of W-1 were characterized by scanning electron microscope (SEM), differential scanning calorimetry (DSC) and X-ray powder diffraction (XRPD). The SNEDDS was formulated by medium-chain lipids, characterized by droplet particle size. The plasma concentrations of W-1 were measured by high performance liquid chromatography (HPLC). The results indicated that W-1 compound were presented as crystalline forms, A and B, the degree of crystallization in form B was higher than that in form A. The SNEDDS of W-1 displayed a significant increase in the dissolution rate than W-1 powder. Furthermore, after oral administration of W-1 (100 mg/kg), the pharmacokinetic parameters of form A, form B, and W-1 SNEDDS were as follows: AUC 0-t 526.4 ± 123.5, 305.1 ± 58.5 and 2297 ± 451 ng h/mL (p < .05, when W-1 SNEDDS were compared with either form A or form B), respectively. With SNEDDS formulation, the relative bioavailabilities were enhanced by 4.36-fold and 7.53-fold over the form A and form B of W-1, respectively. In conclusion, the present results suggested that the crystalline states of W-1 might lead to the lower oral bioavailability, and SNEDDS formulation is a promising strategy of improving bioavailability, in spite of that crystalline states usually carry small lot-to-lot variability.
Haque, M Aminul
2017-04-01
Landfill solid waste management system poses the potential source of silent wide-spread heavy metals like nickel poisoning in the entire ecosystem of nearby environment. Nickel containing demolish solid wastes are disposed at landfill zones to a great extent from where nickel migrate into the food chain through the surface water body as well as groundwater. Consequently, nickel exposure may cause different environmental problems. From this sense, it may be an attractive proposal to recycle the waste as a sustainable product. Herein is presented a long-term feasibility study on potential leaching behavioral pattern of nickel from different sizes and mixes based solidified landfill waste mixed mortar block. The calculated results revealed the larger sizes block entrapped more nickel content than the smaller in relation to the available for leaching. Moreover, the specimen bearing the higher amount of waste resulted the significant nickel immobilization within the crystalline structure. The study observed the fixation results 97.72%-99.35%, 97.08%-99.11%, 96.19%-98.58% and 95.86%-91.6% under the stabilizing agent to fine aggregate mixing combination 1:1, 1:1.5, 1:2 and 1:2.5 respectively where 30% of the total volume of fine aggregate was replaced by landfill waste. Although, mechanical strength test of all surrogate waste forms was also conducted that showed acceptable performance for land disposal, the current research pointing out that constructed green products were non-hazardous except the specimens having mixture ratio 1:2.5 because nickel ion release mechanism was observed under this ratio by surface decay or physical erosion of the monolithic matrices. Furthermore, semi-empirical based dominant leaching mechanism models were justified against the goodness of fit statistical parameters for interpreting the experimental observations of nickel transport profile where the adopted models possessed strong potential for predicting Ni content with high accuracy. Copyright © 2017 Elsevier Ltd. All rights reserved.
Method of manufacturing a hybrid emitter all back contact solar cell
Loscutoff, Paul; Rim, Seung
2017-02-07
A method of manufacturing an all back contact solar cell which has a hybrid emitter design. The solar cell has a thin dielectric layer formed on a backside surface of a single crystalline silicon substrate. One emitter of the solar cell is made of doped polycrystalline silicon that is formed on the thin dielectric layer. A second emitter of the solar cell is formed in the single crystalline silicon substrate and is made of doped single crystalline silicon. The method further includes forming contact holes that allow metal contacts to connect to corresponding emitters.
Effect of Sodium Hydroxide Pretreatment of UOP IONSIV IE-911 Crystalline Silicotitanate Sorbent
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wilmarth, W.R.
2000-08-29
Use of crystalline silicotitanate (CST) to remove cesium represents one of the alternatives identified for High Level Waste pretreatment at the Savannah River Site (SRS). Previous deployment of CST in the Department of Energy complex subjected the material to mildly caustic environments. Processing of SRS waste will expose CST to very alkaline solutions for extended period of time (typically 12 months in the proposed design). Results of elevated temperature stability tests showed that silicon and one of the proprietary materials leached from the CST. UOP personnel indicated to SRS personnel that these materials exist in the sorbent in excess ofmore » required stoichiometry. The authors examined the pretreatment of CST with sodium hydroxide to remove these components prior to placing the CST in radioactive service. Additionally, researchers analyzed solids discovered in the feed line during a test by non-destructive techniques.« less
Region-to-area screening methodology for the Crystalline Repository Project
DOE Office of Scientific and Technical Information (OSTI.GOV)
None
1985-04-01
The purpose of this document is to describe the Crystalline Repository Project's (CRP) process for region-to-area screening of exposed and near-surface crystalline rock bodies in the three regions of the conterminous United States where crystalline rock is being evaluated as a potential host for the second nuclear waste repository (i.e., in the North Central, Northeastern, and Southeastern Regions). This document indicates how the US Department of Energy's (DOE) General Guidelines for the Recommendation of Sites for Nuclear Waste Repositories (10 CFR 960) were used to select and apply factors and variables for the region-to-area screening, explains how these factors andmore » variable are to be applied in the region-to-area screening, and indicates how this methodology relates to the decision process leading to the selection of candidate areas. A brief general discussion of the screening process from the national survey through area screening and site recommendation is presented. This discussion sets the scene for detailed discussions which follow concerning the region-to-area screening process, the guidance provided by the DOE Siting Guidelines for establishing disqualifying factors and variables for screening, and application of the disqualifying factors and variables in the screening process. This document is complementary to the regional geologic and environmental characterization reports to be issued in the summer of 1985 as final documents. These reports will contain the geologic and environmental data base that will be used in conjunction with the methodology to conduct region-to-area screening.« less
Secondary Waste Cast Stone Waste Form Qualification Testing Plan
DOE Office of Scientific and Technical Information (OSTI.GOV)
Westsik, Joseph H.; Serne, R. Jeffrey
2012-09-26
The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the 56 million gallons of radioactive waste stored in 177 underground tanks at the Hanford Site. The WTP includes a pretreatment facility to separate the wastes into high-level waste (HLW) and low-activity waste (LAW) fractions for vitrification and disposal. The LAW will be converted to glass for final disposal at the Integrated Disposal Facility (IDF). Cast Stone – a cementitious waste form, has been selected for solidification of this secondary waste stream after treatment in the ETF. The secondary-waste Cast Stone waste form must be acceptablemore » for disposal in the IDF. This secondary waste Cast Stone waste form qualification testing plan outlines the testing of the waste form and immobilization process to demonstrate that the Cast Stone waste form can comply with the disposal requirements. Specifications for the secondary-waste Cast Stone waste form have not been established. For this testing plan, Cast Stone specifications are derived from specifications for the immobilized LAW glass in the WTP contract, the waste acceptance criteria for the IDF, and the waste acceptance criteria in the IDF Permit issued by the State of Washington. This testing plan outlines the testing needed to demonstrate that the waste form can comply with these waste form specifications and acceptance criteria. The testing program must also demonstrate that the immobilization process can be controlled to consistently provide an acceptable waste form product. This testing plan also outlines the testing needed to provide the technical basis for understanding the long-term performance of the waste form in the disposal environment. These waste form performance data are needed to support performance assessment analyses of the long-term environmental impact of the secondary-waste Cast Stone waste form in the IDF« less
Zhang, Hao; Yang, Ying; Douglas, Jack F.
2015-01-01
Although we often think about crystalline materials in terms of highly organized arrays of atoms, molecules, or even colloidal particles, many of the important properties of this diverse class of materials relating to their catalytic behavior, thermodynamic stability, and mechanical properties derive from the dynamics and thermodynamics of their interfacial regions, which we find they have a dynamics more like glass-forming (GF) liquids than crystals at elevated temperatures. This is a general problem arising in any attempt to model the properties of naturally occurring crystalline materials since many aspects of the dynamics of glass-forming liquids remain mysterious. We examine the nature of this phenomenon in the “simple” case of the (110) interface of crystalline Ni, based on a standard embedded-atom model potential, and we then quantify the collective dynamics in this interfacial region using newly developed methods for characterizing the cooperative dynamics of glass-forming liquids. As in our former studies of the interfacial dynamics of grain-boundaries and the interfacial dynamics of crystalline Ni nanoparticles (NPs), we find that the interface of bulk crystalline Ni exhibits all the characteristics of glass-forming materials, even at temperatures well below the equilibrium crystal melting temperature, Tm. This perspective offers a new approach to modeling and engineering the properties of crystalline materials. PMID:25725748
Phase-Pure and Multiphase Ceramic Waste Forms: Microstructure Evolution and Cesium Immobilization
NASA Astrophysics Data System (ADS)
Tumurugoti, Priyatham
Efforts of this thesis are directed towards developing ceramic waste forms as a potential replacement for the conventional glass waste forms for the safe immobilization and disposal of nuclear wastes from the legacy weapons programs as well as commercial power production. The body of this work consists of two equal parts with first focused on multiphase waste form containing hollandite as major phase and the later, on single-phase hollandites for Cs incorporation. Part I: Multiphase waste forms:. Hollandite-rich multiphase waste form compositions processed by melt-solidification and spark plasma sintering (SPS) were characterized, compared, and validated for nuclear waste incorporation. Phase identification by X-ray diffraction (XRD) and electron back-scattered diffraction (EBSD) confirm hollandite as the major phase present in these samples along with perovskite, pyrochlore and zirconolite. Distribution of select elements observed by wavelength dispersive spectroscopy (WDS) maps indicate that Cs forms a secondary phase during SPS processing, which is considered undesirable. On the other hand Cs partitioned into hollandite phase in melt-processed samples. Further analysis of hollandite structure in melt-processed composition, by selected area electron diffraction (SAED), reveals ordered arrangement of tunnel ions (Ba/Cs) and vacancies, suggesting efficient Cs incorporation into the lattice. Following the microstructural analysis, the crystallization behavior of the multiphase composition during melt-processing was studied. The phase assemblage and evolution of hollandite, zirconolite, pyrochlore, and perovskite type structures during melt processing were studied using thermal analysis, in-situ XRD, and scanning electron microscopy (SEM). Samples prepared by melting followed by annealing and quenching were analyzed to determine and measure the progression of the phase assemblage. Samples were melted at 1500°C and heat-treated at crystallization temperatures of 1285°C and 1325°C corresponding to exothermic events identified from differential scanning calorimetry (DSC) measurements. Results indicate that the selected multiphase composition partially melts at 1500°C with hollandite coexisting as crystalline phase. Perovskite and zirconolite phases crystallized from the residual melt at temperatures below 1350°C. Depending on their respective thermal histories, different quenched samples were found to have different phase assemblages including phases such as perovskite, zirconolite and TiO2. Part II: Single phase waste forms. Hollandites with compositions Ba1.15-xCs2xCr 2.3Ti5.7O16 have been identified as promising lattices to host Cs. Series of compositions with 0 ≤ x ≤ 1.15 were prepared by sol-gel synthesis, characterized, and analyzed for Cs retention properties. Phase-pure hollandites adopting monoclinic symmetry (I2/m) were observed to form in the compositional range 0 ≤ x ≤ 0.4. Structural models for the compositions: x = 0, 0.15, and 0.25, were developed from Rietveld analysis of powder XRD and neutron diffraction data. Refined anisotropic displacement parameters (beta ij) for Ba and Cs ions in the hollandite tunnels indicate local disorder of Ba/Cs along the tunnel direction. In addition, weak super lattice reflections have also been observed in XRD patterns. Our data suggests the presence of supercell structures with ordered tunnel cations for the phase-pure hollandites studied. Finally, the performance of phase-pure hollandites have been evaluated qualitatively by chemical durability testing and ion-irradiation experiments. Elemental analysis of the leachants after 7-day leach tests show that Cs and Cr were extracted from the lattice together. No direct correlation between structural parameters or Cs content was observed. The simulated light-ion (He2+) and heavy-ion (Kr3+) irradiation experiments reveal that all the hollandite compositions studied undergo amorphization during alpha-decay events, and the extent of it increases with the Cs content. In summary, the present work validates melt-processing as an effective method to prepare multiphase waste forms with the desired phase assemblage. Ba1.15-xCs2xCr2.3Ti5.7O16 hollandite has been identified as an effective ceramic host for Cs immobilization and appropriate structural models for hollandites with different Cs levels have been developed. The structural information may be used to study or simulate the lattice-environment interaction.
Driscoll, Rhonda; Hageman, Phillip L.; Benzel, William M.; Diehl, Sharon F.; Adams, David T.; Morman, Suzette; Choate, LaDonna M.
2012-01-01
In this study, four randomly selected copper-bearing minerals were examined—azurite, malachite, bornite, and chalcopyrite. The objectives were to examine and enumerate the crystalline and chemical properties of each of the minerals, to determine which, if any, of the Cu-bearing minerals might adversely affect systems biota, and to provide a multi-procedure reference. Laboratory work included use of computational software for quantifying crystalline and amorphous material and optical and electron imaging instruments to model and project crystalline structures. Chemical weathering, human fluid, and enzyme simulation studies were also conducted. The analyses were conducted systematically: X-ray diffraction and microanalytical studies followed by a series of chemical, bio-leaching, and toxicity experiments.
Evolution of crystallins for a role in the vertebrate eye lens.
Slingsby, Christine; Wistow, Graeme J; Clark, Alice R
2013-04-01
The camera eye lens of vertebrates is a classic example of the re-engineering of existing protein components to fashion a new device. The bulk of the lens is formed from proteins belonging to two superfamilies, the α-crystallins and the βγ-crystallins. Tracing their ancestry may throw light on the origin of the optics of the lens. The α-crystallins belong to the ubiquitous small heat shock proteins family that plays a protective role in cellular homeostasis. They form enormous polydisperse oligomers that challenge modern biophysical methods to uncover the molecular basis of their assembly structure and chaperone-like protein binding function. It is argued that a molecular phenotype of a dynamic assembly suits a chaperone function as well as a structural role in the eye lens where the constraint of preventing protein condensation is paramount. The main cellular partners of α-crystallins, the β- and γ-crystallins, have largely been lost from the animal kingdom but the superfamily is hugely expanded in the vertebrate eye lens. Their structures show how a simple Greek key motif can evolve rapidly to form a complex array of monomers and oligomers. Apart from remaining transparent, a major role of the partnership of α-crystallins with β- and γ-crystallins in the lens is to form a refractive index gradient. Here, we show some of the structural and genetic features of these two protein superfamilies that enable the rapid creation of different assembly states, to match the rapidly changing optical needs among the various vertebrates. Copyright © 2013 The Protein Society.
Evolution of crystallins for a role in the vertebrate eye lens
Slingsby, Christine; Wistow, Graeme J; Clark, Alice R
2013-01-01
The camera eye lens of vertebrates is a classic example of the re-engineering of existing protein components to fashion a new device. The bulk of the lens is formed from proteins belonging to two superfamilies, the α-crystallins and the βγ-crystallins. Tracing their ancestry may throw light on the origin of the optics of the lens. The α-crystallins belong to the ubiquitous small heat shock proteins family that plays a protective role in cellular homeostasis. They form enormous polydisperse oligomers that challenge modern biophysical methods to uncover the molecular basis of their assembly structure and chaperone-like protein binding function. It is argued that a molecular phenotype of a dynamic assembly suits a chaperone function as well as a structural role in the eye lens where the constraint of preventing protein condensation is paramount. The main cellular partners of α-crystallins, the β- and γ-crystallins, have largely been lost from the animal kingdom but the superfamily is hugely expanded in the vertebrate eye lens. Their structures show how a simple Greek key motif can evolve rapidly to form a complex array of monomers and oligomers. Apart from remaining transparent, a major role of the partnership of α-crystallins with β- and γ-crystallins in the lens is to form a refractive index gradient. Here, we show some of the structural and genetic features of these two protein superfamilies that enable the rapid creation of different assembly states, to match the rapidly changing optical needs among the various vertebrates. PMID:23389822
Evaluation of waste mushroom logs as a potential biomass resource for the production of bioethanol.
Lee, Jae-Won; Koo, Bon-Wook; Choi, Joon-Weon; Choi, Don-Ha; Choi, In-Gyu
2008-05-01
In order to investigate the possibility of using waste mushroom logs as a biomass resource for alternative energy production, the chemical and physical characteristics of normal wood and waste mushroom logs were examined. Size reduction of normal wood (145 kW h/tone) required significantly higher energy consumption than waste mushroom logs (70 kW h/tone). The crystallinity value of waste mushroom logs was dramatically lower (33%) than normal wood (49%) after cultivation by Lentinus edodes as spawn. Lignin, an enzymatic hydrolysis inhibitor in sugar production, decreased from 21.07% to 18.78% after inoculation of L. edodes. Total sugar yields obtained by enzyme and acid hydrolysis were higher in waste mushroom logs than in normal wood. After 24h fermentation, 12 g/L ethanol was produced on waste mushroom logs, while normal wood produced 8 g/L ethanol. These results indicate that waste mushroom logs are economically suitable lignocellulosic material for the production of fermentable sugars related to bioethanol production.
NASA Astrophysics Data System (ADS)
Hadgu, T.; Kalinina, E.; Klise, K. A.; Wang, Y.
2015-12-01
Numerical modeling of disposal of nuclear waste in a deep geologic repository in fractured crystalline rock requires robust characterization of fractures. Various methods for fracture representation in granitic rocks exist. In this study we used the fracture continuum model (FCM) to characterize fractured rock for use in the simulation of flow and transport in the far field of a generic nuclear waste repository located at 500 m depth. The FCM approach is a stochastic method that maps the permeability of discrete fractures onto a regular grid. The method generates permeability fields using field observations of fracture sets. The original method described in McKenna and Reeves (2005) was designed for vertical fractures. The method has since then been extended to incorporate fully three-dimensional representations of anisotropic permeability, multiple independent fracture sets, and arbitrary fracture dips and orientations, and spatial correlation (Kalinina et al. 20012, 2014). For this study the numerical code PFLOTRAN (Lichtner et al., 2015) has been used to model flow and transport. PFLOTRAN solves a system of generally nonlinear partial differential equations describing multiphase, multicomponent and multiscale reactive flow and transport in porous materials. The code is designed to run on massively parallel computing architectures as well as workstations and laptops (e.g. Hammond et al., 2011). Benchmark tests were conducted to simulate flow and transport in a specified model domain. Distributions of fracture parameters were used to generate a selected number of realizations. For each realization, the FCM method was used to generate a permeability field of the fractured rock. The PFLOTRAN code was then used to simulate flow and transport in the domain. Simulation results and analysis are presented. The results indicate that the FCM approach is a viable method to model fractured crystalline rocks. The FCM is a computationally efficient way to generate realistic representation of complex fracture systems. This approach is of interest for nuclear waste disposal models applied over large domains.
Dias, Pablo; Javimczik, Selene; Benevit, Mariana; Veit, Hugo; Bernardes, Andréa Moura
2016-11-01
Photovoltaic modules (or panels) are important power generators with limited lifespans. The modules contain known pollutants and valuable materials such as silicon, silver, copper, aluminum and glass. Thus, recycling such waste is of great importance. To date, there have been few published studies on recycling silver from silicon photovoltaic panels, even though silicon technology represents the majority of the photovoltaic market. In this study, the extraction of silver from waste modules is justified and evaluated. It is shown that the silver content in crystalline silicon photovoltaic modules reaches 600g/t. Moreover, two methods to concentrate silver from waste modules were studied, and the use of pyrolysis was evaluated. In the first method, the modules were milled, sieved and leached in 64% nitric acid solution with 99% sodium chloride; the silver concentration yield was 94%. In the second method, photovoltaic modules were milled, sieved, subjected to pyrolysis at 500°C and leached in 64% nitric acid solution with 99% sodium chloride; the silver concentration yield was 92%. The first method is preferred as it consumes less energy and presents a higher yield of silver. This study shows that the use of pyrolysis does not assist in the extraction of silver, as the yield was similar for both methods with and without pyrolysis. Copyright © 2016 Elsevier Ltd. All rights reserved.
Ma, Dongyang; Wang, Zhendong; Guo, Min; Zhang, Mei; Liu, Jingbo
2014-11-01
Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceived and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO3/g, comparable to commercially-available zeolite (310 mg CaCO3/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China. Copyright © 2014 Elsevier Ltd. All rights reserved.
Esposito, Gennaro; Garvey, Megan; Alverdi, Vera; Pettirossi, Fabio; Corazza, Alessandra; Fogolari, Federico; Polano, Maurizio; Mangione, P. Patrizia; Giorgetti, Sofia; Stoppini, Monica; Rekas, Agata; Bellotti, Vittorio; Heck, Albert J. R.; Carver, John A.
2013-01-01
The interaction at neutral pH between wild-type and a variant form (R3A) of the amyloid fibril-forming protein β2-microglobulin (β2m) and the molecular chaperone αB-crystallin was investigated by thioflavin T fluorescence, NMR spectroscopy, and mass spectrometry. Fibril formation of R3Aβ2m was potently prevented by αB-crystallin. αB-crystallin also prevented the unfolding and nonfibrillar aggregation of R3Aβ2m. From analysis of the NMR spectra collected at various R3Aβ2m to αB-crystallin molar subunit ratios, it is concluded that the structured β-sheet core and the apical loops of R3Aβ2m interact in a nonspecific manner with the αB-crystallin. Complementary information was derived from NMR diffusion coefficient measurements of wild-type β2m at a 100-fold concentration excess with respect to αB-crystallin. Mass spectrometry acquired in the native state showed that the onset of wild-type β2m oligomerization was effectively reduced by αB-crystallin. Furthermore, and most importantly, αB-crystallin reversibly dissociated β2m oligomers formed spontaneously in aged samples. These results, coupled with our previous studies, highlight the potent effectiveness of αB-crystallin in preventing β2m aggregation at the various stages of its aggregation pathway. Our findings are highly relevant to the emerging view that molecular chaperone action is intimately involved in the prevention of in vivo amyloid fibril formation. PMID:23645685
Final environmental impact statement. Waste Isolation Pilot Plant
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
1980-10-01
This volume contains the appendices for the Final Environmental Impact Statement for the Waste Isolation Pilot Plant (WIPP). Alternative geologic environs are considered. Salt, crystalline rock, argillaceous rock, and tuff are discussed. Studies on alternate geologic regions for the siting of WIPP are reviewed. President Carter's message to Congress on the management of radioactive wastes and the findings and recommendations of the interagency review group on nuclear waste management are included. Selection criteria for the WIPP site including geologic, hydrologic, tectonic, physicochemical compatability, and socio-economic factors are presented. A description of the waste types and the waste processing procedures aremore » given. Methods used to calculate radiation doses from radionuclide releases during operation are presented. A complete description of the Los Medanos site, including archaeological and historic aspects is included. Environmental monitoring programs and long-term safety analysis program are described. (DMC)« less
Material and structural characterization of alkali activated low-calcium brown coal fly ash.
Skvára, Frantisek; Kopecký, Lubomír; Smilauer, Vít; Bittnar, Zdenek
2009-09-15
The waste low-calcium Czech brown coal fly ash represents a considerable environmental burden due to the quantities produced and the potentially high content of leachable heavy metals. The heterogeneous microstucture of the geopolymer M(n) [-(Si-O)(z)-Al-O](n).wH(2)O, that forms during the alkaline activation, was examined by means of microcalorimetry, XRD, TGA, DSC, MIP, FTIR, NMR MAS ((29)Si, (27)Al, (23)Na), ESEM, EDS, and EBSD. The leaching of heavy metals and the evolution of compressive strength were also monitored. The analysis of raw fly ash identified a number of different morphologies, unequal distribution of elements, Fe-rich rim, high internal porosity, and minor crystalline phases of mullite and quartz. Microcalorimetry revealed exothermic reactions with dependence on the activator alkalinity. The activation energy of the geopolymerization process was determined as 86.2kJ/mol. The X-ray diffraction analysis revealed no additional crystalline phases associated with geopolymer formation. Over several weeks, the (29)Si NMR spectrum testified a high degree of polymerization and Al penetration into the SiO(4) tetrahedra. The (23)Na NMR MAS spectrum hypothesized that sodium is bound in the form of Na(H(2)O)(n) rather than Na(+), thus causing efflorescence in a moisture-gradient environment. As and Cr(6+) are weakly bonded in the geopolymer matrix, while excellent immobilization of Zn(2+), Cu(2+), Cd(2+), and Cr(3+) are reported.
Thermal oxidation of single crystal aluminum antimonide and materials having the same
Sherohman, John William; Yee, Jick Hong; Coombs, III, Arthur William; Wu, Kuang Jen J.
2012-12-25
In one embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a partial vacuum atmosphere at a temperature conducive for air adsorbed molecules to desorb, surface molecule groups to decompose, and elemental Sb to evaporate from a surface of the AlSb crystal and exposing the AlSb crystal to an atmosphere comprising oxygen to form a crystalline oxide layer on the surface of the AlSb crystal. In another embodiment, a method for forming a non-conductive crystalline oxide layer on an AlSb crystal includes heat treating an AlSb crystal in a non-oxidizing atmosphere at a temperature conducive for decomposition of an amorphous oxidized surface layer and evaporation of elemental Sb from the AlSb crystal surface and forming stable oxides of Al and Sb from residual surface oxygen to form a crystalline oxide layer on the surface of the AlSb crystal.
Synthesis of YBa2CU3O7 using sub-atmospheric processing
Wiesmann, Harold; Solovyov, Vyacheslav
2004-09-21
The present invention is a method of forming thick films of crystalline YBa.sub.2 Cu.sub.3 O.sub.7 that includes forming a precursor film comprising barium fluoride (BaF.sub.2), yttrium (Y) and copper (Cu). The precursor film is heat-treated at a temperature above 500.degree. C. in the presence of oxygen, nitrogen and water vapor at sub-atmospheric pressure to form a crystalline structure. The crystalline structure is then annealed at about 500.degree. C. in the presence of oxygen to form the crystalline YBa.sub.2 Cu.sub.3 O.sub.7 film. The YBa.sub.2 Cu.sub.3 O.sub.7 film formed by this method has a resistivity of from about 100 to about 600 .mu.Ohm-cm at room temperature and a critical current density measured at 77 K in a magnetic field of 1 Tesla of about 1.0.times.10.sup.5 Ampere per square centimeter (0.1 MA/cm.sup.2) or greater.
Iron phosphate compositions for containment of hazardous metal waste
Day, Delbert E.
1998-01-01
An improved iron phosphate waste form for the vitrification, containment and long-term disposition of hazardous metal waste such as radioactive nuclear waste is provided. The waste form comprises a rigid iron phosphate matrix resulting from the cooling of a melt formed by heating a batch mixture comprising the metal waste and a matrix-forming component. The waste form comprises from about 30 to about 70 weight percent P.sub.2 O.sub.5 and from about 25 to about 50 weight percent iron oxide and has metals present in the metal waste chemically dissolved therein. The concentration of iron oxide in the waste form along with a high proportion of the iron in the waste form being present as Fe.sup.3+ provide a waste form exhibiting improved chemical resistance to corrosive attack. A method for preparing the improved iron phosphate waste forms is also provided.
Iron phosphate compositions for containment of hazardous metal waste
Day, D.E.
1998-05-12
An improved iron phosphate waste form for the vitrification, containment and long-term disposition of hazardous metal waste such as radioactive nuclear waste is provided. The waste form comprises a rigid iron phosphate matrix resulting from the cooling of a melt formed by heating a batch mixture comprising the metal waste and a matrix-forming component. The waste form comprises from about 30 to about 70 weight percent P{sub 2}O{sub 5} and from about 25 to about 50 weight percent iron oxide and has metals present in the metal waste chemically dissolved therein. The concentration of iron oxide in the waste form along with a high proportion of the iron in the waste form being present as Fe{sup 3+} provide a waste form exhibiting improved chemical resistance to corrosive attack. A method for preparing the improved iron phosphate waste forms is also provided. 21 figs.
Shiota, Kenji; Nakamura, Takafumi; Takaoka, Masaki; Aminuddin, Siti Fatimah; Oshita, Kazuyuki; Fujimori, Takashi
2017-11-01
Environmentally sound treatments are required to dispose of municipal solid waste incineration fly ash (MSWIFA) contaminated with radioactive cesium (Cs) from the Fukushima Daiichi nuclear power plant accident in Japan. This study focuses on the stabilization of Cs using an alkali-activated MSWIFA and pyophyllite-based system. Three composite solid products were synthesized after mixtures of raw materials (dehydrated pyrophyllite, MSWIFA, 14 mol/L aqueous sodium hydroxide, and sodium silicate solution) were cured at 105 °C for 24 h. Three types of MSWIFAs were prepared as raw fly ash, raw fly ash with 0.1% CsCl, and raw fly ash with 40% CsCl to understand the stabilization mechanism of Cs. Cs stabilization in two solid products was successful, with less than 6.9% leaching observed from two types tests, and was partly successful for the solid product with the highest concentration of Cs. X-ray diffraction showed that all of the solid products produced several crystalline phases, and that pollucite was formed in the highest Cs concentration product. The X-ray absorption fine structure and scanning electron microscopy with X-ray analysis suggested that most Cs species formed pollucite in the two solid products from MSWIFA with added CsCl. This system provides a technique for the direct stabilization of Cs in MSWIFA. Copyright © 2017 Elsevier Ltd. All rights reserved.
The Effect of Compaction Force on the Transition to Hydrate of Anhydrous Aripiprazole.
Togo, Taichiro; Taniguchi, Toshiya; Nakata, Yoshitaka
2018-01-01
Aripiprazole (APZ) is used to treat schizophrenia and is administered as a tablet containing the anhydrous form of APZ. In this study, the effect of compaction force on the crystal form transition was investigated. The crystalline state was observed by X-ray diffraction (XRD). APZ Anhydrous Form II was compacted into tablets. The XRD intensity of anhydrous APZ became lower with higher compressive force. The degree of crystallinity decreased with the compaction force. The powder and the compacted tablets of anhydrous APZ were stored for one week under 60°C and 75% relative humidity. The powder showed no crystal form transition after storage. For the tablets, however, XRD peaks of APZ hydrate were observed after storage. The tablets compacted with higher force showed the higher XRD diffraction intensity of hydrate form. We concluded that the crystallinity reduction of APZ Anhydrous Form II by compaction caused and accelerated the transition to hydrate under high temperature and humidity conditions. In order to manufacture crystallographically stable tablets containing anhydrous APZ, it is important to prevent this crystallinity reduction during compaction.
Method of making silicon on insalator material using oxygen implantation
Hite, Larry R.; Houston, Ted; Matloubian, Mishel
1989-01-01
The described embodiments of the present invention provide a semiconductor on insulator structure providing a semiconductor layer less susceptible to single event upset errors (SEU) due to radiation. The semiconductor layer is formed by implanting ions which form an insulating layer beneath the surface of a crystalline semiconductor substrate. The remaining crystalline semiconductor layer above the insulating layer provides nucleation sites for forming a crystalline semiconductor layer above the insulating layer. The damage caused by implantation of the ions for forming an insulating layer is left unannealed before formation of the semiconductor layer by epitaxial growth. The epitaxial layer, thus formed, provides superior characteristics for prevention of SEU errors, in that the carrier lifetime within the epitaxial layer, thus formed, is less than the carrier lifetime in epitaxial layers formed on annealed material while providing adequate semiconductor characteristics.
Engineering-Scale Demonstration of DuraLith and Ceramicrete Waste Forms
DOE Office of Scientific and Technical Information (OSTI.GOV)
Josephson, Gary B.; Westsik, Joseph H.; Pires, Richard P.
2011-09-23
To support the selection of a waste form for the liquid secondary wastes from the Hanford Waste Immobilization and Treatment Plant, Washington River Protection Solutions (WRPS) has initiated secondary waste form testing on four candidate waste forms. Two of the candidate waste forms have not been developed to scale as the more mature waste forms. This work describes engineering-scale demonstrations conducted on Ceramicrete and DuraLith candidate waste forms. Both candidate waste forms were successfully demonstrated at an engineering scale. A preliminary conceptual design could be prepared for full-scale production of the candidate waste forms. However, both waste forms are stillmore » too immature to support a detailed design. Formulations for each candidate waste form need to be developed so that the material has a longer working time after mixing the liquid and solid constituents together. Formulations optimized based on previous lab studies did not have sufficient working time to support large-scale testing. The engineering-scale testing was successfully completed using modified formulations. Further lab development and parametric studies are needed to optimize formulations with adequate working time and assess the effects of changes in raw materials and process parameters on the final product performance. Studies on effects of mixing intensity on the initial set time of the waste forms are also needed.« less
Kushida, Ikuo
2012-03-01
The objective of this study was to develop a quantitative crystallinity analysis method for the bulk drug of E1010 ((+)-(4R,5S,6S)-6-[(R)-1-hydroxyethyl]-3-[(2S,4S)-2-[(R)-1-hydroxy-1-[(R)-pyrrolidin-3 -yl]methyl]pyrrolidin-4-yl]thio-4-methyl-7-oxo-1-azabicyclo[3.2.0]hept-2-ene-2-carboxylic acid monohydrochloride), a novel carbapenem antibiotic. X-ray analyses, thermal analyses and hygroscopicity measurements were used to elucidate the crystal structure and the solid state properties. To develop a quantitative method for the crystallinity of E1010 bulk drug, the relationship between enthalpy change obtained by differential scanning calorimetry (DSC) and crystalline form ratio was investigated. E1010 bulk drug was found to exist in a crystalline trihydrate formed in two layers, i.e. a layer of E1010 free form, and a layer consisting of chloride ions and water molecules. The thermal analysis showed an endothermic peak derived from dehydration with the loss of crystal lattices at around 100°C as an onset. The enthalpy change value for the endothermic peak correlated well with crystalline content in binary physical mixtures of the crystalline trihydrate and the amorphous form. In addition, for nine lots of the bulk drug, a positive correlation between the enthalpy change and chemical stability in the solid state was observed. This quantitative analysis of crystallinity using DSC could be applicable for the quality control of the bulk drug to detect variability among manufacturing batches and to estimate the chemical stability of partially amorphous samples. © 2011 The Author. JPP © 2011 Royal Pharmaceutical Society.
Phase transformations in amorphous fullerite C60 under high pressure and high temperature
NASA Astrophysics Data System (ADS)
Borisova, P. A.; Blanter, M. S.; Brazhkin, V. V.; Somenkov, V. A.; Filonenko, V. P.
2015-08-01
First phase transformations of amorphous fullerite C60 at high temperatures (up to 1800 K) and high pressures (up to 8 GPa) have been investigated and compared with the previous studies on the crystalline fullerite. The study was conducted using neutron diffraction and Raman spectroscopy. The amorphous fullerite was obtained by ball-milling. We have shown that under thermobaric treatment no crystallization of amorphous fullerite into С60 molecular modification is observed, and it transforms into amorphous-like or crystalline graphite. A kinetic diagram of phase transformation of amorphous fullerite in temperature-pressure coordinates was constructed for the first time. Unlike in crystalline fullerite, no crystalline polymerized phases were formed under thermobaric treatment on amorphous fullerite. We found that amorphous fullerite turned out to be less resistant to thermobaric treatment, and amorphous-like or crystalline graphite were formed at lower temperatures than in crystalline fullerite.
Structure and thermodynamics of uranium-containing iron garnets
Guo, Xiaofeng; Navrotsky, Alexandra; Kukkadapu, Ravi K.; ...
2016-09-15
Use of crystalline garnet as a waste form phase appears to be advantageous for accommodating actinides from nuclear waste. Previous studies show that large amounts of uranium (U) and its analogues such as cerium (Ce) and thorium (Th) can be incorporated into the garnet structure. In this study, we synthesized U loaded garnet phases, Ca 3U xZr 2–xFe 3O 12 (x = 0.5–0.7), along with the endmember phase, Ca 3(Zr 2)SiFe 3+ 2O 12, for comparison. The oxidation states of U were determined by X-ray photoelectron and absorption spectroscopies, revealing the presence of mixed pentavalent and hexavalent uranium in themore » phases with x = 0.6 and 0.7. The oxidation states and coordination environments of Fe were measured using transmission 57Fe-Mössbauer spectroscopy, which shows that all iron is tetrahedrally coordinated Fe 3+. U substitution had a significant effect on local environments, the extent of U substitution within this range had a minimal effect on the structure, and unlike in the x = 0 sample, Fe exists in two different environments in the substituted garnets. The enthalpies of formation of garnet phases from constituent oxides and elements were first time determined by high temperature oxide melt solution calorimetry. The results indicate that these substituted garnets are thermodynamically stable under reducing conditions. Furthermore, our structural and thermodynamic analysis further provides explanation for the formation of natural uranium garnet, elbrusite-(Zr), and supports the potential use of Ca 3U xZr 2–xFe 3O 12 as viable waste form phases for U and other actinides.« less
A Proposed Borehole Scientific Laboratory in Quay County, New Mexico, USA
NASA Astrophysics Data System (ADS)
Nielson, Dennis; Eckels, Marc; Mast, Peter; Zellman, Mark; Creed, Robert
2017-04-01
Our team has received funding from the US Department of Energy to initiate a Deep Borehole Field Test that will develop a subsurface test site to evaluate the drilling and scientific aspects of deep borehole disposal of nuclear waste in crystalline rock. Phase 1 of the project will focus on Public Outreach and land acquisition whereas Phase 2 will generate a drilling and testing plan and secure regulatory approvals. Phase 3 will complete the Drilling and Testing Plan and Phase 4 will include the drilling and testing. Phase 5 will be devoted to borehole science and experiments with emplacement technology. Although we are specifically considering issues associated with the disposal of waste, this project is a proof of concept, and no waste will be emplaced at our site. In brief, the concept envisions an 8-1/2 inch open-hole completion at a depth of 5000 m in crystalline rock. There will be an extensive program of sample collection (including core) and analysis as well as geophysical logging and borehole testing. Critical issues will be low permeability in the crystalline rock as well as the ability to manage borehole quality. Our team has proposed a site in Quay County, New Mexico that has an 850 meter thick Paleozoic section overlying homogeneous Precambrian granite. A subsequent phase of the project may drill a second hole with a 17-1/2 inch completion located about 200 m from the first. Our long-term plan is that this site will be managed as a deep scientific observatory that also provides a facility for scientific experiments and testing of borehole infrastructure and drilling equipment.
NASA Astrophysics Data System (ADS)
McKisson, R. L.; Grantham, L. F.; Guon, J.; Recht, H. L.
1983-02-01
Results of an estimate of the waste management costs of the commercial high level waste from a 3000 metric ton per year reprocessing plant show that the judicious use of the ceramic waste form can save about $2 billion during a 20 year operating campaign relative to the use of the glass waste form. This assumes PWR fuel is processed and the waste is encapsulated in 0.305-m-diam canisters with ultimate emplacement in a BWIP-type horizontal-borehole repository. Waste loading and waste form density are the driving factors in that the low waste loading (25%) and relatively low density (3.1 g cu cm) characteristic of the glass form require several times as many canisters to handle a given waste throughput than is needed for the ceramic waste form whose waste loading capability exceeds 60% and whose waste density is nominally 5.2 cu cm.
Micromachined cutting blade formed from {211}-oriented silicon
Fleming, James G.; Sniegowski, Jeffry J.; Montague, Stephen
2003-09-09
A cutting blade is disclosed fabricated of micromachined silicon. The cutting blade utilizes a monocrystalline silicon substrate having a {211} crystalline orientation to form one or more cutting edges that are defined by the intersection of {211} crystalline planes of silicon with {111} crystalline planes of silicon. This results in a cutting blade which has a shallow cutting-edge angle .theta. of 19.5.degree.. The micromachined cutting blade can be formed using an anisotropic wet etching process which substantially terminates etching upon reaching the {111} crystalline planes of silicon. This allows multiple blades to be batch fabricated on a common substrate and separated for packaging and use. The micromachined cutting blade, which can be mounted to a handle in tension and optionally coated for increased wear resistance and biocompatibility, has multiple applications including eye surgery (LASIK procedure).
Micromachined cutting blade formed from {211}-oriented silicon
Fleming, James G [Albuquerque, NM; Fleming, legal representative, Carol; Sniegowski, Jeffry J [Tijeras, NM; Montague, Stephen [Albuquerque, NM
2011-08-09
A cutting blade is disclosed fabricated of micromachined silicon. The cutting blade utilizes a monocrystalline silicon substrate having a {211} crystalline orientation to form one or more cutting edges that are defined by the intersection of {211} crystalline planes of silicon with {111} crystalline planes of silicon. This results in a cutting blade which has a shallow cutting-edge angle .theta. of 19.5.degree.. The micromachined cutting blade can be formed using an anisotropic wet etching process which substantially terminates etching upon reaching the {111} crystalline planes of silicon. This allows multiple blades to be batch fabricated on a common substrate and separated for packaging and use. The micromachined cutting blade, which can be mounted to a handle in tension and optionally coated for increased wear resistance and biocompatibility, has multiple applications including eye surgery (LASIK procedure).
Liquid crystalline composites containing phyllosilicates
Chaiko,; David, J [Naperville, IL
2007-05-08
The present invention provides barrier films having reduced gas permeability for use in packaging and coating applications. The barrier films comprise an anisotropic liquid crystalline composite layer formed from phyllosilicate-polymer compositions. Phyllosilicate-polymer liquid crystalline compositions of the present invention can contain a high percentage of phyllosilicate while remaining transparent. Because of the ordering of the particles in the liquid crystalline composite, barrier films comprising liquid crystalline composites are particularly useful as barriers to gas transport.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jantzen, C. M.; Crawford, C. L.; Bannochie, C. J.
The U.S. Department of Energy’s Office of River Protection (ORP) is responsible for the retrieval, treatment, immobilization, and disposal of Hanford’s tank waste. A key aspect of the River Protection Project (RPP) cleanup mission is to construct and operate the Hanford Tank Waste Treatment and Immobilization Plant (WTP). The WTP will separate the tank waste into high-level and low-activity waste (LAW) fractions, both of which will subsequently be vitrified. The projected throughput capacity of the WTP LAW Vitrification Facility is insufficient to complete the RPP mission in the time frame required by the Hanford Federal Facility Agreement and Consent Order,more » also known as the Tri-Party Agreement (TPA), i.e. December 31, 2047. Supplemental Treatment is likely to be required both to meet the TPA treatment requirements as well as to more cost effectively complete the tank waste treatment mission. The Supplemental Treatment chosen will immobilize that portion of the retrieved LAW that is not sent to the WTP’s LAW Vitrification facility into a solidified waste form. The solidified waste will then be disposed on the Hanford site in the Integrated Disposal Facility (IDF). Fluidized Bed Steam Reforming (FBSR) offers a moderate temperature (700-750°C) continuous method by which LAW can be processed irrespective of whether the waste contain organics, nitrates, sulfates/sulfides, chlorides, fluorides, volatile radionuclides or other aqueous components. The FBSR technology can process these wastes into a crystalline ceramic (mineral) waste form. The mineral waste form that is produced by co-processing waste with kaolin clay in an FBSR process has been shown to be comparable to LAW glass, i.e. leaches Tc-99, Re and Na at <2g/m 2 during ASTM C1285 (Product Consistency) durability testing. Monolithing of the granular FBSR product was investigated to prevent dispersion during transport or burial/storage. Monolithing in an inorganic geopolymer binder, which is amorphous, macro-encapsulates the granules, and the monoliths pass ANSI/ANS 16.1 and ASTM C1308 durability testing with Re achieving a Leach Index (LI) of 9 (the Hanford Integrated Disposal Facility, IDF, criteria for Tc-99) after a few days and Na achieving an LI of >6 (the Hanford IDF criteria for Na) in the first few hours. The granular and monolithic waste forms also pass the EPA Toxicity Characteristic Leaching Procedure (TCLP) for all Resource Conservation and Recovery Act (RCRA) components at the Universal Treatment Standards (UTS). Two identical Benchscale Steam Reformers (BSR) were designed and constructed at SRNL, one to treat non-radioactive simulants and the other to treat actual radioactive wastes. The results from the non-radioactive BSR were used to determine the parameters needed to operate the radioactive BSR in order to confirm the findings of non-radioactive FBSR pilot scale and engineering scale tests and to qualify an FBSR LAW waste form for applications at Hanford. Radioactive testing commenced using SRS LAW from Tank 50 chemically trimmed to look like Hanford’s blended LAW known as the Rassat simulant as this simulant composition had been tested in the non-radioactive BSR, the non-radioactive pilot scale FBSR at the Science Applications International Corporation-Science and Technology Applications Research (SAIC-STAR) facility in Idaho Falls, ID and in the TTT Engineering Scale Technology Demonstration (ESTD) at Hazen Research Inc. (HRI) in Denver, CO. This provided a “tie back” between radioactive BSR testing and non-radioactive BSR, pilot scale, and engineering scale testing. Approximately six hundred grams of non-radioactive and radioactive BSR product were made for extensive testing and comparison to the non-radioactive pilot scale tests performed in 2004 at SAIC-STAR and the engineering scale test performed in 2008 at HRI with the Rassat simulant. The same mineral phases and off-gas species were found in the radioactive and non-radioactive testing. The granular ESTD and BSR products (radioactive and non-radioactive) were analyzed for total constituents and durability tested as a granular waste form. A subset of the granular material was stabilized in a clay based geopolymer matrix at 42% and 65% FBSR loadings and durability tested as a monolith waste form. The 65 wt% FBSR loaded monolith made with clay (radioactive) was more durable than the 67-68 wt% FBSR loaded monoliths made from fly ash (non-radioactive) based on short term PCT testing. Long term, 90 to 107 day, ASTM C1308 testing (similar to ANSI/ANS 16.1 testing) was only performed on two fly ash geopolymer monoliths at 67-68 wt% FBSR loading and three clay geopolymer monoliths at 42 wt% FBSR loading. More clay geopolymers need to be made and tested at longer times at higher FBSR loadings for comparison to the fly ash monoliths. Monoliths made with metakaolin (heat treated) clay are of a more constant composition and are very reactive as the heat treated clay is amorphous and alkali activated. The monoliths made with fly ash are subject to the inherent compositional variation found in fly ash as it is a waste product from burning coal and it contains unreactive components such as mullite. However, both the fly ash and the clay based monoliths perform well in long term ASTM C1308 testing.« less
Martino, Piera Di; Magnoni, Federico; Peregrina, Dolores Vargas; Gigliobianco, Maria Rosa; Censi, Roberta; Malaj, Ledjan
2016-01-01
Drugs and excipients used for pharmaceutical applications generally exist in the solid (crystalline or amorphous) state, more rarely as liquid materials. In some cases, according to the physicochemical nature of the molecule, or as a consequence of specific technological processes, a compound may exist exclusively in the amorphous state. In other cases, as a consequence of specific treatments (freezing and spray drying, melting and co-melting, grinding and compression), the crystalline form may convert into a completely or partially amorphous form. An amorphous material shows physical and thermodynamic properties different from the corresponding crystalline form, with profound repercussions on its technological performance and biopharmaceutical properties. Several physicochemical techniques such as X-ray powder diffraction, thermal methods of analysis, spectroscopic techniques, gravimetric techniques, and inverse gas chromatography can be applied to characterize the amorphous form of a compound (drug or excipient), and to evaluate its thermodynamic stability. This review offers a survey of the technologies used to convert a crystalline solid into an amorphous form, and describes the most important techniques for characterizing the amorphous state of compounds of pharmaceutical interest.
NASA Astrophysics Data System (ADS)
Ayoub, Muhammad; Sufian, Suriati; Mekuria Hailegiorgis, Sintayehu; Ullah, Sami; Uemura, Yoshimitsu
2017-08-01
The alkaline catalyst derived from the duck-bones was used for conversion of glycerol to polyglycerol via solvent free etherification process. The physicochemical properties of prepared materials were duck-bones were systematically investigated as a catalyst by latest techniques of Thermo gravimetric analysis (TGA), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface properties. TGA showed different trends of duck-bones decomposition from room temperature to 1000C. XRD pattern showed a clear and sharp peaks of a crystalline phase of CaO. The activity of the catalysts was in line with the basic amount of the strong base sites, surface area, and crystalline phase in the catalysts. The prepared catalyst derived from duck-bones provided high activity (99 %) for glycerol conversion and around 68 % yield for polyglycerol production. These ample wastes of duck-bones have good potential to be used as polyglycerol production catalysts due to have high quantity of Ca compare to other types of bones like cow, chicken and fish bones.
DOE Office of Scientific and Technical Information (OSTI.GOV)
McCloy, John S.; Riley, Brian J.; Goel, Ashutosh
2012-10-26
The immobilization of 99Tc in a suitable host matrix has proved to be an arduous task for the researchers in nuclear waste community around the world. At the Hanford site in Washington State, the total amount of 99Tc in low-activity waste (LAW) is ~1300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility/retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant because of the similarity between theirmore » ionic radii and other chemical aspects. The glasses containing Re (0 – 10,000 ppm by mass) were synthesized in vacuum-sealed quartz ampoules in order to minimize the loss of Re by volatilization during melting at 1000 °C. The rhenium was found to predominantly exist as Re (VII) in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be ~3000 ppm (by mass) with inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of crystalline inclusions that were detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). The implications of these results on the immobilization of 99Tc from radioactive wastes in borosilicate glasses have been discussed.« less
Stamp forming optimization for formability and crystallinity
NASA Astrophysics Data System (ADS)
Donderwinkel, T. G.; Rietman, B.; Haanappel, S. P.; Akkerman, R.
2016-10-01
The stamp forming process is well suited for high volume production of thermoplastic composite parts. The process can be characterized as highly non-isothermal as it involves local quench-cooling of a molten thermoplastic composite blank where it makes contact with colder tooling. The formability of the thermoplastic composite depends on the viscoelastic material behavior of the matrix material, which is sensitive to temperature and degree of crystallinity. An experimental study was performed to determine the effect of temperature and crystallinity on the storage modulus during cooling for a woven glass fiber polyamide-6 composite material. An increase of two decades in modulus was observed during crystallization. As this will significantly impede the blank formability, the onset of crystallization effectively governs the time available for forming. Besides the experimental work, a numerical model is developed to study the temperature and crystallinity throughout the stamp forming process. A process window can be determined by feeding the model with the experimentally obtained data on crystallization.
NASA Astrophysics Data System (ADS)
Hadgu, T.; Kalinina, E.; Klise, K. A.; Wang, Y.
2016-12-01
Disposal of high-level radioactive waste in a deep geological repository in crystalline host rock is one of the potential options for long term isolation. Characterization of the natural barrier system is an important component of the disposal option. In this study we present numerical modeling of flow and transport in fractured crystalline rock using an updated fracture continuum model (FCM). The FCM is a stochastic method that maps the permeability of discrete fractures onto a regular grid. The original method by McKenna and Reeves (2005) has been updated to provide capabilities that enhance representation of fractured rock. As reported in Hadgu et al. (2015) the method was first modified to include fully three-dimensional representations of anisotropic permeability, multiple independent fracture sets, and arbitrary fracture dips and orientations, and spatial correlation. More recently the FCM has been extended to include three different methods. (1) The Sequential Gaussian Simulation (SGSIM) method uses spatial correlation to generate fractures and define their properties for FCM (2) The ELLIPSIM method randomly generates a specified number of ellipses with properties defined by probability distributions. Each ellipse represents a single fracture. (3) Direct conversion of discrete fracture network (DFN) output. Test simulations were conducted to simulate flow and transport using ELLIPSIM and direct conversion of DFN methods. The simulations used a 1 km x 1km x 1km model domain and a structured with grid block of size of 10 m x 10m x 10m, resulting in a total of 106 grid blocks. Distributions of fracture parameters were used to generate a selected number of realizations. For each realization, the different methods were applied to generate representative permeability fields. The PFLOTRAN (Hammond et al., 2014) code was used to simulate flow and transport in the domain. Simulation results and analysis are presented. The results indicate that the FCM approach is a viable method to model fractured crystalline rocks. The FCM is a computationally efficient way to generate realistic representation of complex fracture systems. This approach is of interest for nuclear waste disposal models applied over large domains. SAND2016-7509 A
The relationship between crystalline methamphetamine use and methamphetamine dependence.
McKetin, Rebecca; Kelly, Erin; McLaren, Jennifer
2006-12-01
The aim of the current study was to determine whether crystalline methamphetamine users are more dependent on methamphetamine than people who use other forms of the drug, and if so, whether this could be accounted for by their methamphetamine use history. A structured face-to-face interview was used to assess drug use patterns and demographics among a convenience sample of 309 regular methamphetamine users from Sydney, Australia. Dependence on methamphetamine in the past year was measured using the Severity of Dependence Scale. The use of crystalline methamphetamine in the past year was confirmed using a photographic identification sheet. Participants who had used crystalline methamphetamine in the past year were significantly more likely to be dependent on methamphetamine than participants who took only other forms of methamphetamine during this time (61% versus 39%). Methamphetamine dependence was also associated with injecting or smoking methamphetamine (67% and 58%, respectively versus 30% for intranasal or oral use), using methamphetamine more than weekly (68% versus 34%), having used the drug for more than 5 years (61% versus 36%), and having used 'base' methamphetamine in the past year (59% versus 39%). Crystalline methamphetamine use remained significantly associated with methamphetamine dependence after adjusting for these patterns of methamphetamine use. Methamphetamine users who took crystalline methamphetamine in the past year were more likely to be dependent than methamphetamine users who had not taken the crystalline form of the drug during this time.
NASA Technical Reports Server (NTRS)
Tsapatsis, Michael (Inventor); Lai, Zhiping (Inventor)
2008-01-01
In certain aspects, the invention features methods for forming crystalline membranes (e.g., a membrane of a framework material, such as a zeolite) by inducing secondary growth in a layer of oriented seed crystals. The rate of growth of the seed crystals in the plane of the substrate is controlled to be comparable to the rate of growth out of the plane. As a result, a crystalline membrane can form a substantially continuous layer including grains of uniform crystallographic orientation that extend through the depth of the layer.
Method to reduce dislocation density in silicon using stress
Buonassisi, Anthony; Bertoni, Mariana; Argon, Ali; Castellanos, Sergio; Fecych, Alexandria; Powell, Douglas; Vogl, Michelle
2013-03-05
A crystalline material structure with reduced dislocation density and method of producing same is provided. The crystalline material structure is annealed at temperatures above the brittle-to-ductile transition temperature of the crystalline material structure. One or more stress elements are formed on the crystalline material structure so as to annihilate dislocations or to move them into less harmful locations.
Metastability and instability of organic crystalline substances.
Randzio, Stanislaw L; Kutner, Andrzej
2008-02-07
Discovery of an unexpected and thermodynamically paradoxical transition from a crystalline state to an amorphous dense glassy state induced in pure organic substances by a direct absorption of a quantity of heat under atmospheric pressure and its detailed analysis performed with the use of a sensitive scanning transitiometer are described. The obtained results present first experimental precise evidence for understanding the mechanism of such a structural instability of crystalline substances in the form of c-a transition. The observed c-a transition is a purely physical phenomenon, occurring between two nonequilibrium states, a metastable crystalline phase and a dense glass, occurring through a local transient phenomenon of virtual melting. The metastable state of a crystalline substance can be caused by existence of a number of crystalline imperfections created either during crystallization or by external actions. By measuring extremely sensitive energetic effects, we found the present method to be helpful for quantitative determination of the critical number of imperfections in a crystalline solid, which make it metastable and for an indication under which conditions such a metastable crystalline form becomes unstable. By performing the transitiometric analysis of c-a transitions with two polymorphs of rosiglitazone maleate, we demonstrated to what extent this analysis is important in investigation of stability of crystalline components of drugs.
Multi-crystalline II-VI based multijunction solar cells and modules
Hardin, Brian E.; Connor, Stephen T.; Groves, James R.; Peters, Craig H.
2015-06-30
Multi-crystalline group II-VI solar cells and methods for fabrication of same are disclosed herein. A multi-crystalline group II-VI solar cell includes a first photovoltaic sub-cell comprising silicon, a tunnel junction, and a multi-crystalline second photovoltaic sub-cell. A plurality of the multi-crystalline group II-VI solar cells can be interconnected to form low cost, high throughput flat panel, low light concentration, and/or medium light concentration photovoltaic modules or devices.
The mineralogy of newly formed dust in active galactic nuclei
NASA Astrophysics Data System (ADS)
Srinivasan, Sundar; Kemper, F.; Zhou, Yeyan; Hao, Lei; Gallagher, Sarah C.; Shangguan, Jinyi; Ho, Luis C.; Xie, Yanxia; Scicluna, Peter; Foucaud, Sebastien; Peng, Rita H. T.
2017-12-01
The tori around active galactic nuclei (AGN) are potential formation sites for large amounts of dust, and they may help resolve the so-called dust budget crisis at high redshift. We investigate the dust composition in 53 of the 87 Palomar Green (PG) quasars showing the 9.7 μm silicate feature in emission. By simultaneously fitting the mid-infrared spectroscopic features and the underlying continuum, we estimate the mass fraction in various amorphous and crystalline dust species. We find that the dust consists predominantly of alumina and amorphous silicates, with a small fraction in crystalline form. The mean crystallinity is 8 ±6%, with more than half of the crystallinities greater than 5%, well above the upper limit determined for the Galaxy. Higher values of crystallinity are found for higher oxide fractions and for more luminous sources.
Isolation of levoglucosan from lignocellulosic pyrolysis oil derived from wood or waste newsprint
Moens, Luc
1995-01-01
A method is provided for preparing high purity levoglucosan from lignocellulosic pyrolysis oils derived from wood or waste newsprint. The method includes reducing wood or newsprint to fine particle sizes, treating the particles with a hot mineral acid for a predetermined period of time, and filtering off and drying resulting solid wood or newsprint material; pyrolyzing the dried solid wood or newsprint material at temperatures between about 350.degree. and 375.degree. C. to produce pyrolysis oils; treating the oils to liquid-liquid extraction with methyl isobutyl ketone to remove heavy tar materials from the oils, and to provide an aqueous fraction mixture of the oils containing primarily levoglucosan; treating the aqueous fraction mixtures with a basic metal salt in an amount sufficient to elevate pH values to a range of about 12 to about 12.5 and adding an amount of the salt in excess of the amount needed to obtain the pH range to remove colored materials of impurities from the oil and form a slurry, and freeze-drying the resulting slurry to produce a dry solid residue; and extracting the levoglucosan from the residue using ethyl acetate solvent to produce a purified crystalline levoglucosan.
Isolation of levoglucosan from lignocellulosic pyrolysis oil derived from wood or waste newsprint
Moens, L.
1995-07-11
A method is provided for preparing high purity levoglucosan from lignocellulosic pyrolysis oils derived from wood or waste newsprint. The method includes reducing wood or newsprint to fine particle sizes, treating the particles with a hot mineral acid for a predetermined period of time, and filtering off and drying resulting solid wood or newsprint material; pyrolyzing the dried solid wood or newsprint material at temperatures between about 350 and 375 C to produce pyrolysis oils; treating the oils to liquid-liquid extraction with methyl isobutyl ketone to remove heavy tar materials from the oils, and to provide an aqueous fraction mixture of the oils containing primarily levoglucosan; treating the aqueous fraction mixtures with a basic metal salt in an amount sufficient to elevate pH values to a range of about 12 to about 12.5 and adding an amount of the salt in excess of the amount needed to obtain the pH range to remove colored materials of impurities from the oil and form a slurry, and freeze-drying the resulting slurry to produce a dry solid residue; and extracting the levoglucosan from the residue using ethyl acetate solvent to produce a purified crystalline levoglucosan. 2 figs.
NASA Astrophysics Data System (ADS)
Taer, E.; Susanti, Y.; Awitdrus, Sugianto, Taslim, R.; Setiadi, R. N.; Bahri, S.; Agustino, Dewi, P.; Kurniasih, B.
2018-02-01
The effect of CO2 activation on the synthesis of activated carbon monolith from banana stem waste has been studied. Physical characteristics such as density, degree of crystallinity, surface morphology and elemental content has been analyzed, supporting the finding of an excellent electrochemical properties for the supercapacitor. The synthesis of activated carbon electrode began with pre-carbonization process at temperature of 250°C for 2.5 h. Then the process was continued by chemical activation using KOH as activating agent with a concentration of 0.4 M. The pellets were formed with 8 ton hydrolic pressure. All the samples were carbonized at a temperature of 600°C, followed by physical activation using CO2 gas at a various temperatures ranging from 800°C, 850°C, 900°C and 950°C for 2 h. The carbon content was increased with increasing temperature and the optimum temperature was 900°C. The specific capacitance depends on the activation temperature with the highest specific capacitance of 104.2 F/g at the activation temperature of 900°C.
Immobilization of Technetium in a Metallic Waste Form
DOE Office of Scientific and Technical Information (OSTI.GOV)
S.M. Frank; D. D. Keiser, Jr.; K. C. Marsden
Fission-product technetium accumulated during treatment of spent nuclear fuel will ultimately be disposed of in a geological repository. The exact form of Tc for disposal has yet to be determined; however, a reasonable solution is to incorporate elemental Tc into a metallic waste form similar to the waste form produced during the pyrochemical treatment of spent, sodium-bonded fuel. This metal waste form, produced at the Idaho National Laboratory, has undergone extensive qualification examination and testing for acceptance to the Yucca Mountain geological repository. It is from this extensive qualification effort that the behavior of Tc and other fission products inmore » the waste form has been elucidated, and that the metal waste form is extremely robust in the retention of fission products, such as Tc, in repository like conditions. This manuscript will describe the metal waste form, the behavior of Tc in the waste form; and current research aimed at determining the maximum possible loading of Tc into the metal waste and subsequent determination of the performance of high Tc loaded metal waste forms.« less
Amyloid Fiber Formation in Human γD-Crystallin Induced by UV-B Photodamage
Moran, Sean D.; Zhang, Tianqi O.; Decatur, Sean M.; Zanni, Martin T.
2013-01-01
γD-crystallin is an abundant structural protein of the lens that is found in native and modified forms in cataractous aggregates. We establish that UV-B irradiation of γD-crystallin leads to structurally specific modifications and precipitation via two mechanisms: amorphous aggregates and amyloid fibers. UV-B radiation causes cleavage of the backbone, in large measure near the interdomain interface, where side chain oxidations are also concentrated. 2D IR spectroscopy and expressed protein ligation localize fiber formation exclusively to the C-terminal domain of γD-crystallin. The native β-sandwich domains are not retained upon precipitation by either mechanism. The similarity between the amyloid forming pathway when induced by either UV-B radiation or low pH suggests that it is the propensity for the C-terminal β-sandwich domain to form amyloid β-sheets that determines the misfolding pathway independent of the mechanism of denaturation. PMID:23957864
NASA Astrophysics Data System (ADS)
Martena, Valentina; Censi, Roberta; Hoti, Ela; Malaj, Ledjan; Di Martino, Piera
2012-12-01
The objective of this study is to select very simple and well-known laboratory scale methods able to reduce particle size of indomethacin until the nanometric scale. The effect on the crystalline form and the dissolution behavior of the different samples was deliberately evaluated in absence of any surfactants as stabilizers. Nanocrystals of indomethacin (native crystals are in the γ form) (IDM) were obtained by three laboratory scale methods: A (Batch A: crystallization by solvent evaporation in a nano-spray dryer), B (Batch B-15 and B-30: wet milling and lyophilization), and C (Batch C-20-N and C-40-N: Cryo-milling in the presence of liquid nitrogen). Nanocrystals obtained by the method A (Batch A) crystallized into a mixture of α and γ polymorphic forms. IDM obtained by the two other methods remained in the γ form and a different attitude to the crystallinity decrease were observed, with a more considerable decrease in crystalline degree for IDM milled for 40 min in the presence of liquid nitrogen. The intrinsic dissolution rate (IDR) revealed a higher dissolution rate for Batches A and C-40-N, due to the higher IDR of α form than γ form for the Batch A, and the lower crystallinity degree for both the Batches A and C-40-N. These factors, as well as the decrease in particle size, influenced the IDM dissolution rate from the particle samples. Modifications in the solid physical state that may occur using different particle size reduction treatments have to be taken into consideration during the scale up and industrial development of new solid dosage forms.
Performance Test on Polymer Waste Form - 12137
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lee, Se Yup
Polymer solidification was attempted to produce stable waste form for the boric acid concentrates and the dewatered spent resins. The polymer mixture was directly injected into the mold or drum which was packed with the boric acid concentrates and the dewatered spent resins, respectively. The waste form was produced by entirely curing the polymer mixture. A series of performance tests was conducted including compressive strength test, water immersion test, leach test, thermal stability test, irradiation stability test and biodegradation stability test for the polymer waste forms. From the results of the performance tests for the polymer waste forms, it ismore » believed that the polymer waste form is very stable and can satisfy the acceptance criteria for permanent disposal. At present, performance tests with full scale polymer waste forms are being carried out in order to obtain qualification certificate by the regulatory institute in Korea. Polymer waste forms were prepared with the surrogate of boric acid concentrates and the surrogate of spent ion exchange resins respectively. Waste forms were also made in lab scale and in full scale. Lab. scale waste forms were directly subjected to a series of the performance tests. In the case of full scale waste form, the test specimens for the performance test were taken from a part of waste form by coring. A series of performance tests was conducted including compressive strength test, thermal stability test, irradiation stability test and biodegradation stability test, water immersion test, leach test, and free standing water for the polymer waste forms. In addition, a fire resistance test was performed on the waste forms by the requirement of the regulatory institute in Korea. Every polymer waste forms containing the boric acid concentrates and the spent ion exchange resins had exhibited excellent structural integrity of more than 27.58 MPa (4,000 psi) of compressive strength. On thermal stability testing, biodegradation testing and water immersion testing, no degradation was observed in the waste forms. Also, by measuring the compressive strength after these tests, it was confirmed that the structural integrity was still retained. A leach test was performed by using non radioactive cobalt, cesium and strontium. The leaching of cobalt, cesium and strontium from the polymer waste forms was very low. Also, the polymer waste forms were found to possess adequate fire resistance. From the results of the performance tests, it is believed that the polymer waste form is very stable and can satisfy the acceptance criteria for permanent disposal. At present, Performance tests with full scale polymer waste forms are on-going in order to obtain qualification certificate by the regulatory institute in Korea. (authors)« less
Avliyakulov, Nuraly K; Rajavel, Kavitha S; Le, Khanh Minh T; Guo, Lea; Mirsadraei, Leili; Yong, William H; Liau, Linda M; Li, Sichen; Lai, Albert; Nghiemphu, Phioanh L; Cloughesy, Timothy F; Linetsky, Michael; Haykinson, Michael J; Pope, Whitney B
2014-03-01
Malignant gliomas are the most common human primary brain tumors. Point mutation of amino acid arginine 132 to histidine (R132H) in the IDH1 protein leads to an enzymatic gain-of-function and is thought to promote gliomagenesis. Little is known about the downstream effects of the IDH1 mutation on protein expression and how and whether changes in protein expression are involved in tumor formation or propagation. In the current study, we used 2D DIGE (difference gel electrophoresis) and mass spectrometry to analyze differences in protein expression between IDH1(R132H) mutant and wild type anaplastic (grade III) astrocytoma from human brain cancer tissues. We show that expression levels of many proteins are altered in IDH1(R132H) mutant anaplastic astrocytoma. Some of the most over-expressed proteins in the mutants include several forms of αB-crystallin, a small heat-shock and anti-apoptotic protein. αB-crystallin proteins are elevated up to 22-fold in IDH1(R132H) mutant tumors, and αB-crystallin expression appears to be controlled at the post-translational level. We identified the most abundant form of αB-crystallin as a low molecular weight species that is C-terminally truncated. We also found that overexpression of αB-crystallin can be induced by transfecting U251 human glioblastoma cell lines with the IDH1(R132H) mutation. In conclusion, the association of a C-terminally truncated form of αB-crystallin protein with the IDH1(R132H) mutation is a novel finding that could impact apoptosis and stress response in IDH1 mutant glioma.
Thermally-prepared polymorphic forms of cilostazol.
Stowell, Grayson W; Behme, Robert J; Denton, Stacy M; Pfeiffer, Inigo; Sancilio, Frederick D; Whittall, Linda B; Whittle, Robert R
2002-12-01
Prior to this study, cilostazol, an antithrombotic drug, was thought to exist as a single crystalline phase with a melting point of approximately 159 degrees C (Form A). On cooling, melts often form a glass that, when heated, may crystallize as additional crystalline polymorphic forms. Cilostazol, when reheated, subsequently forms polymorphs that melt at approximately 136 degrees C (Form B) and 146 degrees C (Form C). Free-energy temperature diagrams estimated from calorimetry data reveal that each pair of the cilostazol polymorphs (A-B, B-C, and A-C) is monotropic. Essentially pure samples of suitable crystalline shape and size permitted single crystal structural analysis of Forms A and C. Theoretical solubility ratios calculated using calorimetry data indicate that at 37 degrees C, Form B should be more than four times more soluble and Form C should be more than two times more soluble than Form A. Forms B and C could not be crystallized from solvents. Metastable forms from super cooled melts analyzed by intrinsic dissolution and Fourier transform-Raman experiments demonstrated that Forms B and C undergo a rapid, solvent-mediated recrystallization to Form A, making dissolution rate measurements difficult. Copyright 2002 Wiley-Liss, Inc. and the American Pharmaceutical Association J Pharm Sci 91:2481-2488, 2002
Facile "modular assembly" for fast construction of a highly oriented crystalline MOF nanofilm.
Xu, Gang; Yamada, Teppei; Otsubo, Kazuya; Sakaida, Shun; Kitagawa, Hiroshi
2012-10-10
The preparation of crystalline, ordered thin films of metal-organic frameworks (MOFs) will be a critical process for MOF-based nanodevices in the future. MOF thin films with perfect orientation and excellent crystallinity were formed with novel nanosheet-structured components, Cu-TCPP [TCPP = 5,10,15,20-tetrakis(4-carboxyphenyl)porphyrin], by a new "modular assembly" strategy. The modular assembly process involves two steps: a "modularization" step is used to synthesize highly crystalline "modules" with a nanosized structure that can be conveniently assembled into a thin film in the following "assembly" step. With this method, MOF thin films can easily be set up on different substrates at very high speed with controllable thickness. This new approach also enabled us to prepare highly oriented crystalline thin films of MOFs that cannot be prepared in thin-film form by traditional techniques.
Degradation of partially immersed glass: A new perspective
NASA Astrophysics Data System (ADS)
Chinnam, R. K.; Fossati, P. C. M.; Lee, W. E.
2018-05-01
The International Simple Glass (ISG) is a six-component borosilicate glass which was developed as a reference for international collaborative studies on high level nuclear waste encapsulation. Its corrosion behaviour is typically examined when it is immersed in a leaching solution, or when it is exposed to water vapour. In this study, an alternative situation is considered in which the glass is only partially immersed for 7 weeks at a temperature of 90 °C. In this case, half of the glass sample is directly in the solution itself, and the other half is in contact with a water film formed by condensation of water vapour that evaporated from the solution. This results in a different degradation behaviour compared to standard tests in which the material is fully immersed. In particular, whilst in standard tests the system reaches a steady state with a very low alteration rate thanks to the formation of a protective gel layer, in partially-immersed tests this steady state could not be reached because of the continuous alteration from the condensate water film. The constant input of ions from the emerged part of the sample caused a supersaturation of the solution, which resulted in early precipitation of secondary crystalline phases. This setup mimics storage conditions once small amounts of water have entered a glass waste form containing canister. It offers a more realistic outlook of corrosion mechanisms happening in such situations than standard fully-immersed corrosion tests.
Improvement of nuclide leaching resistance of paraffin waste form with low density polyethylene.
Kim, Chang Lak; Park, Joo Wan; Kim, Ju Youl; Chung, Chang Hyun
2002-01-01
Low-level liquid borate wastes have been immobilized with paraffin wax using a concentrate waste drying system (CWDS) in Korean nuclear power plants. The possibility for improving chemical durability of paraffin waste form was suggested in this study. A small amount of low density polyethylene (LDPE) was added to increase the leaching resistance of the existing paraffin waste form. The influence of LDPE on the leaching behavior of waste form was investigated by performing leaching test according to ANSI/ANS-16.1 procedure during 325 days. It was observed that the leaching of nuclides immobilized within paraffin waste form made a marked reduction although little content of LDPE was added to waste form. The acceptance criteria of paraffin waste form associated with leachability index (LI) and compressive strength after the leaching test were fully satisfied with the help of LDPE.
Solubility advantage of amorphous pharmaceuticals: I. A thermodynamic analysis.
Murdande, Sharad B; Pikal, Michael J; Shanker, Ravi M; Bogner, Robin H
2010-03-01
In recent years there has been growing interest in advancing amorphous pharmaceuticals as an approach for achieving adequate solubility. Due to difficulties in the experimental measurement of solubility, a reliable estimate of the solubility enhancement ratio of an amorphous form of a drug relative to its crystalline counterpart would be highly useful. We have developed a rigorous thermodynamic approach to estimate enhancement in solubility that can be achieved by conversion of a crystalline form to the amorphous form. We rigorously treat the three factors that contribute to differences in solubility between amorphous and crystalline forms. First, we calculate the free energy difference between amorphous and crystalline forms from thermal properties measured by modulated differential scanning calorimetry (MDSC). Secondly, since an amorphous solute can absorb significant amounts of water, which reduces its activity and solubility, a correction is made using water sorption isotherm data and the Gibbs-Duhem equation. Next, a correction is made for differences in the degree of ionization due to differences in solubilities of the two forms. Utilizing this approach the theoretically estimated solubility enhancement ratio of 7.0 for indomethacin (amorphous/gamma-crystal) was found to be in close agreement with the experimentally determined ratio of 4.9. 2009 Wiley-Liss, Inc. and the American Pharmacists Association
NASA Astrophysics Data System (ADS)
Liu, Shuangyi; Huang, Limin; Li, Wanlu; Liu, Xiaohua; Jing, Shui; Li, Jackie; O'Brien, Stephen
2015-07-01
Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity.Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02351c
Glass binder development for a glass-bonded sodalite ceramic waste form
NASA Astrophysics Data System (ADS)
Riley, Brian J.; Vienna, John D.; Frank, Steven M.; Kroll, Jared O.; Peterson, Jacob A.; Canfield, Nathan L.; Zhu, Zihua; Zhang, Jiandong; Kruska, Karen; Schreiber, Daniel K.; Crum, Jarrod V.
2017-06-01
This paper discusses work to develop Na2O-B2O3-SiO2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. Here, five new glasses with ∼20 mass% Na2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion for the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. These improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.
Pankove, J.I.; Wu, C.P.
1982-03-30
A novel hydrogen rich single crystalline silicon material having a band gap energy greater than 1.1 eV can be fabricated by forming an amorphous region of graded crystallinity in a body of single crystalline silicon and thereafter contacting the region with atomic hydrogen followed by pulsed laser annealing at a sufficient power and for a sufficient duration to recrystallize the region into single crystalline silicon without out-gassing the hydrogen. The new material can be used to fabricate semi-conductor devices such as single crystalline silicon solar cells with surface window regions having a greater band gap energy than that of single crystalline silicon without hydrogen. 2 figs.
Pankove, Jacques I.; Wu, Chung P.
1982-01-01
A novel hydrogen rich single crystalline silicon material having a band gap energy greater than 1.1 eV can be fabricated by forming an amorphous region of graded crystallinity in a body of single crystalline silicon and thereafter contacting the region with atomic hydrogen followed by pulsed laser annealing at a sufficient power and for a sufficient duration to recrystallize the region into single crystalline silicon without out-gasing the hydrogen. The new material can be used to fabricate semi-conductor devices such as single crystalline silicon solar cells with surface window regions having a greater band gap energy than that of single crystalline silicon without hydrogen.
Updated Liquid Secondary Waste Grout Formulation and Preliminary Waste Form Qualification
DOE Office of Scientific and Technical Information (OSTI.GOV)
Saslow, Sarah A.; Um, Wooyong; Russell, Renee L.
This report describes the results from liquid secondary waste grout (LSWG) formulation and cementitious waste form qualification tests performed by Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions, LLC (WRPS). New formulations for preparing a cementitious waste form from a high-sulfate liquid secondary waste stream simulant, developed for Effluent Management Facility (EMF) process condensates merged with low activity waste (LAW) caustic scrubber, and the release of key constituents (e.g. 99Tc and 129I) from these monoliths were evaluated. This work supports a technology development program to address the technology needs for Hanford Site Effluent Treatment Facility (ETF) liquid secondarymore » waste (LSW) solidification and supports future Direct Feed Low-Activity Waste (DFLAW) operations. High-priority activities included simulant development, LSWG formulation, and waste form qualification. The work contained within this report relates to waste form development and testing and does not directly support the 2017 integrated disposal facility (IDF) performance assessment (PA). However, this work contains valuable information for use in PA maintenance past FY17, and for future waste form development efforts. The provided data should be used by (i) cementitious waste form scientists to further understanding of cementitious dissolution behavior, (ii) IDF PA modelers who use quantified constituent leachability, effective diffusivity, and partitioning coefficients to advance PA modeling efforts, and (iii) the U.S. Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program. The results obtained help fill existing data gaps, support final selection of a LSWG waste form, and improve the technical defensibility of long-term waste form performance estimates.« less
Waste Acceptance Testing of Secondary Waste Forms: Cast Stone, Ceramicrete and DuraLith
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mattigod, Shas V.; Westsik, Joseph H.; Chung, Chul-Woo
2011-08-12
To support the selection of a waste form for the liquid secondary wastes from WTP, Washington River Protection Solutions has initiated secondary-waste-form testing work at Pacific Northwest National Laboratory (PNNL). In anticipation of a down-selection process for a waste form for the Solidification Treatment Unit to be added to the ETF, PNNL is conducting tests on four candidate waste forms to evaluate their ability to meet potential waste acceptance criteria for immobilized secondary wastes that would be placed in the IDF. All three waste forms demonstrated compressive strengths above the minimum 3.45 MPa (500 psi) set as a target formore » cement-based waste forms. Further, none of the waste forms showed any significant degradation in compressive strength after undergoing thermal cycling (30 cycles in a 10 day period) between -40 C and 60 C or water immersion for 90 days. The three leach test methods are intended to measure the diffusion rates of contaminants from the waste forms. Results are reported in terms of diffusion coefficients and a leachability index (LI) calculated based on the diffusion coefficients. A smaller diffusion coefficient and a larger LI are desired. The NRC, in its Waste Form Technical Position (NRC 1991), provides recommendations and guidance regarding methods to demonstrate waste stability for land disposal of radioactive waste. Included is a recommendation to conduct leach tests using the ANS 16.1 method. The resulting leachability index (LI) should be greater than 6.0. For Hanford secondary wastes, the LI > 6.0 criterion applies to sodium leached from the waste form. For technetium and iodine, higher targets of LI > 9 for Tc and LI > 11 for iodine have been set based on early waste-disposal risk and performance assessment analyses. The results of these three leach tests conducted for a total time between 11days (ASTM C1308) to 90 days (ANS 16.1) showed: (1) Technetium diffusivity: ANSI/ANS 16.1, ASTM C1308, and EPA 1315 tests indicated that all the waste forms had leachability indices better than the target LI > 9 for technetium; (2) Rhenium diffusivity: Cast Stone 2M specimens, when tested using EPA 1315 protocol, had leachability indices better than the target LI > 9 for technetium based on rhenium as a surrogate for technetium. All other waste forms tested by ANSI/ANS 16.1, ASTM C1308, and EPA 1315 test methods had leachability indices that were below the target LI > 9 for Tc based on rhenium release. These studies indicated that use of Re(VII) as a surrogate for 99Tc(VII) in low temperature secondary waste forms containing reductants will provide overestimated diffusivity values for 99Tc. Therefore, it is not appropriate to use Re as a surrogate 99Tc in future low temperature waste form studies. (3) Iodine diffusivity: ANSI/ANS 16.1, ASTM C1308, and EPA 1315 tests indicated that the three waste forms had leachability indices that were below the target LI > 11 for iodine. Therefore, it may be necessary to use a more effective sequestering material than silver zeolite used in two of the waste forms (Ceramicrete and DuraLith); (4) Sodium diffusivity: All the waste form specimens tested by the three leach methods (ANSI/ANS 16.1, ASTM C1308, and EPA 1315) exceeded the target LI value of 6; (5) All three leach methods (ANS 16.1, ASTM C1308 and EPA 1315) provided similar 99Tc diffusivity values for both short-time transient diffusivity effects as well as long-term ({approx}90 days) steady diffusivity from each of the three tested waste forms (Cast Stone 2M, Ceramicrete and DuraLith). Therefore, any one of the three methods can be used to determine the contaminant diffusivities from a selected waste form.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
S.M. Frank
Work describe in this report represents the final year activities for the 3-year International Nuclear Energy Research Initiative (I-NERI) project: Development and Characterization of New High-Level Waste Forms for Achieving Waste Minimization from Pyroprocessing. Used electrorefiner salt that contained actinide chlorides and was highly loaded with surrogate fission products was processed into three candidate waste forms. The first waste form, a high-loaded ceramic waste form is a variant to the CWF produced during the treatment of Experimental Breeder Reactor-II used fuel at the Idaho National Laboratory (INL). The two other waste forms were developed by researchers at the Korean Atomicmore » Energy Research Institute (KAERI). These materials are based on a silica-alumina-phosphate matrix and a zinc/titanium oxide matrix. The proposed waste forms, and the processes to fabricate them, were designed to immobilize spent electrorefiner chloride salts containing alkali, alkaline earth, lanthanide, and halide fission products that accumulate in the salt during the processing of used nuclear fuel. This aspect of the I-NERI project was to demonstrate 'hot cell' fabrication and characterization of the proposed waste forms. The outline of the report includes the processing of the spent electrorefiner salt and the fabrication of each of the three waste forms. Also described is the characterization of the waste forms, and chemical durability testing of the material. While waste form fabrication and sample preparation for characterization must be accomplished in a radiological hot cell facility due to hazardous radioactivity levels, smaller quantities of each waste form were removed from the hot cell to perform various analyses. Characterization included density measurement, elemental analysis, x-ray diffraction, scanning electron microscopy and the Product Consistency Test, which is a leaching method to measure chemical durability. Favorable results from this demonstration project will provide additional options for fission product immobilization and waste management associated the electrochemical/pyrometallurgical processing of used nuclear fuel.« less
Development of iron phosphate ceramic waste form to immobilize radioactive waste solution
NASA Astrophysics Data System (ADS)
Choi, Jongkwon; Um, Wooyong; Choung, Sungwook
2014-09-01
The objective of this research was to develop an iron phosphate ceramic (IPC) waste form using converter slag obtained as a by-product of the steel industry as a source of iron instead of conventional iron oxide. Both synthetic off-gas scrubber solution containing technetium-99 (or Re as a surrogate) and LiCl-KCl eutectic salt, a final waste solution from pyrochemical processing of spent nuclear fuel, were used as radioactive waste streams. The IPC waste form was characterized for compressive strength, reduction capacity, chemical durability, and contaminant leachability. Compressive strengths of the IPC waste form prepared with different types of waste solutions were 16 MPa and 19 MPa for LiCl-KCl eutectic salt and the off-gas scrubber simulant, respectively, which meet the minimum compressive strength of 3.45 MPa (500 psi) for waste forms to be accepted into the radioactive waste repository. The reduction capacity of converter slag, a main dry ingredient used to prepare the IPC waste form, was 4136 meq/kg by the Ce(IV) method, which is much higher than those of the conventional Fe oxides used for the IPC waste form and the blast furnace slag materials. Average leachability indexes of Tc, Li, and K for the IPC waste form were higher than 6.0, and the IPC waste form demonstrated stable durability even after 63-day leaching. In addition, the Toxicity Characteristic Leach Procedure measurements of converter slag and the IPC waste form with LiCl-KCl eutectic salt met the universal treatment standard of the leachability limit for metals regulated by the Resource Conservation and Recovery Act. This study confirms the possibility of development of the IPC waste form using converter slag, showing its immobilization capability for radionuclides in both LiCl-KCl eutectic salt and off-gas scrubber solutions with significant cost savings.
Development of iron phosphate ceramic waste form to immobilize radioactive waste solution
DOE Office of Scientific and Technical Information (OSTI.GOV)
Choi, Jongkwon; Um, Wooyong; Choung, Sungwook
The objective of this research was to develop an iron phosphate ceramic (IPC) waste form using converter slag obtained as a by-product of the steel industry as a source of iron instead of conventional iron oxide. Both synthetic off-gas scrubber solution containing technetium-99 (or Re as a surrogate) and LiCl-KCl eutectic salt, a final waste solution from pyrochemical processing of spent nuclear fuel, were used as radioactive waste streams. The IPC waste form was characterized for compressive strength, reduction capacity, chemical durability, and contaminant leachability. Compressive strengths of the IPC waste form prepared with different types of waste solutions weremore » 16 MPa and 19 MPa for LiCl-KCl eutectic salt and the off-gas scrubber simulant, respectively, which meet the minimum compressive strength of 3.45 MPa (500 psi) for waste forms to be accepted into the radioactive waste repository. The reduction capacity of converter slag, a main dry ingredient used to prepare the IPC waste form, was 4,136 meq/kg by the Ce(IV) method, which is much higher than those of the conventional Fe oxides used for the IPC waste form and the blast furnace slag materials. Average leachability indexes of Tc, Li, and K for the IPC waste form were higher than 6.0, and the IPC waste form demonstrated stable durability even after 63-day leaching. In addition, the Toxicity Characteristic Leach Procedure measurements of converter slag and the IPC waste form with LiCl-KCl eutectic salt met the universal treatment standard of the leachability limit for metals regulated by the Resource Conservation and Recovery Act. This study confirms the possibility of development of the IPC waste form using converter slag, showing its immobilization capability for radionuclides in both LiCl-KCl eutectic salt and off-gas scrubber solutions with significant cost savings.« less
PERMEABILITY CHANGES IN CRYSTALLINE ROCKS DUE TO TEMPERATURE: EFFECTS OF MINERAL ASSEMBLAGE.
Morrow, C.A.; Moore, Diane E.; Byerlee, J.D.; ,
1985-01-01
The change in permeability with time of granite, quartzite, anorthosite and gabbro was measured while these rocks were subjected to a temperature gradient. Permeability reductions of up to two orders of magnitude were observed, with the greatest reactions occurring in the quartzite. These changes are thought to be caused by dissolution of minerals at high temperatures, and redeposition of the dissolved material at lower temperatures. Quartz appears to be an important mineral in this self-sealing process. If very low permeability is desired around a nuclear waste repository in crystalline rocks, then a quartz-rich rock may be the most appropriate host.
Secondary Waste Form Down-Selection Data Package—Fluidized Bed Steam Reforming Waste Form
DOE Office of Scientific and Technical Information (OSTI.GOV)
Qafoku, Nikolla; Westsik, Joseph H.; Strachan, Denis M.
2011-09-12
The Hanford Site in southeast Washington State has 56 million gallons of radioactive and chemically hazardous wastes stored in 177 underground tanks (ORP 2010). The U.S. Department of Energy (DOE), Office of River Protection (ORP), through its contractors, is constructing the Hanford Tank Waste Treatment and Immobilization Plant (WTP) to convert the radioactive and hazardous wastes into stable glass waste forms for disposal. Within the WTP, the pretreatment facility will receive the retrieved waste from the tank farms and separate it into two treated process streams. These waste streams will be vitrified, and the resulting waste canisters will be sentmore » to offsite (high-level waste [HLW]) and onsite (immobilized low-activity waste [ILAW]) repositories. As part of the pretreatment and ILAW processing, liquid secondary wastes will be generated that will be transferred to the Effluent Treatment Facility (ETF) on the Hanford Site for further treatment. These liquid secondary wastes will be converted to stable solid waste forms that will be disposed of in the Integrated Disposal Facility (IDF). To support the selection of a waste form for the liquid secondary wastes from WTP, Washington River Protection Solutions (WRPS) has initiated secondary waste form testing work at Pacific Northwest National Laboratory (PNNL). In anticipation of a down-selection process for a waste form for the Solidification Treatment Unit to be added to the ETF, PNNL is developing data packages to support that down-selection. The objective of the data packages is to identify, evaluate, and summarize the existing information on the four waste forms being considered for stabilizing and solidifying the liquid secondary wastes. At the Hanford Site, the FBSR process is being evaluated as a supplemental technology for treating and immobilizing Hanford LAW radioactive tank waste and for treating secondary wastes from the WTP pretreatment and LAW vitrification processes.« less
Theil, Frank; Milsmann, Johanna; Anantharaman, Sankaran; van Lishaut, Holger
2018-05-07
The preparation of an amorphous solid dispersion (ASD) by dissolving a poorly water-soluble active pharmaceutical ingredient (API) in a polymer matrix can improve the bioavailability by orders of magnitude. Crystallization of the API in the ASD, though, is an inherent threat for bioavailability. Commonly, the impact of crystalline API on the drug release of the dosage form is studied with samples containing spiked crystallinity. These spiked samples possess implicit differences compared to native crystalline samples, regarding size and spatial distribution of the crystals as well as their molecular environment. In this study, we demonstrate that it is possible to grow defined amounts of crystalline API in solid dosage forms, which enables us to study the biopharmaceutical impact of actual crystallization. For this purpose, we studied the crystal growth in fenofibrate tablets over time under an elevated moisture using transmission Raman spectroscopy (TRS). As a nondestructive method to assess API crystallinity in ASD formulations, TRS enables the monitoring of crystal growth in individual dosage forms. Once the kinetic trace of the crystal growth for a certain environmental condition is determined, this method can be used to produce samples with defined amounts of crystallized API. To investigate the biopharmaceutical impact of crystallized API, non-QC dissolution methods were used, designed to identify differences between the various amounts of crystalline materials present. The drug release in the samples manufactured in this fashion was compared to that of samples with spiked crystallinity. In this study, we present for the first time a method for targeted crystallization of amorphous tablets to simulate crystallized ASDs. This methodology is a valuable tool to generate model systems for biopharmaceutical studies on the impact of crystallinity on the bioavailability.
Supplemental Immobilization of Hanford Low-Activity Waste: Cast Stone Screening Tests
DOE Office of Scientific and Technical Information (OSTI.GOV)
Westsik, Joseph H.; Piepel, Gregory F.; Lindberg, Michael J.
2013-09-30
More than 56 million gallons of radioactive and hazardous waste are stored in 177 underground storage tanks at the U.S. Department of Energy’s (DOE’s) Hanford Site in southeastern Washington State. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the wastes and immobilize them in a glass waste form. The WTP includes a pretreatment facility to separate the wastes into a small volume of high-level waste (HLW) containing most of the radioactivity and a larger volume of low-activity waste (LAW) containing most of the nonradioactive chemicals. The HLW will be converted to glass in themore » HLW vitrification facility for ultimate disposal at an offsite federal repository. At least a portion (~35%) of the LAW will be converted to glass in the LAW vitrification facility and will be disposed of onsite at the Integrated Disposal Facility (IDF). The pretreatment and HLW vitrification facilities will have the capacity to treat and immobilize the wastes destined for each facility. However, a second LAW immobilization facility will be needed for the expected volume of LAW requiring immobilization. A cementitious waste form known as Cast Stone is being considered to provide the required additional LAW immobilization capacity. The Cast Stone waste form must be acceptable for disposal in the IDF. The Cast Stone waste form and immobilization process must be tested to demonstrate that the final Cast Stone waste form can comply with the waste acceptance criteria for the disposal facility and that the immobilization processes can be controlled to consistently provide an acceptable waste form product. Further, the waste form must be tested to provide the technical basis for understanding the long-term performance of the waste form in the disposal environment. These waste form performance data are needed to support risk assessment and performance assessment (PA) analyses of the long-term environmental impact of the waste disposal in the IDF. The PA is needed to satisfy both Washington State IDF Permit and DOE Order requirements. Cast Stone has been selected for solidification of radioactive wastes including WTP aqueous secondary wastes treated at the Effluent Treatment Facility (ETF) at Hanford. A similar waste form called Saltstone is used at the Savannah River Site (SRS) to solidify its LAW tank wastes.« less
Sehn, Janaína L; de Leão, Felipe B; da Boit, Kátia; Oliveira, Marcos L S; Hidalgo, Gelsa E; Sampaio, Carlos H; Silva, Luis F O
2016-03-01
Detailed geochemistry similarities between the burning coal cleaning rejects (BCCRs) and non-anthropogenic geological environments are outlined here. While no visible flames were detected, this research revealed that auto-combustion existed in the studied area for many years. The occurrence of several amorphous phases, mullite, hematite and many other Al/Fe-minerals formed by high temperature was found. Bad disposal of coal-dump wastes represents significant environmental concerns due to their potential influence on atmosphere, river sediments, soils and as well as on the surface and groundwater in the surroundings of these areas. The present work using multi-analytical techniques were performed to provide an improved understanding of the complex processes related with sulphide-rich coal waste oxidation, spontaneous combustion and newmineral creation. It recording huge numbers of rare minerals with alunite, montmorillonite, szmolnockite, halotrichite, coquimbite and copiapite at the BCCRs. The information presented the presence of abundant amorphous Si-Al-Fe-Ti as (oxy-)hydroxides and Fe-hydro/oxides with goethite and hematite with various degrees of crystallinity, containing potential hazardous elements (PHEs), such as Cu, Cr, Hf, Hg, Mo, Ni, Se, Pb, Th, U, Zr, and others. Most of the nano-particles and ultra-fine particles found in the burned coal-dump wastes are the same as those commonly associated with coal cleaning rejects, in which oxidation of sulphides plays an important impact to environment and subsequently animal and human health. Copyright © 2015 Elsevier Ltd. All rights reserved.
Polymorph selection: the role of nucleation, crystal growth and molecular modeling.
Erdemir, Deniz; Lee, Alfred Y; Myerson, Allan S
2007-11-01
Solution crystallization is an important separation and purification process used in the chemical, pharmaceutical and food industries. The quality of a crystalline product is generally judged by four main criteria: purity, crystal habit, particle size and solid form. Consistent production of the desired polymorph is crucial as the unanticipated emergence of a different crystal form may have severe consequences. Thus, the selection of a solid-state form for a crystalline product is vital and is ultimately based on knowledge of the properties of the other polymorphs. This review discusses the role of nucleation, crystal growth and molecular modeling on polymorphism in molecular crystals. Examples are presented demonstrating how the first two factors can govern the appearance of a particular crystalline form, and how the latter factor can be used as a tool for understanding polymorphism.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Saslow, Sarah A.; Um, Wooyong; Russell, Renee L.
This report describes the results from grout formulation and cementitious waste form qualification testing performed by Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions, LLC (WRPS). These results are part of a screening test that investigates three grout formulations proposed for wide-range treatment of different waste stream compositions expected for the Hanford Effluent Management Facility (EMF) evaporator bottom waste. This work supports the technical development need for alternative disposition paths for the EMF evaporator bottom wastes and future direct feed low-activity waste (DFLAW) operations at the Hanford Site. High-priority activities included simulant production, grout formulation, and cementitious wastemore » form qualification testing. The work contained within this report relates to waste form development and testing, and does not directly support the 2017 Integrated Disposal Facility (IDF) performance assessment (PA). However, this work contains valuable information for use in PA maintenance past FY 2017 and future waste form development efforts. The provided results and data should be used by (1) cementitious waste form scientists to further the understanding of cementitious leach behavior of contaminants of concern (COCs), (2) decision makers interested in off-site waste form disposal, and (3) the U.S. Department of Energy, their Hanford Site contractors and stakeholders as they assess the IDF PA program at the Hanford Site. The results reported help fill existing data gaps, support final selection of a cementitious waste form for the EMF evaporator bottom waste, and improve the technical defensibility of long-term waste form risk estimates.« less
Ordered organic-organic multilayer growth
Forrest, Stephen R.; Lunt, Richard R.
2016-04-05
An ordered multilayer crystalline organic thin film structure is formed by depositing at least two layers of thin film crystalline organic materials successively wherein the at least two thin film layers are selected to have their surface energies within .+-.50% of each other, and preferably within .+-.15% of each other, whereby every thin film layer within the multilayer crystalline organic thin film structure exhibit a quasi-epitaxial relationship with the adjacent crystalline organic thin film.
Ordered organic-organic multilayer growth
Forrest, Stephen R; Lunt, Richard R
2015-01-13
An ordered multilayer crystalline organic thin film structure is formed by depositing at least two layers of thin film crystalline organic materials successively wherein the at least two thin film layers are selected to have their surface energies within .+-.50% of each other, and preferably within .+-.15% of each other, whereby every thin film layer within the multilayer crystalline organic thin film structure exhibit a quasi-epitaxial relationship with the adjacent crystalline organic thin film.
Kuva, J; Sammaljärvi, J; Parkkonen, J; Siitari-Kauppi, M; Lehtonen, M; Turpeinen, T; Timonen, J; Voutilainen, M
2018-04-01
We set out to study connected porosity of crystalline rock using X-ray microtomography and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS) with caesium chloride as a contrast agent. Caesium is an important radionuclide regarding the final deposition of nuclear waste and also forms dense phases that can be readily distinguished by X-ray microtomography and SEM-EDS. Six samples from two sites, Olkiluoto (Finland) and Grimsel (Switzerland), where transport properties of crystalline rock are being studied in situ, were investigated using X-ray microtomography and SEM-EDS. The samples were imaged with X-ray microtomography, immersed in a saturated caesium chloride (CsCl) solution for 141, 249 and 365 days and imaged again with X-ray microtomography. CsCl inside the samples was successfully detected with X-ray microtomography and it had completely penetrated all six samples. SEM-EDS elemental mapping was used to study the location of caesium in the samples in detail with quantitative mineral information. Precipitated CsCl was found in the connected pore space in Olkiluoto veined gneiss and in lesser amounts in Grimsel granodiorite. Only a very small amount of precipitated CsCl was observed in the Grimsel granodiorite samples. In Olkiluoto veined gneiss caesium was found in pinitised areas of cordierite grains. In the pinitised areas caesium was found in notable excess compared to chloride, possibly due to the combination of small pore size and negatively charged surfaces. In addition, elevated concentrations of caesium were found in kaolinite and sphalerite phases. The findings concerning the location of CsCl were congruent with X-ray microtomography. © 2017 The Authors Journal of Microscopy © 2017 Royal Microscopical Society.
DOE Office of Scientific and Technical Information (OSTI.GOV)
AA KRUGER; A GOEL; CP RODRIGUEZ
2012-08-13
The immobilization of 99Tc in a suitable host matrix has proved a challenging task for researchers in the nuclear waste community around the world. At the Hanford site in Washington State in the U.S., the total amount of 99Tc in low-activity waste (LAW) is {approx} 1,300 kg and the current strategy is to immobilize the 99Tc in borosilicate glass with vitrification. In this context, the present article reports on the solubility and retention of rhenium, a nonradioactive surrogate for 99Tc, in a LAW sodium borosilicate glass. Due to the radioactive nature of technetium, rhenium was chosen as a simulant becausemore » of previously established similarities in ionic radii and other chemical aspects. The glasses containing target Re concentrations varying from 0 to10,000 ppm by mass were synthesized in vacuum-sealed quartz ampoules to minimize the loss of Re by volatilization during melting at 1000 DC. The rhenium was found to be present predominantly as Re7 + in all the glasses as observed by X-ray absorption near-edge structure (XANES). The solubility of Re in borosilicate glasses was determined to be {approx}3,000 ppm (by mass) using inductively coupled plasma-optical emission spectroscopy (ICP-OES). At higher rhenium concentrations, some additional material was retained in the glasses in the form of alkali perrhenate crystalline inclusions detected by X-ray diffraction (XRD) and laser ablation-ICP mass spectrometry (LA-ICP-MS). Assuming justifiably substantial similarities between Re7 + and Tc 7+ behavior in this glass system, these results implied that the processing and immobilization of 99Tc from radioactive wastes should not be limited by the solubility of 99Tc in borosilicate LAW glasses.« less
Glass binder development for a glass-bonded sodalite ceramic waste form
DOE Office of Scientific and Technical Information (OSTI.GOV)
Riley, Brian J.; Vienna, John D.; Frank, Steven M.
This paper discusses work to develop Na 2O-B 2O 3-SiO 2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. In this paper, five new glasses with ~20 mass% Na 2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion formore » the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. Finally, these improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.« less
Glass binder development for a glass-bonded sodalite ceramic waste form
Riley, Brian J.; Vienna, John D.; Frank, Steven M.; ...
2017-06-01
This paper discusses work to develop Na 2O-B 2O 3-SiO 2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. In this paper, five new glasses with ~20 mass% Na 2O were designed to generate waste forms with high sodalite. The glasses were then used to produce ceramic waste forms with a surrogate salt waste. The waste forms made using these new glasses were formulated to generate more sodalite than those made with previous baseline glasses for this type of waste. The coefficients of thermal expansion formore » the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature than previous binder glasses used. Finally, these improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability.« less
Raju, Murugesan; Santhoshkumar, Puttur; Sharma, K. Krishna
2012-01-01
Background A substitution mutation in human αA-crystallin (αAG98R) is associated with autosomal dominant cataract. The recombinant mutant αAG98R protein exhibits altered structure, substrate-dependent chaperone activity, impaired oligomer stability and aggregation on prolonged incubation at 37°C. Our previous studies have shown that αA-crystallin–derived mini-chaperone (DFVIFLDVKHFSPEDLTVK) functions like a molecular chaperone by suppressing the aggregation of denaturing proteins. The present study was undertaken to determine the effect of αA-crystallin–derived mini-chaperone on the stability and chaperone activity of αAG98R-crystallin. Methodology/Principal Findings Recombinant αAG98R was incubated in presence and absence of mini-chaperone and analyzed by chromatographic and spectrometric methods. Transmission electron microscope was used to examine the effect of mini-chaperone on the aggregation propensity of mutant protein. Mini-chaperone containing photoactive benzoylphenylalanine was used to confirm the interaction of mini-chaperone with αAG98R. The rescuing of chaperone activity in mutantα-crystallin (αAG98R) by mini-chaperone was confirmed by chaperone assays. We found that the addition of the mini-chaperone during incubation of αAG98R protected the mutant crystallin from forming larger aggregates that precipitate with time. The mini-chaperone-stabilized αAG98R displayed chaperone activity comparable to that of wild-type αA-crystallin. The complexes formed between mini-αA–αAG98R complex and ADH were more stable than the complexes formed between αAG98R and ADH. Western-blotting and mass spectrometry confirmed the binding of mini-chaperone to mutant crystallin. Conclusion/Significance These results demonstrate that mini-chaperone stabilizes the mutant αA-crystallin and modulates the chaperone activity of αAG98R. These findings aid in our understanding of how to design peptide chaperones that can be used to stabilize mutant αA-crystallins and preserve the chaperone function. PMID:22970163
NREL Technologies Win National Awards
percent for a prototype module, 7.6 percent for a commercial module) from amorphous silicon, which is less expensive to produce than crystalline silicon used in most commercial solar cells. The resulting product is biomass resources such as wood waste or plant material into gas for electric power generation. The new
Equilibrium Temperature Profiles within Fission Product Waste Forms
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kaminski, Michael D.
2016-10-01
We studied waste form strategies for advanced fuel cycle schemes. Several options were considered for three waste streams with the following fission products: cesium and strontium, transition metals, and lanthanides. These three waste streams may be combined or disposed separately. The decay of several isotopes will generate heat that must be accommodated by the waste form, and this heat will affect the waste loadings. To help make an informed decision on the best option, we present computational data on the equilibrium temperature of glass waste forms containing a combination of these three streams.
Geomechanical Considerations for the Deep Borehole Field Test
NASA Astrophysics Data System (ADS)
Park, B. Y.
2015-12-01
Deep borehole disposal of high-level radioactive waste is under consideration as a potential alternative to shallower mined repositories. The disposal concept consists of drilling a borehole into crystalline basement rocks to a depth of 5 km, emplacement of canisters containing solid waste in the lower 2 km, and plugging and sealing the upper 3 km of the borehole. Crystalline rocks such as granites are particularly attractive for borehole emplacement because of their low permeability and porosity at depth, and high mechanical strength to resist borehole deformation. In addition, high overburden pressures contribute to sealing of some of the fractures that provide transport pathways. We present geomechanical considerations during construction (e.g., borehole breakouts, disturbed rock zone development, and creep closure), relevant to both the smaller-diameter characterization borehole (8.5") and the larger-diameter field test borehole (17"). Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
Transesterification of sago starch and waste palm cooking oil in densified CO2
NASA Astrophysics Data System (ADS)
Muljana, H.; Sugih, A. K.; Christina, N.; Fangdinata, K.; Renaldo, J.; Rudy; Heeres, H. J.; Picchioni, F.
2017-07-01
In this work, the synthesis of biodegradable and yet renewable thermoplastics materials through a transesterification reaction of sago starch and waste palm cooking oil (WPO) in densified CO2 as the solvent is reported. The aim of this research is to investigate the potential used of sago starch and WPO as raw materials in the thermoplastics starch synthesis. The starch esters was successfully synthesized using sago starch and WPO as reagent in densified CO2 as shown from the presence of carbonyl group (C=O, 1743 cm-1) in the FT-IR spectra coupled with the presence of the proton (1H-NMR) of the fatty acid in the starch backbone (0.8 - 2 ppm). The product crystallinity decreases as shown in XRD results and resulting with a change in the thermal properties (melting and crystalline temperature) of the products. In addition, the products show a different granular morphology and a higher hydrophobicity compared with native sago starch. This research shows the potential used of sago starch and WPO in the thermoplastics starch synthesis and opens a new perspective on the product application.
Weijma, Jan; De Hoop, Klaas; Bosma, Wobby; Dijkman, Henk
2002-01-01
Lead paste, a solid mixture containing PbSO(4), PbO(2), PbO/Pb(OH)(2) precipitate, and elemental Pb, is one of the main waste fractions from spent car batteries. Biological sulfidation represents a new process for recovery of lead from this waste. In this process the lead salts in lead paste are converted to galena (PbS) by sulfate-reducing bacteria. This paper investigates a continuous process for sulfidation of anglesite (PbSO(4)), the main constituent of lead paste, and lead paste, consisting of a laboratory-scale gas-lift bioreactor to which a slurry of anglesite or lead paste was supplied. Sulfate or elemental sulfur was added as an additional sulfur source. Hydrogen gas served as an electron donor for the biological reduction of sulfate and elemental sulfur to sulfide by sulfate- and sulfur-reducing bacteria. Anglesite was almost completely converted to galena at a loading rate of 19 kg of PbSO(4) m(-)(3) day(-)(1), producing a sludge of which the crystalline lead phases consisted of >98% PbS (galena) and 1-2% elemental Pb. With lead paste, stable sulfidation rates of up to 17 kg of lead paste m(-)(3) day(-)(1) were demonstrated, producing a sludge of which the crystalline lead phases consisted of an estimated >96% PbS, 1-2% elemental Pb, and 1-2% PbO(2).
NASA Astrophysics Data System (ADS)
Kaur, Taranjot; Pal Singh, Gurwinder; Kaur, Gurneet; Kaur, Sukhvir; Gill, Prabhjot Kaur
2016-08-01
Biosilification is an economically viable, energy saving and green approach for the commercial scale synthesis of oxide nanomaterials. The room temperature synthesis of oxide nanocomposites from cost effective agro-based waste is a particular example of biosilification. In this study, synthesis of Si/SiO2 nanocomposites from inexpensive agro-based waste material i.e. rice husks (RH) and wheat bran (WB) has been carried out by means of various eukaryotic microorganisms, i.e. Actinomycete, Fusarium oxysporum, Aspergillus niger, Trichoderma sp. and Penicillium sp., under ambient conditions. The XRD diffrectrograms represents that the synthesized nanomaterials exhibits silicon, amorphous silica and other crystal arrays such as cristobalite, trydimite and quartz, depending upon the type microorganism and time period used for extraction. All of the aforesaid microorganism bio transformed the naturally occurring amorphous silica to crystalline structures within the period of 24 h. However, the Actinomycete and Trichoderma sp. took 48 h in case of rice husks for biotransformation of naturally occurring plant silica to crystalline nanocomposite. While in case of wheat bran, Actinomycete and Trichoderma sp. took 24 h for biotransformation. The extracted nanocomposites exhibits band edge in the range 230-250 nm and blue emission. The procedure described in study can be used for commercial level production of Si/SiO2 nanocomposites from agro based waste materials.
Jin, Jian; Li, Xiao-dong; Chi, Yong; Yan, Jian-hua
2010-04-01
A sodium carbonate assisted hydrothermal process was induced to stabilize the fly ash from medical waste incinerator. The results showed that sodium carbonate assisted hydrothermal process reduced the heavy metals leachability of fly ash, and the heavy metal waste water from the process would not be a secondary pollution. The leachability of heavy metals studied in this paper were Cd 1.97 mg/L, Cr 1.56 mg/L, Cu 2.56 mg/L, Mn 17.30 mg/L, Ni 1.65 mg/L, Pb 1.56 mg/L and Zn 189.00 mg/L, and after hydrothermal process with the optimal experimental condition (Na2CO3/fly ash dosage = 5/20, reaction time = 8 h, L/S ratio = 10/1) the leachability reduced to < 0.02 mg/L for Cd, Cr, Cu, Mn, Ni, Pb, and 0.05 mg/L for Zn, according to GB 5085.3-2007. Meanwhile, the concentrations of heavy metals in effluent after hydrothermal process were less than 0.8 mg/L. The heavy metals leachability and concentration in effluent reduced with prolonged reaction time. Prolonged aging can affect the leachability of metals as solids become more crystalline, and heavy metals transferred inside of crystalline. The mechanism of heavy metal stabilization can be concluded to the co precipitation and adsorption effect of aluminosilicates formation, crystallization and aging process.
Microscopic studies of polycrystalline nanoparticle growth in free space
NASA Astrophysics Data System (ADS)
Mohan, A.; Kaiser, M.; Verheijen, M. A.; Schropp, R. E. I.; Rath, J. K.
2017-06-01
We have extensively studied by multiple microscopic techniques the growth and crystallization of silicon nanoparticles in pulsed SiH4/Ar plasmas. We observe that the crystallinity of the particles can be tuned from amorphous to crystalline by altering the plasma ON time, tON. Three phases can be identified as a function of tON. Microscopic studies reveal that, in the initial gas phase (phase I) single particles of polycrystalline nature are formed which according to our hypothesis grow out of a single nucleus. The individual crystallites of the polycrystalline particles become bigger crystalline regions which marks the onset of cauliflower shaped particles (phase II). At longer tON (phase III) distinct cauliflower particles are formed by the growth of these crystalline regions by local epitaxy.
NASA Astrophysics Data System (ADS)
Stefanovsky, S. V.; Stefanovsky, O. I.; Kadyko, M. I.; Nikonov, B. S.
2018-03-01
Sodium aluminum (iron) phosphate glass ceramics containing of up to 20 wt.% rare earth (RE) oxides simulating pyroprocessing waste were produced by melting at 1250 °C followed by either quenching or slow cooling to room temperature. The iron-free glass-ceramics were composed of major glass and minor phosphotridymite and monazite. The iron-bearing glass-ceramics were composed of major glass and minor monazite and Na-Al-Fe orthophosphate at low waste loadings (5-10 wt.%) and major orthophosphate and minor monazite as well as interstitial glass at high waste loadings (15-20 wt.%). Slowly cooled samples contained higher amount of crystalline phases than quenched ones. Monazite is major phase for REs. Leach rates from the materials of major elements (Na, Al, Fe, P) are 10-5-10-7 g cm-2 d-1, RE elements - lower than 10-5 g cm-2 d-1.
New approach for extraction of cellulose from tucumã's endocarp and its structural characterization
NASA Astrophysics Data System (ADS)
Manzato, L.; Rabelo, L. C. A.; de Souza, S. M.; da Silva, C. G.; Sanches, E. A.; Rabelo, D.; Mariuba, L. A. M.; Simonsen, J.
2017-09-01
The recycling of plant wasted materials into useful products represents a green alternative to prevent environmental problems. Tucumã palm fruit (Astrocaryum aculeatum Meyer) is widely used in Amazon region for food and crafts. Due to the large amount of wasted Tucumã's endocarp, this work proposes a new approach for extraction of cellulose and its structural characterization. X-ray Diffraction (XRD), Rietveld Refinement, Scanning Electron Microscopy (SEM), Infrared-transform Fourier Spectroscopy (FTIR) and Thermal Analysis (TG/DSC) have been used for characterization of the extracted cellulose. XRD patterns of the in natura tucumã's endocarp has showed a natural crystalline content embedded in a non-crystalline matrix. Nanocrystals of cellulose have been observed in the XRD pattern of the extracted cellulose, showing a good agreement with type II. Rietveld refinement allowed the cell parameters obtainment (a = 8.43(1) Å, b = 9.50(1) Å, c = 9.39(3) Å and γ = 118.43(4)°). Apparent average crystallite size and microstrain were, respectively, 20.0 Å and 0.1%. Two different methods were applied for estimative of crystallinity percentage. In the first method the height ratio between the intensity of the crystalline peak and the total intensity after the subtraction of the non-crystalline content was applied, leading to 48.5%. The second approach was performed using the amorphous area and the total area of the (1 1 0) peak from the experimental diffractogram, leading to 31.5%. The difference in crystallinity percentage concerning these two used approaches may be explained due to the first method does not consider the broad peaks resulted from nanocrystals diffraction. FTIR spectroscopy has evidenced a cellulose type II structure. SEM images showed micrometric sized fibers with ranged thicknesses. However, a new morphology of spherical nanostructures was observed on the type II matrix fibers. Thermal analysis suggests that the extracted cellulose have low thermal stability, which resulted from poor ordered, packed chains. A large exothermic band was found in DSC curve and associated to the release of energy from the amorphous phase degradation. Thus, this work successfully extracted cellulose from tucumã's endocarp and allowed its structural, morphological and thermal characterization.
Mercado, D Fabio; Magnacca, Giuliana; Malandrino, Mery; Rubert, Aldo; Montoneri, Enzo; Celi, Luisella; Bianco Prevot, Alessandra; Gonzalez, Mónica C
2014-03-26
This paper describes the synthesis of paramegnetic iron-containing hydroxyapatite nanoparticles and their increased Cu(2+) sorbent capacity when using Ca(2+) complexes of soluble bioorganic substrates from urban wastes as synthesis precursors. A thorough characterization of the particles by TEM, XRD, FTIR spectroscopy, specific surface area, TGA, XPS, and DLS indicates that loss of crystallinity, a higher specific area, an increased surface oxygen content, and formation of surface iron phases strongly enhance Cu(2+) adsorption capacity of hydroxyapatite-based materials. However, the major effect of the surface and morphologycal modifications is the size diminution of the aggregates formed in aqueous solutions leading to an increased effective surface available for Cu(2+) adsorption. Maximum sorption values of 550-850 mg Cu(2+) per gram of particles suspended in an aqueous solution at pH 7 were determined, almost 10 times the maximum values observed for hydroxyapatite nanoparticles suspensions under the same conditions.
Solution-grown organic single-crystalline p-n junctions with ambipolar charge transport.
Fan, Congcheng; Zoombelt, Arjan P; Jiang, Hao; Fu, Weifei; Wu, Jiake; Yuan, Wentao; Wang, Yong; Li, Hanying; Chen, Hongzheng; Bao, Zhenan
2013-10-25
Organic single-crystalline p-n junctions are grown from mixed solutions. First, C60 crystals (n-type) form and, subsequently, C8-BTBT crystals (p-type) nucleate heterogeneously on the C60 crystals. Both crystals continue to grow simultaneously into single-crystalline p-n junctions that exhibit ambipolar charge transport characteristics. This work provides a platform to study organic single-crystalline p-n junctions. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Ermolina, I; Darkwah, J; Smith, G
2014-04-01
The control of the amorphous and crystalline states of drugs and excipients is important in many instances of product formulation, manufacture, and packaging, such as the formulation of certain (freeze-dried) fast melt tablets. This study examines the use of terahertz-pulsed spectroscopy (TPS) coupled with two different data analytical methods as an off-line tool (in the first instance) for assessing the degree of crystallinity in a binary mixture of amorphous and polycrystalline sucrose. The terahertz spectrum of sucrose was recorded in the wave number range between 3 and 100 cm(-1) for both the pure crystalline form and for a mixture of the crystalline and amorphous (freeze-dried) form. The THz spectra of crystalline sucrose showed distinct absorption bands at ∼48, ∼55, and ∼60 cm(-1) while all these features were absent in the amorphous sucrose. Calibration models were constructed based on (1) peak area analysis and (2) partial least square regression analysis, with the latter giving the best LOD and LOQ of 0.76% and 2.3%, respectively. The potential for using THz spectroscopy, as a quantitative in-line tool for percent crystallinity in a range of complex systems such as conventional tablets and freeze-dried formulations, is suggested in this study.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pires, Richard P.; Westsik, Joseph H.; Serne, R. Jeffrey
2011-07-14
Screening tests are being conducted to evaluate waste forms for immobilizing secondary liquid wastes from the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Plans are underway to add a stabilization treatment unit to the Effluent Treatment Facility to provide the needed capacity for treating these wastes from WTP. The current baseline is to use a Cast Stone cementitious waste form to solidify the wastes. Through a literature survey, DuraLith alkali-aluminosilicate geopolymer, fluidized-bed steam reformation (FBSR) granular product encapsulated in a geopolymer matrix, and a Ceramicrete phosphate-bonded ceramic were identified both as candidate waste forms and alternatives to the baseline.more » These waste forms have been shown to meet waste disposal acceptance criteria, including compressive strength and universal treatment standards for Resource Conservation and Recovery Act (RCRA) metals (as measured by the toxicity characteristic leaching procedure [TCLP]). Thus, these non-cementitious waste forms should also be acceptable for land disposal. Information is needed on all four waste forms with respect to their capability to minimize the release of technetium. Technetium is a radionuclide predicted to be in the secondary liquid wastes in small quantities, but the Integrated Disposal Facility (IDF) risk assessment analyses show that technetium, even at low mass, produces the largest contribution to the estimated IDF disposal impacts to groundwater.« less
Janikowski, Stuart K.
2000-01-01
A waste destruction method using a reactor vessel to combust and destroy organic and combustible waste, including the steps of introducing a supply of waste into the reactor vessel, introducing a supply of an oxidant into the reactor vessel to mix with the waste forming a waste and oxidant mixture, introducing a supply of water into the reactor vessel to mix with the waste and oxidant mixture forming a waste, water and oxidant mixture, reciprocatingly compressing the waste, water and oxidant mixture forming a compressed mixture, igniting the compressed mixture forming a exhaust gas, and venting the exhaust gas into the surrounding atmosphere.
Farias, Marco Antônio Dos Santos; Soares, Frederico Luis Felipe; Carneiro, Renato Lajarim
2016-03-20
Ezetimibe (EZT), in its anhydrous form, is a drug used for cholesterol and lipids reduction in blood plasma. The presence of EZT monohydrate in commercial tablets can change the solubility rate of the API, decreasing its activity. The objective of this work was to verify if the humidity present in the excipients could promote the phase transition from EZT anhydrous to hydrate. Initially the stability of the pure anhydrous form was monitored by Raman, at room temperature (23°C) and relative humidity (75%). The MCR-ALS method showed that almost all EZT changed to hydrated form in 30 min. Then tablets of ezetimibe in the presence of its excipients were prepared and vacuum packed using a polyethylene film. Such tablet was monitored by Raman spectroscopy for 24h in order to quantify the mixture of the crystalline forms. A multivariate calibration model using Raman spectroscopy and Partial Least Square (PLS) regression was built, with validation and cross validation errors around 0.6% (wt/wt), for both crystalline forms, and R(2) higher than 0.96. The PLS model was used to quantify the crystalline mixture of ezetimibe in the monitored tablet, after 24h more than 70% of ezetimibe changed to the hydrated form. Copyright © 2016 Elsevier B.V. All rights reserved.
Improvement of Leaching Resistance of Low-level Waste Form in Korea
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kim, J.Y.; Lee, B.C.; Kim, C.L.
2006-07-01
Low-level liquid concentrate wastes including boric acid have been immobilized with paraffin wax using concentrate waste drying system in Korean nuclear power plants since 1995. Small amount of low density polyethylene (LDPE) was added to increase the leaching resistance of the existing paraffin waste form and the influence of LDPE on the leaching behavior of waste form was investigated. It was observed that the leaching of nuclides immobilized within paraffin waste form remarkably reduced as the content of LDPE increased. The acceptance criteria of paraffin waste form associated with leachability index and compressive strength after the leaching test were successfullymore » satisfied with the help of LDPE. (authors)« less
Allan, Phoebe K.; Griffin, John M.; Darwiche, Ali; ...
2016-01-29
We use operando pair distribution function (PDF) analysis and ex situ 23Na magic-angle spinning solid-state nuclear magnetic resonance (MAS ssNMR) spectroscopy to gain insight into the alloying mechanism of high-capacity antimony anodes for sodium-ion batteries. Subtraction of the PDF of crystalline Na xSb phases from the total PDF, an approach constrained by chemical phase information gained from 23Na ssNMR in reference to relevant model compounds, identifies two previously uncharacterized intermediate species formed electrochemically; a-Na 3–xSb (x ≈ 0.4–0.5), a structure locally similar to crystalline Na 3Sb (c-Na 3Sb) but with significant numbers of sodium vacancies and a limited correlation length,more » and a-Na1.7Sb, a highly amorphous structure featuring some Sb–Sb bonding. The first sodiation breaks down the crystalline antimony to form first a-Na 3–xSb and, finally, crystalline Na 3Sb. Desodiation results in the formation of an electrode formed of a composite of crystalline and amorphous antimony networks. We link the different reactivity of these networks to a series of sequential sodiation reactions manifesting as a cascade of processes observed in the electrochemical profile of subsequent cycles. The amorphous network reacts at higher voltages reforming a-Na 1.7Sb, then a-Na 3–xSb, whereas lower potentials are required for the sodiation of crystalline antimony, which reacts to form a-Na 3–xSb without the formation of a-Na 1.7Sb. a-Na 3–xSb is converted to crystalline Na 3Sb at the end of the second discharge. In the end, we find no evidence of formation of NaSb. Variable temperature 23Na NMR experiments reveal significant sodium mobility within c-Na 3Sb; this is a possible contributing factor to the excellent rate performance of Sb anodes.« less
2016-01-01
Operando pair distribution function (PDF) analysis and ex situ 23Na magic-angle spinning solid-state nuclear magnetic resonance (MAS ssNMR) spectroscopy are used to gain insight into the alloying mechanism of high-capacity antimony anodes for sodium-ion batteries. Subtraction of the PDF of crystalline NaxSb phases from the total PDF, an approach constrained by chemical phase information gained from 23Na ssNMR in reference to relevant model compounds, identifies two previously uncharacterized intermediate species formed electrochemically; a-Na3–xSb (x ≈ 0.4–0.5), a structure locally similar to crystalline Na3Sb (c-Na3Sb) but with significant numbers of sodium vacancies and a limited correlation length, and a-Na1.7Sb, a highly amorphous structure featuring some Sb–Sb bonding. The first sodiation breaks down the crystalline antimony to form first a-Na3–xSb and, finally, crystalline Na3Sb. Desodiation results in the formation of an electrode formed of a composite of crystalline and amorphous antimony networks. We link the different reactivity of these networks to a series of sequential sodiation reactions manifesting as a cascade of processes observed in the electrochemical profile of subsequent cycles. The amorphous network reacts at higher voltages reforming a-Na1.7Sb, then a-Na3–xSb, whereas lower potentials are required for the sodiation of crystalline antimony, which reacts to form a-Na3–xSb without the formation of a-Na1.7Sb. a-Na3–xSb is converted to crystalline Na3Sb at the end of the second discharge. We find no evidence of formation of NaSb. Variable temperature 23Na NMR experiments reveal significant sodium mobility within c-Na3Sb; this is a possible contributing factor to the excellent rate performance of Sb anodes. PMID:26824406
DOE Office of Scientific and Technical Information (OSTI.GOV)
Allan, Phoebe K.; Griffin, John M.; Darwiche, Ali
We use operando pair distribution function (PDF) analysis and ex situ 23Na magic-angle spinning solid-state nuclear magnetic resonance (MAS ssNMR) spectroscopy to gain insight into the alloying mechanism of high-capacity antimony anodes for sodium-ion batteries. Subtraction of the PDF of crystalline Na xSb phases from the total PDF, an approach constrained by chemical phase information gained from 23Na ssNMR in reference to relevant model compounds, identifies two previously uncharacterized intermediate species formed electrochemically; a-Na 3–xSb (x ≈ 0.4–0.5), a structure locally similar to crystalline Na 3Sb (c-Na 3Sb) but with significant numbers of sodium vacancies and a limited correlation length,more » and a-Na1.7Sb, a highly amorphous structure featuring some Sb–Sb bonding. The first sodiation breaks down the crystalline antimony to form first a-Na 3–xSb and, finally, crystalline Na 3Sb. Desodiation results in the formation of an electrode formed of a composite of crystalline and amorphous antimony networks. We link the different reactivity of these networks to a series of sequential sodiation reactions manifesting as a cascade of processes observed in the electrochemical profile of subsequent cycles. The amorphous network reacts at higher voltages reforming a-Na 1.7Sb, then a-Na 3–xSb, whereas lower potentials are required for the sodiation of crystalline antimony, which reacts to form a-Na 3–xSb without the formation of a-Na 1.7Sb. a-Na 3–xSb is converted to crystalline Na 3Sb at the end of the second discharge. In the end, we find no evidence of formation of NaSb. Variable temperature 23Na NMR experiments reveal significant sodium mobility within c-Na 3Sb; this is a possible contributing factor to the excellent rate performance of Sb anodes.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Allan, Phoebe K.; Griffin, John M.; Darwiche, Ali
Operando pair distribution function (PDF) analysis and ex situ Na-23 magic-angle spinning solid-state nuclear magnetic resonance (MAS ssNMR) spectroscopy are used to gain insight into the alloying mechanism of high-capacity antimony anodes for sodium-ion batteries. Subtraction of the PDF of crystalline NaxSb phases from the total PDF, an approach constrained by chemical phase information gained from Na-23 ssNMR in reference to relevant model compounds, identifies two previously uncharacterized intermediate species formed electro-chemically; a-Na3-xSb (x approximate to 0.4-0.5), a structure locally similar to crystalline Na3Sb (c-Na3Sb) but with significant numbers of sodium vacancies and a limited correlation length, and a-Na1.7Sb, amore » highly amorphous structure featuring some Sb-Sb bonding. The first sodiation breaks down the crystalline antimony to form first a-Na3-xSb and, finally, crystalline Na3Sb. Desodiation results in the formation of an electrode formed of a composite of crystalline and amorphous antimony networks. We link the different reactivity of these networks to a series of sequential sodiation reactions manifesting as a cascade of processes observed in the electrochemical profile of subsequent cycles. The amorphofis network reacts at higher voltages reforming a-Na1.7Sb, then a-Na3-xSb, whereas lower potentials are required for the sodiation of crystalline antimony, which reacts to form a-Na3-xSb without the formation of a-Na3-xSb. a-Na3-xSb is converted to crystalline Na3Sb at the end of the second discharge. We find no evidence of formation of NaSb. Variable temperature Na-23 NMR experiments reveal significant sodium mobility within c-Na3Sb; this is a possible contributing factor to the excellent rate performance of Sb anodes.« less
Cellulose promotes extracellular assembly of Clostridium cellulovorans cellulosomes.
Matano, Y; Park, J S; Goldstein, M A; Doi, R H
1994-01-01
Cellulosome synthesis by Clostridium cellulovorans was investigated by growing the cells in media containing different carbon sources. Supernatant from cells grown with cellobiose contained no cellulosomes and only the free forms of cellulosomal major subunits CbpA, P100, and P70 and the minor subunits with enzymatic activity. Supernatant from cells grown on pebble-milled cellulose and Avicel contained cellulosomes capable of degrading crystalline cellulose. Supernatants from cells grown with cellobiose, pebble-milled cellulose, and Avicel contained about the same amount of carboxymethyl cellulase activity. Although the supernatant from the medium containing cellobiose did not initially contain active cellulosomes, the addition of crystalline cellulose to the cell-free supernatant fraction converted the free major forms to cellulosomes with the ability to degrade crystalline cellulose. The binding of P100 and P70 to crystalline cellulose was dependent on their attachment to the endoglucanase-binding domains of CbpA. These data strongly indicate that crystalline cellulose promotes cellulosome assembly. Images PMID:7961457
Method of forming grooves in the [011] crystalline direction
NASA Technical Reports Server (NTRS)
Marinelli, Donald Paul (Inventor)
1977-01-01
An A-B etchant is applied to a (100) surface of a body of semiconductor material, a portion of which along the (100) surface of the body is either gallium arsenide or gallium aluminum arsenide. The etchant is applied for at least 15 seconds at a temperature of approximately 80.degree. C. The A-B etchant is a solution by weight percent of 47.5%, water, 0.2% silver nitrate, 23.8% chromium trioxide and 28.5% of a 48% aqueous solution of hydrofluoric acid. As a result of the application of the A-B etchant a pattern of elongated etch pits form having their longitudinal axes along the [011] crystalline direction. Grooves are formed in the body at a surface opposite the (100) surface on which was applied the etchant. The grooves are formed along the [011] crystalline direction by aligning the longitudinal axes of the grooves with the longitudinal axes of the etch pits.
A U-bearing composite waste form for electrochemical processing wastes
NASA Astrophysics Data System (ADS)
Chen, X.; Ebert, W. L.; Indacochea, J. E.
2018-04-01
Metallic/ceramic composite waste forms are being developed to immobilize combined metallic and oxide waste streams generated during electrochemical recycling of used nuclear fuel. Composites were made for corrosion testing by reacting HT9 steel to represent fuel cladding, Zr and Mo to simulate metallic fuel waste, and a mixture of ZrO2, Nd2O3, and UO2 to represent oxide wastes. More than half of the added UO2 was reduced to metal and formed Fe-Zr-U intermetallics and most of the remaining UO2 and all of the Nd2O3 reacted to form zirconates. Fe-Cr-Mo intermetallics were also formed. Microstructure characterization of the intermetallic and ceramic phases that were generated and tests conducted to evaluate their corrosion behaviors indicate composite waste forms can accommodate both metallic and oxidized waste streams in durable host phases.
A U-bearing composite waste form for electrochemical processing wastes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, X.; Ebert, W. L.; Indacochea, J. E.
Metallic/ceramic composite waste forms are being developed to immobilize combined metallic and oxide waste streams generated during electrochemical recycling of used nuclear fuel. Composites were made for corrosion testing by reacting HT9 steel to represent fuel cladding, Zr and Mo to simulate metallic fuel waste, and a mixture of ZrO2, Nd2O3, and UO2 to represent oxide wastes. More than half of the added UO2 was reduced to metal and formed Fe-Zr-U intermetallics and most of the remaining UO2 and all of the Nd2O3 reacted to form zirconates. Fe-Cr-Mo intermetallics were also formed. Microstructure characterization of the intermetallic and ceramic phasesmore » that were generated and tests conducted to evaluate their corrosion behaviors indicate composite waste forms can accommodate both metallic and oxidized waste streams in durable host phases. (c) 2018 Elsevier B.V. All rights reserved.« less
Stabilization and disposal of Argonne-West low-level mixed wastes in ceramicrete waste forms.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Barber, D. B.; Singh, D.; Strain, R. V.
1998-02-17
The technology of room-temperature-setting phosphate ceramics or Ceramicrete{trademark} technology, developed at Argonne National Laboratory (ANL)-East is being used to treat and dispose of low-level mixed wastes through the Department of Energy complex. During the past year, Ceramicrete{trademark} technology was implemented for field application at ANL-West. Debris wastes were treated and stabilized: (a) Hg-contaminated low-level radioactive crushed light bulbs and (b) low-level radioactive Pb-lined gloves (part of the MWIR {number_sign} AW-W002 waste stream). In addition to hazardous metals, these wastes are contaminated with low-level fission products. Initially, bench-scale waste forms with simulated and actual waste streams were fabricated by acid-base reactionsmore » between mixtures of magnesium oxide powders and an acid phosphate solution, and the wastes. Size reduction of Pb-lined plastic glove waste was accomplished by cryofractionation. The Ceramicrete{trademark} process produces dense, hard ceramic waste forms. Toxicity Characteristic Leaching Procedure (TCLP) results showed excellent stabilization of both Hg and Pb in the waste forms. The principal advantage of this technology is that immobilization of contaminants is the result of both chemical stabilization and subsequent microencapsulation of the reaction products. Based on bench-scale studies, Ceramicrete{trademark} technology has been implemented in the fabrication of 5-gal waste forms at ANL-West. Approximately 35 kg of real waste has been treated. The TCLP is being conducted on the samples from the 5-gal waste forms. It is expected that because the waste forms pass the limits set by the EPAs Universal Treatment Standard, they will be sent to a radioactive-waste disposal facility.« less
2012-08-30
improve oxidation resistance due to a rapidly forming ceramic-like, passivating and self - healing silica layer when exposed to high incident fluxes...have stronger bond dissociation energies (-8.3 eV). The POSS cage is not destroyed by the AO, but forms a passivating self -rigidizing/ self - healing ...polymers (including amorphous, semi-crystalline, crystalline, and rubber , etc.) possess con- siderable amounts of internal and external free volume
Liquid secondary waste: Waste form formulation and qualification
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cozzi, A. D.; Dixon, K. L.; Hill, K. A.
The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams generated during site cleanup activities. When the Hanford Tank Waste Treatment and Immobilization Plant (WTP) begins operations, including Direct Feed Low Activity Waste (DFLAW) vitrification, a liquid secondary waste (LSW) stream from the WTP will need to be treated. The volume of effluent for treatment at the ETF will increase significantly. The powdered salt waste form produced by the ETF will be replaced by a stabilized solidified waste form for disposal in Hanford’s Integrated Disposal Facility (IDF). Washington River Protection Solutions is implementing a Secondary Liquid Waste Immobilizationmore » Technology Development Plan to address the technology needs for a waste form and solidification process to treat the increased volume of waste planned for disposal at the IDF. Waste form testing to support this plan is composed of work in the near term to provide data as input to a performance assessment (PA) for Hanford’s IDF. In 2015, three Hanford Liquid Secondary Waste simulants were developed based on existing and projected waste streams. Using these waste simulants, fourteen mixes of Hanford Liquid Secondary Waste were prepared and tested varying the waste simulant, the water-to-dry materials ratio, and the dry materials blend composition.1 In FY16, testing was performed using a simulant of the EMF process condensate blended with the caustic scrubber—from the Low Activity Waste (LAW) melter—, processed through the ETF. The initial EMF-16 simulant will be based on modeling efforts performed to determine the mass balance of the ETF for the DFLAW.2 The compressive strength of all of the mixes exceeded the target of 3.4 MPa (500 psi) to meet the requirements identified as potential IDF Waste Acceptance Criteria in Table 1 of the Secondary Liquid Waste Immobilization Technology Development Plan.3 The hydraulic properties of the waste forms tested (hydraulic conductivity and water characteristic curves) were comparable to the properties measured on the Savannah River Site (SRS) Saltstone waste form. Future testing should include efforts to first; 1) determine the rate and amount of ammonia released during each unit operation of the treatment process to determine if additional ammonia management is required, then; 2) reduce the ammonia content of the ETF concentrated brine prior to solidification, making the waste more amenable to grouting, or 3) manage the release of ammonia during production and ongoing release during storage of the waste form, or 4) develop a lower pH process/waste form thereby precluding ammonia release.« less
TANK 26F SUPERNATANT AND 2F EVAPORATOR EDUCTOR PUMP SAMPLE CHARACTERIZATION RESULTS
DOE Office of Scientific and Technical Information (OSTI.GOV)
King, W.; Hay, M.; Coleman, C.
2011-08-23
In an effort to understand the reasons for system plugging problems in the SRS 2F evaporator, supernatant samples were retrieved from the evaporator feed tank (Tank 26F) and solids were collected from the evaporator eductor feed pump for characterization. The variable depth supernatant samples were retrieved from Tank 26F in early December of 2010 and samples were provided to SRNL and the F/H Area laboratories for analysis. Inspection and analysis of the samples at SRNL was initiated in early March of 2011. During the interim period, samples were frequently exposed to temperatures as low as 12 C with daily temperaturemore » fluctuations as high as 10 C. The temperature at the time of sample collection from the waste tank was 51 C. Upon opening the supernatant bottles at SRNL, many brown solids were observed in both of the Tank 26F supernatant samples. In contrast, no solids were observed in the supernatant samples sent to the F/H Area laboratories, where the analysis was completed within a few days after receipt. Based on these results, it is believed that the original Tank 26F supernatant samples did not contain solids, but solids formed during the interim period while samples were stored at ambient temperature in the SRNL shielded cells without direct climate control. Many insoluble solids (>11 wt. % for one sample) were observed in the Tank 26F supernatant samples after three months of storage at SRNL which would not dissolve in the supernatant solution in two days at 51 C. Characterization of these solids along with the eductor pump solids revealed the presence of sodium oxalate and clarkeite (uranyl oxyhydroxide) as major crystalline phases. Sodium nitrate was the dominant crystalline phase present in the unwashed Eductor Pump solids. Crystalline sodium nitrate may have formed during the drying of the solids after filtration or may have been formed in the Tank 26F supernatant during storage since the solution was found to be very concentrated (9-12 M Na{sup +}). Concentrated mineral acids and elevated temperature were required to dissolve all of these solids. The refractory nature of some of the solids is consistent with the presence of metal oxides such as aluminosilicates (observed as a minor phase by XRD). Characterization of the water wash solutions and the digested solids confirmed the presence of oxalate salts in both solid samples. Sulfate enrichment was also observed in the Tank 26F solids wash solution, indicating the presence of sulfate precipitates such as burkeite. OLI modeling of the Tank 26F filtered supernatant composition revealed that sodium oxalate has a very low solubility in this solution. The model predicts that the sodium oxalate solubility in the Tank 26F supernatant is only 0.0011 M at 50 C. The results indicate that the highly concentrated nature of the evaporator feed solution and the addition of oxalate anion to the waste stream each contribute to the formation of insoluble solids in the 2F evaporator system.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Garn, Troy G; Law, Jack D; Greenhalgh, Mitchell R
A composite media including at least one crystalline aluminosilicate material in polyacrylonitrile. A method of forming a composite media is also disclosed. The method comprises dissolving polyacrylonitrile in an organic solvent to form a matrix solution. At least one crystalline aluminosilicate material is combined with the matrix solution to form a composite media solution. The organic solvent present in the composite media solution is diluted. The composite media solution is solidified. In addition, a method of processing a fluid stream is disclosed. The method comprises providing a beads of a composite media comprising at least one crystalline aluminosilicate material dispersedmore » in a polyacrylonitrile matrix. The beads of the composite media are contacted with a fluid stream comprising at least one constituent. The at least one constituent is substantially removed from the fluid stream.« less
Cesium titanium silicate and method of making
Balmer, Mari L.
1997-01-01
The invention is the new material, a ternary compound of cesium, silica, and titania, together with a method of making the ternary compound, cesium titanium silicate pollucite. More specifically, the invention is Cs.sub.2 Ti.sub.2 Si.sub.4 O.sub.13 pollucite which is a new crystalline phase representing a novel class of Ti-containing zeolites. Compositions contain relatively high Cs.sub.2 O and TiO.sub.2 loadings and are durable glass and ceramic materials. The amount of TiO.sub.2 and Cs.sub.2 that can be incorporated into these glasses and crystalline ceramics far exceeds the limits set for the borosilicate high level waste glass.
Cesium titanium silicate and method of making
Balmer, M.L.
1997-01-07
The invention is the new material, a ternary compound of cesium, silica, and titania, together with a method of making the ternary compound, cesium titanium silicate pollucite. More specifically, the invention is Cs{sub 2}Ti{sub 2}Si{sub 4}O{sub 13} pollucite which is a new crystalline phase representing a novel class of Ti-containing zeolites. Compositions contain relatively high Cs{sub 2}O and TiO{sub 2} loadings and are durable glass and ceramic materials. The amount of TiO{sub 2} and Cs{sub 2} that can be incorporated into these glasses and crystalline ceramics far exceeds the limits set for the borosilicate high level waste glass. 10 figs.
Method of preparing nuclear wastes for tansportation and interim storage
Bandyopadhyay, Gautam; Galvin, Thomas M.
1984-01-01
Nuclear waste is formed into a substantially water-insoluble solid for temporary storage and transportation by mixing the calcined waste with at least 10 weight percent powdered anhydrous sodium silicate to form a mixture and subjecting the mixture to a high humidity environment for a period of time sufficient to form cementitious bonds by chemical reaction. The method is suitable for preparing an interim waste form from dried high level radioactive wastes.
Mixture design and treatment methods for recycling contaminated sediment.
Wang, Lei; Kwok, June S H; Tsang, Daniel C W; Poon, Chi-Sun
2015-01-01
Conventional marine disposal of contaminated sediment presents significant financial and environmental burden. This study aimed to recycle the contaminated sediment by assessing the roles and integration of binder formulation, sediment pretreatment, curing method, and waste inclusion in stabilization/solidification. The results demonstrated that the 28-d compressive strength of sediment blocks produced with coal fly ash and lime partially replacing cement at a binder-to-sediment ratio of 3:7 could be used as fill materials for construction. The X-ray diffraction analysis revealed that hydration products (calcium hydroxide) were difficult to form at high sediment content. Thermal pretreatment of sediment removed 90% of indigenous organic matter, significantly increased the compressive strength, and enabled reuse as non-load-bearing masonry units. Besides, 2-h CO2 curing accelerated early-stage carbonation inside the porous structure, sequestered 5.6% of CO2 (by weight) in the sediment blocks, and acquired strength comparable to 7-d curing. Thermogravimetric analysis indicated substantial weight loss corresponding to decomposition of poorly and well crystalline calcium carbonate. Moreover, partial replacement of contaminated sediment by various granular waste materials notably augmented the strength of sediment blocks. The metal leachability of sediment blocks was minimal and acceptable for reuse. These results suggest that contaminated sediment should be viewed as useful resources. Copyright © 2014 Elsevier B.V. All rights reserved.
Majuste, Daniel; Mansur, Marcelo Borges
2008-05-01
The argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking industry is a hazardous waste due to the presence of chromium. While its coarse fraction is usually recycled into the own industrial process, the fine fraction is normally disposed in landfills. Techniques such as briquetting or magnetic separation were found to be inadequate to treat it for reuse purposes. So, in this work, the fine fraction of the AOD-L sludge was characterized aiming to find alternative methods to treat it. This sludge consists of a fine powder (mean diameter of 1 microm) containing 34 +/- 2% (w/w) of iron, 10.2 +/- 0.9% (w/w) of chromium and 1.4 +/- 0.1% (w/w) of nickel. The main crystalline phases identified in this study were chromite (FeCr(2)O(4)), magnetite (Fe(3)O(4)), hematite (Fe(2)O(3)) and calcite (CaCO(3)). In the digestion tests, the addition of HClO(4) has favored the dissolution of chromite which is a very stable oxide in aqueous media. Nickel was found in very fine particles, probably in the metallic form or associated with iron and oxygen. The sludge was classified as hazardous waste, so its disposal in landfills should be avoided.
NASA Astrophysics Data System (ADS)
Pet'kov, Vladimir; Asabina, Elena; Loshkarev, Vladimir; Sukhanov, Maksim
2016-04-01
We have summarized our data and literature ones on the thermophysical properties and hydrolytic stability of Sr0.5Zr2(PO4)3 compound as a host NaZr2(PO4)3-type (NZP) structure for immobilization of 90Sr-containing radioactive waste. Absence of any polymorphic transformations on the temperature dependence of its heat capacity between 7 and 665 K is caused by the stability of crystalline Sr0.5Zr2(PO4)3. Calculated values of thermal conductivity coefficients at zero porosity in the range 298-673 K were 1.86-2.40 W·m-1 K-1. The compound may be classified as low thermal expanding material due to its average linear thermal expansion coefficient. Study of the hydrolytic stability in acid and alkaline media has shown that the relative mass fraction of Sr2+ ions, released into aggressive leaching media, didn't exceed 1% of the mass of sample. Soxhlet leaching studies have shown substantial resistance towards the release of Sr2+ ions into distilled water. Feeble sinterability constrains practical applications of NZP substances, that is why known in literature methods of Sr0.5Zr2(PO4)3 dense ceramics obtaining have been reviewed.
Wang, Yuguo; Tang, Rentao; Tao, Jin; Gao, Gui; Wang, Xiaonan; Mu, Ying; Feng, Yan
2011-09-01
For the efficient degradation and bioconversion of cellulosic biomass, it is important to efficiently disrupt and convert crystalline regions of cellulose into easily hydrolyzable regions than to simply hydrolyze cellulose. Expansin-like proteins such as swollenins have disruptive functions on lignocellulose, including crystalline cellulose, via non-hydrolytic mechanisms. In this work, we produced the swollenin from Trichoderma asperellum in Escherichia coli. The recombinant protein was then refolded into the bioactive form with simultaneous purification via a novel cellulose-assisted process. We devised a novel, simple, and efficient method to quantitatively determine the non-hydrolytic disruptive activity of swollenin on crystalline cellulose. This method is based on the synergism of the swollenin and the endoglucanase FnCel5A from Fervidobacterium nodosum. The change from crystalline regions into easily hydrolyzable forms, due to non-hydrolytic disruption, might be slight and not easily be observed. However, disrupted regions of cellulose could be hydrolyzed by FnCel5A, and reducing sugars were formed by the synergism. The disruptive function of the swollenin was quantitatively characterized by measuring the release of reducing sugars. These methods and processes will be useful for further research on non-hydrolytic disruptive bioactivities and provide novel approaches for the efficient and economical bioconversion of cellulosic biomass.
Alloy and method of producing the same
Hufnagel, Todd C.; Ott, Ryan T.; Fan, Cang; Kecskes, Laszlo
2005-07-19
In accordance with a preferred embodiment of the invention, an alloy or other composite material is provided formed of a bulk metallic glass matrix with a microstructure of crystalline metal particles. The alloy preferably has a composition of (X.sub.a Ni.sub.b Cu.sub.c).sub.100-d-c Y.sub.d Al.sub.c, wherein the sum of a, b and c equals 100, wherein 40.ltoreq.a.ltoreq.80, 0.ltoreq.b.ltoreq.35, 0.ltoreq.c.ltoreq.40, 4.ltoreq.d.ltoreq.30, and 0.ltoreq.e.ltoreq.20, and wherein preferably X is composed of an early transition metal and preferably Y is composed of a refractory body-centered cubic early transition metal. A preferred embodiment of the invention also provides a method of producing an alloy composed of two or more phases at ambient temperature. The method includes the steps of providing a metastable crystalline phase composed of at least two elements, heating the metastable crystalline phase together with at least one additional element to form a liquid, casting the liquid, and cooling the liquid to form the alloy. In accordance with a preferred embodiment of the invention, the composition and cooling rate of the liquid can be controlled to determine the volume fraction of the crystalline phase and determine the size of the crystalline particles, respectively.
Doycheva, Deshka; Preuss, Beate; Deuter, Christoph; Zierhut, Manfred; Klein, Reinhild
2012-02-01
A high incidence of autoantibodies to lens proteins has been found in sera of patients with uveitis. We showed previously that the anti-lens antibodies reacted predominantly with α-crystallins. The aim of the present study was to identify immunodominant epitopes within the protein chains of human αA- and αB-crystallin. Epitope specificities of antibodies to αA- and αB-crystallin were examined by ELISA using synthetic overlapping peptides, spanning the entire length of both α-crystallins. The peptides consisted of 25 amino acid residues, with an overlap of at least eight amino acids each. The synthetic peptides were tested against sera of 110 patients with different uveitis forms, classified according to anatomical location of intraocular inflammation. Four immunodominant regions within the protein chains of αA- and αB-crystallin could be identified. These regions were recognized by antibodies in sera of 56% of uveitis patients. Anti-lens antibodies of IgG-type reacted preferentially with regions located at amino acid (aa) residues aa:69-93 and aa:137-161 of αA-crystallin as well as aa:69-110 and aa:137-161 of αB-crystallin. IgM antibodies recognized predominantly region aa:149-173 of αA-crystallin, and aa:69-110 and aa:151-175 of αB-crystallin. IgM antibodies directed to peptide aa:69-93 of αB-crystallin were found in sera of 30% of patients with intermediate uveitis. Four immunodominant B-cell epitopes within the protein chains of αA- and αB-crystallin have been identified; however, no clear correlation with the anatomically defined uveitis subtypes has been found except for intermediate uveitis. Whether there may be a correlation with uveitis forms with similar etiopathogenesis has to be evaluated in further studies.
Liquid secondary waste. Waste form formulation and qualification
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cozzi, A. D.; Dixon, K. L.; Hill, K. A.
The Hanford Site Effluent Treatment Facility (ETF) currently treats aqueous waste streams generated during Site cleanup activities. When the Hanford Tank Waste Treatment and Immobilization Plant (WTP) begins operations, a liquid secondary waste (LSW) stream from the WTP will need to be treated. The volume of effluent for treatment at the ETF will increase significantly. Washington River Protection Solutions is implementing a Secondary Liquid Waste Immobilization Technology Development Plan to address the technology needs for a waste form and solidification process to treat the increased volume of waste planned for disposal at the Integrated Disposal Facility IDF). Waste form testingmore » to support this plan is composed of work in the near term to demonstrate the waste form will provide data as input to a performance assessment (PA) for Hanford’s IDF.« less
Science is the first step to siting nuclear waste repositories
Neuzil, Christopher E.
2014-01-01
As Shaw [2014] notes, U.S. research on shale as a repository host was halted before expending anything close to the effort devoted to studying crystalline rock, salt, and - most notably - tuff at Yucca Mountain. The new political reality regarding Yucca Mountain may allow reconsideration of the decision to abandon research on shale as a repository host.
LITERATURE REVIEWS TO SUPPORT ION EXCHANGE TECHNOLOGY SELECTION FOR MODULAR SALT PROCESSING
DOE Office of Scientific and Technical Information (OSTI.GOV)
King, W
2007-11-30
This report summarizes the results of literature reviews conducted to support the selection of a cesium removal technology for application in a small column ion exchange (SCIX) unit supported within a high level waste tank. SCIX is being considered as a technology for the treatment of radioactive salt solutions in order to accelerate closure of waste tanks at the Savannah River Site (SRS) as part of the Modular Salt Processing (MSP) technology development program. Two ion exchange materials, spherical Resorcinol-Formaldehyde (RF) and engineered Crystalline Silicotitanate (CST), are being considered for use within the SCIX unit. Both ion exchange materials havemore » been studied extensively and are known to have high affinities for cesium ions in caustic tank waste supernates. RF is an elutable organic resin and CST is a non-elutable inorganic material. Waste treatment processes developed for the two technologies will differ with regard to solutions processed, secondary waste streams generated, optimum column size, and waste throughput. Pertinent references, anticipated processing sequences for utilization in waste treatment, gaps in the available data, and technical comparisons will be provided for the two ion exchange materials to assist in technology selection for SCIX. The engineered, granular form of CST (UOP IE-911) was the baseline ion exchange material used for the initial development and design of the SRS SCIX process (McCabe, 2005). To date, in-tank SCIX has not been implemented for treatment of radioactive waste solutions at SRS. Since initial development and consideration of SCIX for SRS waste treatment an alternative technology has been developed as part of the River Protection Project Waste Treatment Plant (RPP-WTP) Research and Technology program (Thorson, 2006). Spherical RF resin is the baseline media for cesium removal in the RPP-WTP, which was designed for the treatment of radioactive waste supernates and is currently under construction in Hanford, WA. Application of RF for cesium removal in the Hanford WTP does not involve in-riser columns but does utilize the resin in large scale column configurations in a waste treatment facility. The basic conceptual design for SCIX involves the dissolution of saltcake in SRS Tanks 1-3 to give approximately 6 M sodium solutions and the treatment of these solutions for cesium removal using one or two columns supported within a high level waste tank. Prior to ion exchange treatment, the solutions will be filtered for removal of entrained solids. In addition to Tanks 1-3, solutions in two other tanks (37 and 41) will require treatment for cesium removal in the SCIX unit. The previous SCIX design (McCabe, 2005) utilized CST for cesium removal with downflow supernate processing and included a CST grinder following cesium loading. Grinding of CST was necessary to make the cesium-loaded material suitable for vitrification in the SRS Defense Waste Processing Facility (DWPF). Because RF resin is elutable (and reusable) and processing requires conversion between sodium and hydrogen forms using caustic and acidic solutions more liquid processing steps are involved. The WTP baseline process involves a series of caustic and acidic solutions (downflow processing) with water washes between pH transitions across neutral. In addition, due to resin swelling during conversion from hydrogen to sodium form an upflow caustic regeneration step is required. Presumably, one of these basic processes (or some variation) will be utilized for MSP for the appropriate ion exchange technology selected. CST processing involves two primary waste products: loaded CST and decontaminated salt solution (DSS). RF processing involves three primary waste products: spent RF resin, DSS, and acidic cesium eluate, although the resin is reusable and typically does not require replacement until completion of multiple treatment cycles. CST processing requires grinding of the ion exchange media, handling of solids with high cesium loading, and handling of liquid wash and conditioning solutions. RF processing requires handling and evaporation of cesium eluates, disposal of spent organic resin, and handling of the various liquid wash and regenerate solutions used. In both cases, the DSS will be immobilized in a low activity waste form. It appears that both technologies are mature, well studied, and generally suitable for this application. Technology selection will likely be based on downstream impacts or preferences between the various processing options for the two materials rather than on some unacceptable performance property identified for one material. As a result, the following detailed technical review and summary of the two technologies should be useful to assist in technology selection for SCIX.« less
High-level waste program progress report, April 1, 1980-June 30, 1980
DOE Office of Scientific and Technical Information (OSTI.GOV)
None
1980-08-01
The highlights of this report are on: waste management analysis for nuclear fuel cycles; fixation of waste in concrete; study of ceramic and cermet waste forms; alternative high-level waste forms development; and high-level waste container development.
International Collaboration Activities on Engineered Barrier Systems
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jove-Colon, Carlos F.
The Used Fuel Disposition Campaign (UFDC) within the DOE Fuel Cycle Technologies (FCT) program has been engaging in international collaborations between repository R&D programs for high-level waste (HLW) disposal to leverage on gathered knowledge and laboratory/field data of near- and far-field processes from experiments at underground research laboratories (URL). Heater test experiments at URLs provide a unique opportunity to mimetically study the thermal effects of heat-generating nuclear waste in subsurface repository environments. Various configurations of these experiments have been carried out at various URLs according to the disposal design concepts of the hosting country repository program. The FEBEX (Full-scale Engineeredmore » Barrier Experiment in Crystalline Host Rock) project is a large-scale heater test experiment originated by the Spanish radioactive waste management agency (Empresa Nacional de Residuos Radiactivos S.A. – ENRESA) at the Grimsel Test Site (GTS) URL in Switzerland. The project was subsequently managed by CIEMAT. FEBEX-DP is a concerted effort of various international partners working on the evaluation of sensor data and characterization of samples obtained during the course of this field test and subsequent dismantling. The main purpose of these field-scale experiments is to evaluate feasibility for creation of an engineered barrier system (EBS) with a horizontal configuration according to the Spanish concept of deep geological disposal of high-level radioactive waste in crystalline rock. Another key aspect of this project is to improve the knowledge of coupled processes such as thermal-hydro-mechanical (THM) and thermal-hydro-chemical (THC) operating in the near-field environment. The focus of these is on model development and validation of predictions through model implementation in computational tools to simulate coupled THM and THC processes.« less
Jew, A.D.; Kim, C.S.; Rytuba, J.J.; Gustin, M.S.; Brown, Gordon E.
2011-01-01
Mercury in the environment is of prime concern to both ecosystem and human health. Determination of the molecular-level speciation of Hg in soils and mine wastes is important for understanding its sequestration, mobility, and availability for methylation. Extended X-ray absorption fine structure (EXAFS) spectroscopy carried out under ambient P-T conditions has been used in a number of past studies to determine Hg speciation in complex mine wastes and associated soils. However, this approach cannot detect elemental (liquid) mercury in Hg-polluted soils and sediments due to the significant structural disorder of liquid Hg at ambient-temperature. A new sample preparation protocol involving slow cooling through the crystallization temperature of Hg(0) (234 K) results in its transformation to crystalline ??-Hg(0). The presence and proportion of Hg(0), relative to other crystalline Hg-bearing phases, in samples prepared in this way can be quantified by low-temperature (77 K) EXAFS spectroscopy. Using this approach, we have determined the relative concentrations of liquid Hg(0) in Hg mine wastes from several sites in the California Coast Range and have found that they correlate well with measured fluxes of gaseous Hg released during light and dark exposure of the same samples, with higher evasion ratios from samples containing higher concentrations of liquid Hg(0). Two different linear relationships are observed in plots of the ratio of Hg emission under light and dark conditions vs % Hg(0), corresponding to silica-carbonate- and hot springs-type Hg deposits, with the hot springs-type samples exhibiting higher evasion fluxes than silica-carbonate type samples at similar Hg(0) concentrations. Our findings help explain significant differences in Hg evasion data for different mine sites in the California Coast Range. ?? 2011 American Chemical Society.
Spent fuel treatment and mineral waste form development at Argonne National Laboratory-West
DOE Office of Scientific and Technical Information (OSTI.GOV)
Goff, K.M.; Benedict, R.W.; Bateman, K.
1996-07-01
At Argonne National Laboratory-West (ANL-West) there are several thousand kilograms of metallic spent nuclear fuel containing bond sodium. This fuel will be treated in the Fuel Conditioning Facility (FCF) at ANL-West to produce stable waste forms for storage and disposal. Both mineral and metal high-level waste forms will be produced. The mineral waste form will contain the active metal fission products and the transuranics. Cold small-scale waste form testing has been on-going at Argonne in Illinois. Large-scale testing is commencing at ANL-West.
Durability and degradation of HT9 based alloy waste forms with variable Ni and Cr content
DOE Office of Scientific and Technical Information (OSTI.GOV)
Olson, L.
2016-12-31
Short-term electrochemical and long-term hybrid electrochemical corrosion tests were performed on alloy waste forms in reference aqueous solutions that bound postulated repository conditions. The alloy waste forms investigated represent candidate formulations that can be produced with advanced electrochemical treatment of used nuclear fuel. The studies helped to better understand the alloy waste form durability with differing concentrations of nickel and chromium, species that can be added to alloy waste forms to potentially increase their durability and decrease radionuclide release into the environment.
Options for the Separation and Immobilization of Technetium
DOE Office of Scientific and Technical Information (OSTI.GOV)
Serne, R Jeffrey; Crum, Jarrod V.; Riley, Brian J.
Among radioactive constituents present in the Hanford tank waste, technetium-99 (Tc) presents a unique challenge in that it is significantly radiotoxic, exists predominantly in the liquid low-activity waste (LAW), and has proven difficult to effectively stabilize in a waste form for ultimate disposal. Within the Hanford Tank Waste Treatment and Immobilization Plant, the LAW fraction will be converted to a glass waste form in the LAW vitrification facility, but a significant fraction of Tc volatilizes at the high glass-melting temperatures and is captured in the off-gas treatment system. This necessitates recycle of the off-gas condensate solution to the LAW glassmore » melter feed. The recycle process is effective in increasing the loading of Tc in the immobilized LAW (ILAW), but it also disproportionately increases the sulfur and halides in the LAW melter feed, which have limited solubility in the LAW glass and thus significantly reduce the amount of LAW (glass waste loading) that can be vitrified and still maintain good waste form properties. This increases both the amount of LAW glass and either the duration of the LAW vitrification mission or requires the need for supplemental LAW treatment capacity. Several options are being considered to address this issue. Two approaches attempt to minimize the off-gas recycle by removing Tc at one of several possible points within the tank waste processing flowsheet. The separated Tc from these two approaches must then be dispositioned in a manner such that the Tc can be safely disposed. Alternative waste forms that do not have the Tc volatility issues associated with the vitrification process are being sought for immobilization of Tc for subsequent storage and disposal. The first objective of this report is to provide insights into the compositions and volumes of the Tc-bearing waste streams including the ion exchange eluate from processing LAW and the off-gas condensate from the melter. The first step to be assessed will be the processing of ion exchange eluate. The second objective of this report is to assess the compatibility of the available waste forms with the anticipated waste streams. Two major categories of Tc-specific waste forms are considered in this report including mineral and metal waste forms. Overall, it is concluded that a metal alloy waste form is the most promising and mature Tc-specific waste form and offers several benefits. One obvious advantage of the disposition of Tc in the metal alloy waste form is the significant reduction of the generated waste form volume, which leads to a reduction of the required storage facility footprint. Among mineral waste forms, glass-bonded sodalite and possibly goethite should also be considered for the immobilization of Tc.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
None
1982-01-01
Some of the conclusions reached as a result of this study are summarized. Waste form parameters for the reference cermet waste form are available only by analogy. Detail design of the waste payload would require determination of actual waste form properties. The billet configuration constraints for the cermet waste form limit the packing efficiency to slightly under 75% net volume. The effect of this packing inefficiency in reducing the net waste form per waste payload can be seen graphically. The cermet waste form mass per unit mass of waste payload is lower than that of the iodine waste form evenmore » though the cermet has a higher density (6.5 versus 5.5). This is because the lead iodide is cast achieving almost 100% efficiency in packing. This inefficiency in the packing of the cermet results in a 20% increase in number of flights which increases both cost and risk. Alternative systems for waste mixes requiring low flight rates (technetium-99, iodine-129) can make effective use of the existing 65K space transportation system in either single- or dual-launch scenarios. A comprehensive trade study would be required to select the optimum orbit transfer system for low-launch-rate systems. This study was not conducted as part of the present effort due to selection of the cermet waste form as the reference for the study. Several candidates look attractive for both single- and dual-launch systems (see sec. 4.4), but due to the relatively small number of missions, a comprehensive comparison of life cycle costs including DDT and E would be required to select the best system. The reference system described in sections 5.0, 6.0, 7.0, and 8.0 offers the best combination of cost, risk, and alignment with ongoing NASA technology development efforts for disposal of the reference cermet waste form.« less
Moisture induced polymorphic transition of mannitol and its morphological transformation.
Yoshinari, Tomohiro; Forbes, Robert T; York, Peter; Kawashima, Yoshiaki
2002-10-24
The effects of moisture on the polymorphic transition of crystalline mannitol were investigated. Mannitol has three polymorphic forms, and was classified as alpha, beta, and delta form, respectively, by Walter-Lévy (C.R. Acad. Sc. Paris Ser. C (1968) 267, 1779). The water uptake of delta form crystalline was greater than that of the beta form when each crystalline form was stored at 97%RH (25 degrees C). The different powder X-ray diffraction patterns obtained before and after humidification confirmed that a moisture induced polymorphic transition from the delta to beta form had occurred. Morphological changes were also observed with an increase in the specific surface area of the delta sample from 0.4 to 2.3 m(2)/g being found on exposure to humidity. Thus it was suggested that the observed higher hygroscopicity of the newly formed beta form arose from the gradual increase in the surface area with the polymorphic transition from the delta to beta form. When considering the mechanism of this polymorphic transition, the results from molecular modelling, cross-polarisation/magic angle spinning (CP/MAS) solid-state NMR spectra and scanning electron-micrographs suggest that water molecules act as a molecular loosener to facilitate conversion from delta to the beta form as a result of multi-nucleation. Copyright 2002 Elsevier Science B.V.
Solid-phase zirconium and fluoride species in alkaline zircaloy cladding waste at Hanford.
Reynolds, Jacob G; Huber, Heinz J; Cooke, Gary A; Pestovich, John A
2014-08-15
The United States Department of Energy Hanford Site, near Richland, Washington, USA, processed plutonium between 1944 and 1987. Fifty-six million gallons of waste of various origins remain, including waste from removing zircaloy fuel cladding using the so-called Zirflex process. The speciation of zirconium and fluoride in this waste is important because of the corrosivity and reactivity of fluoride as well as the (potentially) high density of Zr-phases. This study evaluates the solid-phase speciation of zirconium and fluoride using X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS). Two waste samples were analyzed: one waste sample that is relatively pure zirconium cladding waste from tank 241-AW-105 and another that is a blend of zirconium cladding wastes and other high-level wastes from tank 241-C-104. Villiaumite (NaF) was found to be the dominant fluoride species in the cladding waste and natrophosphate (Na7F[PO4]2 · 19H2O) was the dominant species in the blended waste. Most zirconium was present as a sub-micron amorphous Na-Zr-O phase in the cladding waste and a Na-Al-Zr-O phase in the blended waste. Some zirconium was present in both tanks as either rounded or elongated crystalline needles of Na-bearing ZrO2 that are up to 200 μm in length. These results provide waste process planners the speciation data needed to develop disposal processes for this waste. Copyright © 2014 Elsevier B.V. All rights reserved.
Hrma, Pavel
2014-12-18
The melter feed, slurry, or calcine charged on the top of a pool of molten glass forms a floating layer of reacting material called the cold cap. Between the cold-cap top, which is covered with boiling slurry, and its bottom, where bubbles separate it from molten glass, the temperature changes by up to 1000 K. The processes that occur over this temperature interval within the cold cap include liberation of gases, conduction and consumption of heat, dissolution of quartz particles, formation and dissolution of intermediate crystalline phases, and generation of foam and gas cavities. These processes have been investigated usingmore » thermal analyses, optical and electronic microscopies, x-ray diffraction, as well as other techniques. Properties of the reacting feed, such as heat conductivity and density, were measured as functions of temperature. Investigating the structure of quenched cold caps produced in a laboratory-scale melter complemented the crucible studies. The cold cap consists of two main layers. The top layer contains solid particles dissolving in the glass-forming melt and open pores through which gases are escaping. The bottom layer contains bubbly melt or foam where bubbles coalesce into larger cavities that move sideways and release the gas to the atmosphere. The feed-to-glass conversion became sufficiently understood for representing the cold-cap processes via mathematical models. These models, which comprise heat transfer, mass transfer, and reaction kinetics models, have been developed with the final goal to relate feed parameters to the rate of glass melting.« less
West Valley demonstration project: Alternative processes for solidifying the high-level wastes
NASA Astrophysics Data System (ADS)
Holton, L. K.; Larson, D. E.; Partain, W. L.; Treat, R. L.
1981-10-01
Two pretreatment approaches and several waste form processes for radioactive wastes were selected for evaluation. The two waste treatment approaches were the salt/sludge separation process and the combined waste process. Both terminal and interim waste form processes were studied.
Sialon ceramic compositions and methods of fabrication
O'Brien, Michael H.; Park, Blair H.
1994-01-01
A method of fabricating a SiAlON ceramic body includes: a) combining quantities of Si.sub.3 N.sub.4, Al.sub.2 O.sub.3 and CeO.sub.2 to produce a mixture; b) forming the mixture into a desired body shape; c) heating the body to a densification temperature of from about 1550.degree. C. to about 1850.degree. C.; c) maintaining the body at the densification temperature for a period of time effective to densify the body; d) cooling the densified body to a devitrification temperature of from about 1200.degree. C. to about 1400.degree. C.; and e) maintaining the densified body at the devitrification temperature for a period of time effective to produce a .beta.'-SiAlON crystalline phase in the body having elemental or compound form Ce incorporated in the .beta.'-SiAlON crystalline phase. Further, a SiAlON ceramic body comprises: a) an amorphous phase; and b) a crystalline phase, the crystalline phase comprising .beta.'-SiAlON having lattice substituted elemental or compound form Ce.
SiAlON ceramic compositions and methods of fabrication
O'Brien, M.H.; Park, B.H.
1994-05-31
A method of fabricating a SiAlON ceramic body includes: (a) combining quantities of Si[sub 3]N[sub 4], Al[sub 2]O[sub 3] and CeO[sub 2] to produce a mixture; (b) forming the mixture into a desired body shape; (c) heating the body to a densification temperature of from about 1,550 C to about 1,850 C; (d) maintaining the body at the densification temperature for a period of time effective to densify the body; (e) cooling the densified body to a devitrification temperature of from about 1,200 C to about 1,400 C; and (f) maintaining the densified body at the devitrification temperature for a period of time effective to produce a [beta][prime]-SiAlON crystalline phase in the body having elemental or compound form Ce incorporated in the [beta][prime]-SiAlON crystalline phase. Further, a SiAlON ceramic body comprises: (a) an amorphous phase; and (b) a crystalline phase, the crystalline phase comprising [beta][prime]-SiAlON having lattice substituted elemental or compound form Ce.
NASA Astrophysics Data System (ADS)
Kowalski, Piotr; Kasina, Monika; Michalik, Marek
2017-04-01
Bottom ash (BA) from municipal solid waste incineration (MSWI) is composed of grainy ash material, residual components and metallic fragments (from few µm up to 3-5 cm). Its mineral and chemical composition is related to the composition of the waste stream in the incinerator operational area. Wide use of thermal techniques in management of solid waste makes important the studies on valuable components and their distribution within the material in terms of their further processing. By using various valorization or extraction techniques it is possible to extend the range of its possible further application. To investigate metallic elements distribution within metallic fragments of the MSWI BA material produced in municipal waste incineration plant in Poland were collected in 2015 and 2016. BA and its components were investigated using spectroscopic methods of chemical analysis: ICP-OES, ICP-MS, LECO and EDS (used for microanalysis during SEM observations). BA is a material rich in Si (22.5 wt%), Ca (13.4 wt%), Fe (4 wt%), Al (5.2 wt%) and Na (3.5 wt%), composed of equal part of amorphous (silicate glass dominated) and crystalline phase (rich in silicates, aluminosilicates, oxides of non- and metallic elements and sulphates). The content of metallic elements (Al, Fe, Mg, Ti, Mn, Cr, Ni, Sc, Mo, Cu, Pb, Zn, Sn) is 11.5 wt% with domination of Al (5.2 wt%) and Fe (4 wt%) and elevated values of Mg (1 wt%), Ti (0.54 wt%), Cu (0.26 wt%) and Zn (0.27 wt%) (Kowalski et al., 2016). They were mostly concentrated in the form of metallic fragments, mainly as metallic inclusions in the size of 1-20 µm and separated metallic grains in the size of 50-300 µm. Metallic fragments present in the BA are characterized by their composition heterogeneity and various oxygen content. Fragments are rarely composed of single metallic element and usually in their composition up to few main elements dominated over others. The most common were Fe-, Al- and Zn-rich fragments forming respectively 70%, 15% and 5% of the total amount of fragments. Fe occurred mainly as component of metallic inclusions and separate grains. Al was mostly present in metallic fragments on grains boundaries and also and as separate grains (often oxidised), moreover Al was important component of aluminosilicates and amorphous phase. Zn-rich metallic fragments were mostly in the form of separate grains. In complex composition of metallic fragments some regularities in elements co-occurrences were observed: Fe often co-existed with Si, Ca, P, Al and Ti; Al co-occurred with Fe, Si and Ca; Zn co-existed with Ca, Al and Si. Forms and composition of metallic fragments allows to evaluate them as potential polymetallic resource, however an economically reasonable extraction techniques must be applied. Acknowledgment Research was funded by Polish National Science Centre (NCN). Scientific grant No. UMO-2014/15/B/ST10/04171. Reference Kowalski, P.R., Kasina, M. and Michalik M.: Metallic elements fractionation in municipal solid waste incineration residues, Energy Procedia, 97, 31-36, doi: 10.1016/j.egypro.2016.10.013, 2016.
Ca2+-binding Motif of βγ-Crystallins*
Srivastava, Shanti Swaroop; Mishra, Amita; Krishnan, Bal; Sharma, Yogendra
2014-01-01
βγ-Crystallin-type double clamp (N/D)(N/D)XX(S/T)S motif is an established but sparsely investigated motif for Ca2+ binding. A βγ-crystallin domain is formed of two Greek key motifs, accommodating two Ca2+-binding sites. βγ-Crystallins make a separate class of Ca2+-binding proteins (CaBP), apparently a major group of CaBP in bacteria. Paralleling the diversity in βγ-crystallin domains, these motifs also show great diversity, both in structure and in function. Although the expression of some of them has been associated with stress, virulence, and adhesion, the functional implications of Ca2+ binding to βγ-crystallins in mediating biological processes are yet to be elucidated. PMID:24567326
Letter Report: LAW Simulant Development for Cast Stone Screening Test
DOE Office of Scientific and Technical Information (OSTI.GOV)
Russell, Renee L.; Westsik, Joseph H.; Swanberg, David J.
2013-03-27
More than 56 million gallons of radioactive and hazardous waste are stored in 177 underground storage tanks at the U.S. Department of Energy’s (DOE’s) Hanford Site in southeastern Washington State. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is being constructed to treat the wastes and immobilize them in a glass waste form. The WTP includes a pretreatment facility to separate the wastes into a small volume of high-level waste (HLW) containing most of the radioactivity and a larger volume of low-activity waste (LAW) containing most of the nonradioactive chemicals. The HLW will be converted to glass in themore » HLW vitrification facility for ultimate disposal at an offsite federal repository. At least a portion (~35%) of the LAW will be converted to glass in the LAW vitrification facility and will be disposed of onsite at the Integrated Disposal Facility (IDF). The pretreatment and HLW vitrification facilities will have the capacity to treat and immobilize the wastes destined for each facility. However, a second facility will be needed for the expected volume of additional LAW requiring immobilization. A cementitious waste form known as Cast Stone is being considered to provide the required additional LAW immobilization capacity. The Cast Stone waste form must be acceptable for disposal in the IDF. The Cast Stone waste form and immobilization process must be tested to demonstrate that the final Cast Stone waste form can comply with waste acceptance criteria for the IDF disposal facility and that the immobilization processes can be controlled to consistently provide an acceptable waste form product. Further, the waste form must be tested to provide the technical basis for understanding the long term performance of the waste form in the IDF disposal environment. These waste form performance data are needed to support risk assessment and performance assessment (PA) analyses of the long-term environmental impact of the waste disposal in the IDF. A testing program was developed in fiscal year (FY) 2012 describing in some detail the work needed to develop and qualify Cast Stone as a waste form for the solidification of Hanford LAW (Westsik et al. 2012). Included within Westsik et al. (2012) is a section on the near-term needs to address Tri-Party Agreement Milestone M-062-40ZZ. The objectives of the testing program to be conducted in FY 2013 and FY 2014 are to: • Determine an acceptable formulation for the LAW Cast Stone waste form. • Evaluate sources of dry materials for preparing the LAW Cast Stone. • Demonstrate the robustness of the Cast Stone waste form for a range of LAW compositions. • Demonstrate the robustness of the formulation for variability in the Cast Stone process. • Provide Cast Stone contaminant release data for PA and risk assessment evaluations. The first step in determining an acceptable formulation for the LAW Cast Stone waste form is to conduct screening tests to examine expected ranges in pretreated LAW composition, waste stream concentrations, dry-materials sources, and mix ratios of waste feed to dry blend. A statistically designed test matrix will be used to evaluate the effects of these key parameters on the properties of the Cast Stone as it is initially prepared and after curing. The second phase of testing will focus on selection of a baseline Cast Stone formulation for LAW and demonstrating that Cast Stone can meet expected waste form requirements for disposal in the IDF. It is expected that this testing will use the results of the screening tests to define a smaller suite of tests to refine the composition of the baseline Cast Stone formulation (e.g. waste concentration, water to dry mix ratio, waste loading).« less
40 CFR 761.345 - Form of the waste to be sampled.
Code of Federal Regulations, 2013 CFR
2013-07-01
... Characterization for PCB Disposal in Accordance With § 761.62, and Sampling PCB Remediation Waste Destined for Off-Site Disposal, in Accordance With § 761.61 § 761.345 Form of the waste to be sampled. PCB bulk product waste and PCB remediation waste destined for off-site disposal must be in the form of either flattened...
Underground waste barrier structure
Saha, Anuj J.; Grant, David C.
1988-01-01
Disclosed is an underground waste barrier structure that consists of waste material, a first container formed of activated carbonaceous material enclosing the waste material, a second container formed of zeolite enclosing the first container, and clay covering the second container. The underground waste barrier structure is constructed by forming a recessed area within the earth, lining the recessed area with a layer of clay, lining the clay with a layer of zeolite, lining the zeolite with a layer of activated carbonaceous material, placing the waste material within the lined recessed area, forming a ceiling over the waste material of a layer of activated carbonaceous material, a layer of zeolite, and a layer of clay, the layers in the ceiling cojoining with the respective layers forming the walls of the structure, and finally, covering the ceiling with earth.
Xu, Hui; Gong, Weiliang; Syltebo, Larry; Lutze, Werner; Pegg, Ian L
2014-08-15
The binary furnace slag-metakaolin DuraLith geopolymer waste form, which has been considered as one of the candidate waste forms for immobilization of certain Hanford secondary wastes (HSW) from the vitrification of nuclear wastes at the Hanford Site, Washington, was extended to a ternary fly ash-furnace slag-metakaolin system to improve workability, reduce hydration heat, and evaluate high HSW waste loading. A concentrated HSW simulant, consisting of more than 20 chemicals with a sodium concentration of 5 mol/L, was employed to prepare the alkaline activating solution. Fly ash was incorporated at up to 60 wt% into the binder materials, whereas metakaolin was kept constant at 26 wt%. The fresh waste form pastes were subjected to isothermal calorimetry and setting time measurement, and the cured samples were further characterized by compressive strength and TCLP leach tests. This study has firstly established quantitative linear relationships between both initial and final setting times and hydration heat, which were never discovered in scientific literature for any cementitious waste form or geopolymeric material. The successful establishment of the correlations between setting times and hydration heat may make it possible to efficiently design and optimize cementitious waste forms and industrial wastes based geopolymers using limited testing results. Copyright © 2014 Elsevier B.V. All rights reserved.
Direct observation of vast off-stoichiometric defects in single crystalline SnSe
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wu, Di; Wu, Lijun; He, Dongsheng
Single crystalline tin selenide (SnSe) recently emerged as a very promising thermoelectric material for waste heat harvesting and thermoelectric cooling, due to its record high figure of merit ZT in mediate temperature range. The most striking feature of SnSe lies in its extremely low lattice thermal conductivity as ascribed to the anisotropic and highly distorted Sn-Se bonds as well as the giant bond anharmonicity by previous studies, yet no theoretical models so far can give a quantitative explanation to such low a lattice thermal conductivity. Here, we presented direct observation of an astonishingly vast number of off-stoichiometric Sn vacancies andmore » Se interstitials, using sophisticated aberration corrected scanning transmission electron microscope; and credited the previously reported ultralow thermal conductivity of the SnSe single crystalline samples partly to their off-stoichiometric feature. In order to further validate the conclusion, we also synthesized stoichiometric SnSe single crystalline samples, and illustrated that the lattice thermal conductivity is deed much higher as compared with the off-stoichiometric single crystals. Finally, the scattering efficiency of individual point defect on heat-carrying phonons was then discussed in the state-of-art Debye-Callaway model.« less
Direct observation of vast off-stoichiometric defects in single crystalline SnSe
Wu, Di; Wu, Lijun; He, Dongsheng; ...
2017-04-06
Single crystalline tin selenide (SnSe) recently emerged as a very promising thermoelectric material for waste heat harvesting and thermoelectric cooling, due to its record high figure of merit ZT in mediate temperature range. The most striking feature of SnSe lies in its extremely low lattice thermal conductivity as ascribed to the anisotropic and highly distorted Sn-Se bonds as well as the giant bond anharmonicity by previous studies, yet no theoretical models so far can give a quantitative explanation to such low a lattice thermal conductivity. Here, we presented direct observation of an astonishingly vast number of off-stoichiometric Sn vacancies andmore » Se interstitials, using sophisticated aberration corrected scanning transmission electron microscope; and credited the previously reported ultralow thermal conductivity of the SnSe single crystalline samples partly to their off-stoichiometric feature. In order to further validate the conclusion, we also synthesized stoichiometric SnSe single crystalline samples, and illustrated that the lattice thermal conductivity is deed much higher as compared with the off-stoichiometric single crystals. Finally, the scattering efficiency of individual point defect on heat-carrying phonons was then discussed in the state-of-art Debye-Callaway model.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vienna, John D.; Todd, Terry A.; Gray, Kimberly D.
The U.S. Department of Energy, Office of Nuclear Energy has chartered an effort to develop technologies to enable safe and cost effective recycle of commercial used nuclear fuel (UNF) in the U.S. Part of this effort includes the evaluation of exiting waste management technologies for effective treatment of wastes in the context of current U.S. regulations and development of waste forms and processes with significant cost and/or performance benefits over those existing. This study summarizes the results of these ongoing efforts with a focus on the highly radioactive primary waste streams. The primary streams considered and the recommended waste formsmore » include: •Tritium separated from either a low volume gas stream or a high volume water stream. The recommended waste form is low-water cement in high integrity containers. •Iodine-129 separated from off-gas streams in aqueous processing. There are a range of potentially suitable waste forms. As a reference case, a glass composite material (GCM) formed by the encapsulation of the silver Mordenite (AgZ) getter material in a low-temperature glass is assumed. A number of alternatives with distinct advantages are also considered including a fused silica waste form with encapsulated nano-sized AgI crystals. •Carbon-14 separated from LWR fuel treatment off-gases and immobilized as a CaCO3 in a cement waste form. •Krypton-85 separated from LWR and SFR fuel treatment off-gases and stored as a compressed gas. •An aqueous reprocessing high-level waste (HLW) raffinate waste which is immobilized by the vitrification process in one of three forms: a single phase borosilicate glass, a borosilicate based glass ceramic, or a multi-phased titanate ceramic [e.g., synthetic rock (Synroc)]. •An undissolved solids (UDS) fraction from aqueous reprocessing of LWR fuel that is either included in the borosilicate HLW glass or is immobilized in the form of a metal alloy in the case of glass ceramics or titanate ceramics. •Zirconium-based LWR fuel cladding hulls and stainless steel (SS) fuel assembly hardware that are washed and super-compacted for disposal or as an alternative Zr purification and reuse (or disposal as low-level waste, LLW) by reactive gas separations. •Electrochemical process salt HLW which is immobilized in a glass bonded Sodalite waste form known as the ceramic waste form (CWF). •Electrochemical process UDS and SS cladding hulls which are melted into an iron based alloy waste form. Mass and volume estimates for each of the recommended waste forms based on the source terms from a representative flowsheet are reported.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Not Available
This volume contains appendices for the following: Rocky Flats Plant and Idaho National Engineering Laboratory waste process information; TRUPACT-II content codes (TRUCON); TRUPACT-II chemical list; chemical compatibility analysis for Rocky Flats Plant waste forms; chemical compatibility analysis for waste forms across all sites; TRU mixed waste characterization database; hazardous constituents of Rocky Flats Transuranic waste; summary of waste components in TRU waste sampling program at INEL; TRU waste sampling program; and waste analysis data.
Topical delivery of roxithromycin solid-state forms entrapped in vesicles.
Csongradi, Candice; du Plessis, Jeanetta; Aucamp, Marique Elizabeth; Gerber, Minja
2017-05-01
Recently, considerable interest developed in using newer/improved antibiotics for the treatment of Acne vulgaris. During this study, different roxithromycin solid-state forms (i.e. crystalline and amorphous) were encapsulated into vesicle systems (niosomes, proniosomes, ufosomes and pro-ufosomes) for dermis targeted delivery. Characterization of the vesicles was done with transmission electron microscopy, light microscopy, droplet size, droplet size distribution, pH, zeta-potential and entrapment efficiency percentage. Finally, comparative release and topical diffusion studies were performed, to evaluate if targeted topical delivery was obtained and if the roxithromycin solid-state amorphous forms resulted in improved topical delivery. Vesicle systems containing different roxithromycin (2%) solid-state forms were successfully prepared and characterized. The vesicles showed optimal properties for topical delivery. All carrier systems had topical delivery to the epidermis-dermis, whilst no roxithromycin was found in the receptor compartment or stratum corneum-epidermis. The niosomes were the leading formulation and the two amorphous forms had better topical delivery than the crystalline form. Successful targeted delivery of roxithromycin was obtained in the dermis, where the activity against Propionibacterium acnes is needed. The amorphous forms seemed to have held their solid-state form during formulation and in the vesicles, showing improved topical delivery in comparison to the crystalline form. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Riley, Brian J.; Pierce, David A.; Frank, Steven M.; Matyáš, Josef; Burns, Carolyne A.
2015-04-01
This paper describes the various approaches evaluated for making solution-derived sodalite with a LiCl-Li2O oxide reduction salt selected to dissolve used uranium oxide fuel so the uranium can be recovered and recycled. The approaches include modified sol-gel and solution-based synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na2O-B2O3-SiO2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to form halite in solution and Li2O and SiO2 to form lithium silicates (e.g., Li2SiO3 or Li2Si2O5) in the calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions in the crystalline product (∼92 mass%) and low porosities using a solution-based approach and this LiCl-Li2O salt but that the incorporation of Li into the sodalite is low.
NASA Astrophysics Data System (ADS)
Zahoor, Mehvish; Arshad, Amara; Khan, Yaqoob; Iqbal, Mazhar; Bajwa, Sadia Zafar; Soomro, Razium Ali; Ahmad, Ishaq; Butt, Faheem K.; Iqbal, M. Zubair; Wu, Aiguo; Khan, Waheed S.
2018-03-01
This study presents the synthesis of CeO2-TiO2 nanocomposite and its potential application for the visible light-driven photocatalytic degradation of model crystal violet dye as well as real industrial waste water. The ceria-titania (CeO2-TiO2) nanocomposite material was synthesised using facile hydrothermal route without the assistance of any template molecule. As-prepared composite was characterised by SEM, TEM, HRTEM, XRD, XPS for surface features, morphological and crystalline characters. The formed nanostructures were determined to possess crystal-like geometrical shape and average size less than 100 nm. The as-synthesised nanocomposite was further investigated for their heterogeneous photocatalytic potential against the oxidative degradation of CV dye taken as model pollutant. The photo-catalytic performance of the as-synthesised material was evaluated both under ultra-violet as well as visible light. Best photocatalytic performance was achieved under visible light with complete degradation (100%) exhibited within 60 min of irradiation time. The kinetics of the photocatalytic process were also considered and the reaction rate constant for CeO2-TiO2 nanocomposite was determined to be 0.0125 and 0.0662 min-1 for ultra-violet and visible region, respectively. In addition, the as-synthesised nanocomposite demonstrated promising results when considered for the photo-catalytic degradation of coloured industrial waste water collected from local textile industry situated in Faisalabad region of Pakistan. Enhanced photo-catalytic performance of CeO2-TiO2 nanocomposite was proposed owing to heterostructure formation leading to reduced electron-hole recombination.
Monique LaPerriere Nelson; Charles C. Rhoades; Kathleen A. Dwire
2011-01-01
We characterized the water chemistry of nine slope wetlands and adjacent headwater streams in Colorado subalpine forests and compared sites in basins formed on crystalline bedrock with those formed in basins with a mixture of crystalline and sedimentary bedrock. The pH, Ca2+, Mg2+, NH4 +, acid neutralizing capacity, and electrical conductivity of wetland porewater and...
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zain, Nor Fazelin Mat; Yusop, Salma Mohamad; Ahmad, Ishak
Citrus peel is one of the under-utilized waste materials that have potential in producing a valuable fibre, which are cellulose and cellulose nanocrystal. Cellulose was first isolated from pomelo (C. Grandis Osbeck) albedo by combination of alkali treatment and bleaching process, followed by acid hydrolysis (65% H{sub 2}SO{sub 4}, 45 °C, 45min) to produce cellulose nanocrystal. The crystalline, structural, morphological and chemical properties of both materials were studied. Result reveals the crystallinity index obtained from X-ray diffraction for cellulose nanocrystal was found higher than extracted cellulose with the value of 60.27% and 57.47%, respectively. Fourier transform infrared showed that themore » chemical treatments removed most of the hemicellulose and lignin from the pomelo albedo fibre. This has been confirmed further by SEM and TEM for their morphological studies. These results showed that cellulose and cellulose nanocrystal were successfully obtained from pomelo albedo and might be potentially used in producing functional fibres for food application.« less
NASA Astrophysics Data System (ADS)
Miranda, Daniel; Yin, Chaoqing; Runt, James
Fluorinated semi-crystalline polymer films are attractive for dielectric film applications due to their chemical inertness, heat resistance, and high thermal stability. In the present investigation we explore the influence of orientation induced by uniaxial drawing on the crystalline microstructure and relaxation processes of poly(ethylene-tetrafluoroethylene) (ETFE), in order to ascertain how morphological control can benefit polymer dielectric design. When drawn below or near the Tg, the crystallinity of the drawn films is unchanged, and oriented amorphous structures and crystalline microfibrils form at high draw ratios. This orientation slows segmental relaxation, reflected by an increase in the dynamic Tg, and also delays the transition to the high temperature crystalline form of ETFE. When drawing above the Tg, the films undergo strain-induced crystallization at high draw ratios. For these films an increase in the dynamic Tg is also observed, in addition to a second segmental relaxation process, appearing as a shoulder on the primary process. We propose that this represents a contribution from a rigid amorphous fraction, having slowed chain dynamics. Supported by Office of Naval Research.
Aluminum phosphate ceramics for waste storage
Wagh, Arun; Maloney, Martin D
2014-06-03
The present disclosure describes solid waste forms and methods of processing waste. In one particular implementation, the invention provides a method of processing waste that may be particularly suitable for processing hazardous waste. In this method, a waste component is combined with an aluminum oxide and an acidic phosphate component in a slurry. A molar ratio of aluminum to phosphorus in the slurry is greater than one. Water in the slurry may be evaporated while mixing the slurry at a temperature of about 140-200.degree. C. The mixed slurry may be allowed to cure into a solid waste form. This solid waste form includes an anhydrous aluminum phosphate with at least a residual portion of the waste component bound therein.
Reverse-phase HPLC analysis of human alpha crystallin.
Swamy, M S; Abraham, E C
1991-03-01
A rapid and highly sensitive reverse-phase HPLC (RP-HPLC) method was used to separate crystallin subunits from human alpha crystallin. Three distinct peaks were separated; by electrophoretic and immunological analyses the first and second peaks were identified as alpha B and alpha A respectively. On the other hand, peak 3 appeared to be a modified form of alpha crystallin. The ratio of alpha A and alpha B proteins was 3:1 in 1 day old lenses which gradually changed to 2:1 in 17 year old lenses and to 1:1 in the 50 and 82 year old whole lenses and 82 year old lens cortex, with a concomitant increase in the modified alpha, suggesting that alpha A subunits are relatively more involved in aggregation. Analysis of the 82 year old lens nucleus also supported this conclusion. The RP-HPLC analysis of the HMW aggregate fraction showed substantial enrichment of the modified alpha. The alpha A and alpha B subunits independently reassociated to form polymeric alpha crystallin whereas the modified alpha reassociated to form HMW aggregates as shown by molecular sieve HPLC. Hence it appears that the HMW aggregate peak was constituted by modified alpha crystallin. Only in the peak 3 material the 280 nm absorbance was about 2-fold higher than what was expected from the actual protein content. The data suggest that the changes induced by post-translational modifications may have some role in the formation of modified alpha. The present RP-HPLC method is useful in separating these modified alpha from the unmodified alpha A and alpha B subunits.
Pretreatment of Hanford medium-curie wastes by fractional crystallization.
Nassif, Laurent; Dumont, George; Alysouri, Hatem; Rousseau, Ronald W
2008-07-01
Acceleration of the schedule for decontamination of the Hanford site using bulk vitrification requires implementation of a pretreatment operation. Medium-curie waste must be separated into two fractions: one is to go to a waste treatment and immobilization plant and a second, which is low-activity waste, is to be processed by bulk vitrification. The work described here reports research on using fractional crystallization for that pretreatment. Sodium salts are crystallized by evaporation of water from solutions simulating those removed from single-shell tanks, while leaving cesium in solution. The crystalline products are then recovered and qualified as low-activity waste, which is suitable upon redissolution for processing by bulk vitrification. The experimental program used semibatch operation in which a feed solution was continuously added to maintain a constant level in the crystallizer while evaporating water. The slurry recovered at the end of a run was filtered to recover product crystals, which were then analyzed to determine their composition. The results demonstrated that targets on cesium separation from the solids, fractional recovery of sodium salts, and sulfate content of the recovered salts can be achieved by the process tested.
Yang, Guang; Wang, Jianlong
2018-05-01
In this study, the combined ionizing radiation-acid pretreatment process was firstly applied to enhance hydrogen fermentation of grass waste. Results showed that the combined pretreatment synergistically enhanced hydrogen fermentation of grass waste. The SCOD and soluble polysaccharide contents of grass waste increased by 1.6 and 2.91 times after the combined pretreatment, respectively. SEM observation and crystallinity test showed the combined pretreatment effectively disrupted the grass structure. Owing to the more favorable substrate conditions, the hydrogen yield achieved 68 mL/g-dry grass added after the combined pretreatment, which was 161.5%, 112.5% and 28.3% higher than those from raw, ionizing radiation pretreated and acid pretreated grass waste, respectively. The VS removal also increased from 13.9% to 25.6% by the combined pretreatment. Microbial community analysis showed that the abundance of dominant hydrogen producing genus Clostridium sensu stricto 1 increased from 37.9% to 69.4% after the combined pretreatment, which contributed to more efficient hydrogen fermentation. Copyright © 2018 Elsevier Ltd. All rights reserved.
Branagan, Daniel J.; Burch, Joseph V.
2001-01-01
In one aspect, the invention encompasses a method of forming a steel. A metallic glass is formed and at least a portion of the glass is converted to a crystalline steel material having a nanocrystalline scale grain size. In another aspect, the invention encompasses another method of forming a steel. A molten alloy is formed and cooled the alloy at a rate which forms a metallic glass. The metallic glass is devitrified to convert the glass to a crystalline steel material having a nanocrystalline scale grain size. In yet another aspect, the invention encompasses another method of forming a steel. A first metallic glass steel substrate is provided, and a molten alloy is formed over the first metallic glass steel substrate to heat and devitrify at least some of the underlying metallic glass of the substrate.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pierce, Eric M.; Mattigod, Shas V.; Westsik, Joseph H.
2010-01-30
Pacific Northwest National Laboratory has initiated a waste form testing program to support the long-term durability evaluation of a waste form for secondary wastes generated from the treatment and immobilization of Hanford radioactive tank wastes. The purpose of the work discussed in this report is to identify candidate stabilization technologies and getters that have the potential to successfully treat the secondary waste stream liquid effluent, mainly from off-gas scrubbers and spent solids, produced by the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Down-selection to the most promising stabilization processes/waste forms is needed to support the design of a solidificationmore » treatment unit (STU) to be added to the Effluent Treatment Facility (ETF). To support key decision processes, an initial screening of the secondary liquid waste forms must be completed by February 2010.« less
Shen, Xiao; Hernandez-Pagan, Emil; Zhou, Wu; ...
2014-11-14
The search for optimal thermoelectric materials aims for structures in which the crystalline order is disrupted to lower the thermal conductivity without degradation of the electron conductivity. Here we report the synthesis and characterization of ternary nanoparticles (two cations and one anion) that exhibit a new form of crystal-line order: an uninterrupted, perfect, global Bravais lattice, in which the two cations exhibit a wide array of distinct ordering patterns within the cation sublattice, form-ing interlaced domains and phases. Partitioning into domains and phases is not unique; the corresponding boundaries have no structural defects or strain and entail no energy cost.more » We call this form of crystalline order “interlaced crystals” and present the example of hexagonal-CuInS 2. Interlacing is possible in multi-cation tetrahedral-ly-bonded compound with an average of two electrons per bond. Interlacing has min-imal effect on electronic properties, but should strongly reduce phonon transport, making interlaced crystals attractive for thermoelectric applications.« less
The Nature of Metastable AA’ Graphite: Low Dimensional Nano- and Single-Crystalline Forms
Lee, Jae-Kap; Kim, Jin-Gyu; Hembram, K. P. S. S.; Kim, Yong-Il; Min, Bong-Ki; Park, Yeseul; Lee, Jeon-Kook; Moon, Dong Ju; Lee, Wooyoung; Lee, Sang-Gil; John, Phillip
2016-01-01
Over the history of carbon, it is generally acknowledged that Bernal AB stacking of the sp2 carbon layers is the unique crystalline form of graphite. The universal graphite structure is synthesized at 2,600~3,000 °C and exhibits a micro-polycrystalline feature. In this paper, we provide evidence for a metastable form of graphite with an AA’ structure. The non-Bernal AA’ allotrope of graphite is synthesized by the thermal- and plasma-treatment of graphene nanopowders at ~1,500 °C. The formation of AA’ bilayer graphene nuclei facilitates the preferred texture growth and results in single-crystal AA’ graphite in the form of nanoribbons (1D) or microplates (2D) of a few nm in thickness. Kinetically controlled AA’ graphite exhibits unique nano- and single-crystalline feature and shows quasi-linear behavior near the K-point of the electronic band structure resulting in anomalous optical and acoustic phonon behavior. PMID:28000780
Argillite And Crystalline Disposal Research: Accomplishments And Path-Forward.
DOE Office of Scientific and Technical Information (OSTI.GOV)
McMahon, Kevin A.; Jove-Colon, Carlos F.; Wang, Yifeng
The intention of this document is to provide a path-forward for research and development (R&D) for two host rock media-specific (argillite and crystalline) disposal research work packages within the Used Fuel Disposition Campaign (UFDC). The two work packages, Argillite Disposal R&D and Crystalline Disposal R&D, support the achievement of the overarching mission and objectives of the Department of Energy Office of Nuclear Energy Fuel Cycle Technologies Program. These two work packages cover many of the fundamental technical issues that will have multiple implications to other disposal research work packages by bridging knowledge gaps to support the development of the safetymore » case. The path-forward begins with the assumption of target dates that are set out in the January 2013 DOE Strategy for the Management and Disposal of Used Nuclear Fuel and High-Level Radioactive Waste (http://energy.gov/downloads/strategy-management-and-disposal-used-nuclear-fuel-and-high-levelradioactive- waste). The path-forward will be maintained as a living document and will be updated as needed in response to available funding and the progress of multiple R&D tasks in the Used Fuel Disposition Campaign and the Fuel Cycle Technologies Program. This path forward is developed based on the report of “Used Fuel Disposition Campaign Disposal Research and Development Roadmap (FCR&D-USED- 2011-000065 REV0)” (DOE, 2011). This document delineates the goals and objectives of the UFDC R&D program, needs for generic disposal concept design, and summarizes the prioritization of R&D issues.« less
The synthesis of nanostructured SiC from waste plastics and silicon powder
NASA Astrophysics Data System (ADS)
Ju, Zhicheng; Xu, Liqiang; Pang, Qiaolian; Xing, Zheng; Ma, Xiaojian; Qian, Yitai
2009-09-01
Waste plastics constitute a growing environmental problem. Therefore, the treatment of waste plastics should be considered. Here we synthesize 3C-SiC nanomaterials coexisting with amorphous graphite particles utilizing waste plastics and Si powder at 350-500 °C in a stainless steel autoclave. 3C-SiC could be finally obtained after refluxing with aqueous HClO4 (70 wt%) at 180 °C. X-ray powder diffraction patterns indicate that the product is 3C-SiC with the calculated lattice constant a = 4.36 Å. Transmission electron microscopy (TEM) images show that the SiC samples presented two morphologies: hexagonal platelets prepared by the waste detergent bottles or beverage bottles and nanowires prepared by waste plastic bags respectively. The corresponding selected area electron diffraction (SAED) pattern indicates that either the entire hexagonal platelet or the nanowire is single crystalline. High-resolution TEM shows the planar surfaces of the SiC platelet correspond to {111} planes; the lateral surfaces are {110} planes and the preferential growth direction of the nanowires is along [111]. The output of SiC was ~39% based on the amount of Si powder.
Calcium titanium silicate based glass-ceramic for nuclear waste immobilisation
NASA Astrophysics Data System (ADS)
Sharma, K.; Srivastav, A. P.; Goswami, M.; Krishnan, Madangopal
2018-04-01
Titanate based ceramics (synroc) have been studied for immobilisation of nuclear wastes due to their high radiation and thermal stability. The aim of this study is to synthesis glass-ceramic with stable phases from alumino silicate glass composition and study the loading behavior of actinides in glass-ceramics. The effects of CaO and TiO2 addition on phase evolution and structural properties of alumino silicate based glasses with nominal composition x(10CaO-9TiO2)-y(10Na2O-5 Al2O3-56SiO2-10B2O3); where z = x/y = 1.4-1.8 are reported. The glasses are prepared by melt-quench technique and characterized for thermal and structural properties using DTA and Raman Spectroscopy. Glass transition and peak crystallization temperatures decrease with increase of CaO and TiO2 content, which implies the weakening of glass network and increased tendency of glasses towards crystallization. Sphene (CaTiSiO5) and perovskite (CaTiO3) crystalline phases are confirmed from XRD which are well known stable phase for conditioning of actinides. The microsturcture and elemental analysis indicate the presence of actinide in stable crystalline phases.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Matteo, Edward N.; Hardin, Ernest L.; Hadgu, Teklu
As the title suggests, this report provides a summary of the status and progress for the Preliminary Design Concepts Work Package. Described herein are design concepts and thermal analysis for crystalline and salt host media. The report concludes that thermal management of defense waste, including the relatively small subset of high thermal output waste packages, is readily achievable. Another important conclusion pertains to engineering feasibility, and design concepts presented herein are based upon established and existing elements and/or designs. The multipack configuration options for the crystalline host media pose the greatest engineering challenges, as these designs involve large, heavy wastemore » packages that pose specific challenges with respect to handling and emplacement. Defense-related Spent Nuclear Fuel (DSNF) presents issues for post-closure criticality control, and a key recommendation made herein relates to the need for special packaging design that includes neutron-absorbing material for the DSNF. Lastly, this report finds that the preliminary design options discussed are tenable for operational and post-closure safety, owing to the fact that these concepts have been derived from other published and well-studied repository designs.« less
NASA Astrophysics Data System (ADS)
Kasina, Monika; Kowalski, Piotr R.; Michalik, Marek
2017-04-01
Increasing energy needs, the implementation of the circular economy principles and rising environmental awareness caused that waste management is becoming a major social and economic issue. The EU Member States have committed to a significant reduction in the amount of waste produced and landfilled and to use their inherent energy and raw materials potential. One of the most reasonable option to fulfil these commitments is waste incineration. The aim of the waste incineration is to reduce their volume and toxicity by disinfection and detoxification at high temperatures. Thermal process and reduction of volume allows the recovery of minerals and metallic elements from residues as well as the energy production (waste-to-energy strategy) during incineration. As a result of waste incineration a variety of solid residues (bottom ash, fly ash, air pollution control residues) and technological waste (gas waste, wastewater) are produced. The goal of this study is to characterize fly ash and air pollution control (APC) residues formed as a result of municipal sewage sludge incineration in terms of their chemical and mineral composition and their extractive potential. Residues were sampled quarterly to study their seasonal changes in composition. The fly ash was a Si-P-C-Fe-Al dominated material, whereas the APC residues composition was dominated by Na-rich soluble phases. The removal of soluble phase ( 98% of the material) from the APC residues by dissolution in deionised water caused significant mass reduction and concentration of non-soluble elements. The main mineral phases in fly ash were quartz, hematite, Fe-PO4, whitlockite and feldspar, while in APC thenardite, and in lower amount calcite, apatite and quartz were present. The chemical composition of fly ash was practically invariable in different seasons, but significant differences were observed in APC residues. The lowest concentrations of all elements and the highest TOC content were measured in the samples collected in the spring 2016. The highest concentrations for most of the elements were measured in summer 2016 except for the Ca, Sn, Zn, Cd, Sb, and Ag which concentrations were the highest in the winter time 2015. Even though the seasonal changes in metallic and/or potentially valuable elements concentrations are visible their overall content is low. In addition they are dispersed within crystalline and amorphous phase, therefore it seems to be inappropriate to consider this material as a source of valuable elements. Due to high phosphorus content in the fly ash, equal to the low grade phosphorus ore, both in the form of phosphate minerals as well as dispersed within minerals can be treated as a potential source of this critical raw material. Acknowledgment: The study was supported by Polish National Science Centre. NCN grant No UMO-2014/15/B/ST10/04171
Treatment of mercury containing waste
Kalb, Paul D.; Melamed, Dan; Patel, Bhavesh R; Fuhrmann, Mark
2002-01-01
A process is provided for the treatment of mercury containing waste in a single reaction vessel which includes a) stabilizing the waste with sulfur polymer cement under an inert atmosphere to form a resulting mixture and b) encapsulating the resulting mixture by heating the mixture to form a molten product and casting the molten product as a monolithic final waste form. Additional sulfur polymer cement can be added in the encapsulation step if needed, and a stabilizing additive can be added in the process to improve the leaching properties of the waste form.
Thick crystalline films on foreign substrates
Smith, Henry I.; Atwater, Harry A.; Geis, Michael W.
1986-01-01
To achieve a uniform texture, large crystalline grains or, in some cases, a single crystalline orientation in a thick (>1 .mu.m) film on a foreign substrate, the film is formed so as to be thin (<1 .mu.m) in a certain section. Zone-melting recrystallization is initiated in the thin section and then extended into the thick section. The method may employ planar constriction patterns of orientation filter patterns.
Thick crystalline films on foreign substrates
Smith, H.I.; Atwater, H.A.; Geis, M.W.
1986-03-18
To achieve a uniform texture, large crystalline grains or, in some cases, a single crystalline orientation in a thick (>1 [mu]m) film on a foreign substrate, the film is formed so as to be thin (<1 [mu]m) in a certain section. Zone-melting recrystallization is initiated in the thin section and then extended into the thick section. The method may employ planar constriction patterns of orientation filter patterns. 2 figs.
Health and Environmental Hazards of Electronic Waste in India.
Borthakur, Anwesha
2016-04-01
Technological waste in the form of electronic waste (e-waste) is a threat to all countries. E-waste impacts health and the environment by entering the food chain in the form of chemical toxicants and exposing the population to deleterious chemicals, mainly in the form of polycyclic aromatic hydrocarbons and persistent organic pollutants. This special report tries to trace the environmental and health implications of e-waste in India. The author concludes that detrimental health and environmental consequences are associated with e-waste and the challenge lies in producing affordable electronics with minimum chemical toxicants.
C-terminal interactions mediate the quaternary dynamics of αB-crystallin
Hilton, Gillian R.; Hochberg, Georg K. A.; Laganowsky, Arthur; McGinnigle, Scott I.; Baldwin, Andrew J.; Benesch, Justin L. P.
2013-01-01
αB-crystallin is a highly dynamic, polydisperse small heat-shock protein that can form oligomers ranging in mass from 200 to 800 kDa. Here we use a multifaceted mass spectrometry approach to assess the role of the C-terminal tail in the self-assembly of αB-crystallin. Titration experiments allow us to monitor the binding of peptides representing the C-terminus to the αB-crystallin core domain, and observe individual affinities to both monomeric and dimeric forms. Notably, we find that binding the second peptide equivalent to the core domain dimer is considerably more difficult than the first, suggesting a role of the C-terminus in regulating assembly. This finding motivates us to examine the effect of point mutations in the C-terminus in the full-length protein, by quantifying the changes in oligomeric distribution and corresponding subunit exchange rates. Our results combine to demonstrate that alterations in the C-terminal tail have a significant impact on the thermodynamics and kinetics of αB-crystallin. Remarkably, we find that there is energy compensation between the inter- and intra-dimer interfaces: when one interaction is weakened, the other is strengthened. This allosteric communication between binding sites on αB-crystallin is likely important for its role in binding target proteins. PMID:23530258
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cantrell, Kirk J.; Westsik, Joseph H.; Serne, R Jeffrey
A review of the most up-to-date and relevant data currently available was conducted to develop a set of recommended values for use in the Integrated Disposal Facility (IDF) performance assessment (PA) to model contaminant release from a cementitious waste form for aqueous wastes treated at the Hanford Effluent Treatment Facility (ETF). This data package relies primarily upon recent data collected on Cast Stone formulations fabricated with simulants of low-activity waste (LAW) and liquid secondary wastes expected to be produced at Hanford. These data were supplemented, when necessary, with data developed for saltstone (a similar grout waste form used at themore » Savannah River Site). Work is currently underway to collect data on cementitious waste forms that are similar to Cast Stone and saltstone but are tailored to the characteristics of ETF-treated liquid secondary wastes. Recommended values for key parameters to conduct PA modeling of contaminant release from ETF-treated liquid waste are provided.« less
NASA Technical Reports Server (NTRS)
Haggerty, S. E.
1983-01-01
Stabilization techniques for the storage of radioactive wastes are surveyed, with emphasis on immobilization in a primary barrier of synthetic rock. The composition, half-life, and thermal-emission characteristics of the wastes are shown to require thermally stable immobilization enduring at least 100,000 years. Glass materials are determined to be incapable of withstanding the expected conditions, average temperatures of 100-500 C for the first 100 years. The geological-time stability of crystalline materials, ceramics or synthetic rocks, is examined in detail by comparing their components with similar naturally occurring minerals, especially those containing the same radioactive elements. The high-temperature environment over the first 100 years is seen as stabilizing, since it can recrystallize radiation-induced metamicts. The synthetic-rock stabilization technique is found to be essentially feasible, and improvements are suggested, including the substitution of nepheline with freudenbergite and priderite for alkaline-waste stabilization, the maintenance of low oxygen fugacity, and the dilution of the synthetic-rock pellets into an inert medium.
Li, Guiwei; Zhao, Ji; Wu, Wenzheng; Jiang, Jili; Wang, Bofan; Jiang, Hao; Fuh, Jerry Ying Hsi
2018-05-17
Fused deposition modeling 3D printing has become the most widely used additive manufacturing technology because of its low manufacturing cost and simple manufacturing process. However, the mechanical properties of the 3D printing parts are not satisfactory. Certain pressure and ultrasonic vibration were applied to 3D printed samples to study the effect on the mechanical properties of 3D printed non-crystalline and semi-crystalline polymers. The tensile strength of the semi-crystalline polymer polylactic acid was increased by 22.83% and the bending strength was increased by 49.05%, which were almost twice the percentage increase in the tensile strength and five times the percentage increase in the bending strength of the non-crystalline polymer acrylonitrile butadiene styrene with ultrasonic strengthening. The dynamic mechanical properties of the non-crystalline and semi-crystalline polymers were both improved after ultrasonic enhancement. Employing ultrasonic energy can significantly improve the mechanical properties of samples without modifying the 3D printed material or adjusting the forming process parameters.
Methods for manufacturing geometric multi-crystalline cast materials
Stoddard, Nathan G
2013-11-26
Methods are provided for casting one or more of a semi-conductor, an oxide, and an intermetallic material. With such methods, a cast body of a geometrically ordered multi-crystalline form of the one or more of a semiconductor, an oxide, and an intermetallic material may be formed that is free or substantially free of radially-distributed impurities and defects and having at least two dimensions that are each at least about 10 cm.
Spontaneously Flowing Crystal of Self-Propelled Particles
NASA Astrophysics Data System (ADS)
Briand, Guillaume; Schindler, Michael; Dauchot, Olivier
2018-05-01
We experimentally and numerically study the structure and dynamics of a monodisperse packing of spontaneously aligning self-propelled hard disks. The packings are such that their equilibrium counterparts form perfectly ordered hexagonal structures. Experimentally, we first form a perfect crystal in a hexagonal arena which respects the same crystalline symmetry. Frustration of the hexagonal order, obtained by removing a few particles, leads to the formation of a rapidly diffusing "droplet." Removing more particles, the whole system spontaneously forms a macroscopic sheared flow, while conserving an overall crystalline structure. This flowing crystalline structure, which we call a "rheocrystal," is made possible by the condensation of shear along localized stacking faults. Numerical simulations very well reproduce the experimental observations and allow us to explore the parameter space. They demonstrate that the rheocrystal is induced neither by frustration nor by noise. They further show that larger systems flow faster while still remaining ordered.
Waste forms, packages, and seals working group summary
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sridhar, N.
1995-09-01
This article is a summary of the proceedings of a group discussion which took place at the Workshop on the Role of Natural Analogs in Geologic Disposal of High-Level Nuclear Waste in San Antonio, Texas on July 22-25, 1991. The working group concentrated on the subject of radioactive waste forms and packaging. Also included is a description of the use of natural analogs in waste packaging, container materials and waste forms.
Silicon Whisker and Carbon Nanofiber Composite Anode
NASA Technical Reports Server (NTRS)
Ma, Junqing (Inventor); Newman, Aron (Inventor); Lennhoff, John (Inventor)
2015-01-01
A carbon nanofiber can have a surface and include at least one crystalline whisker extending from the surface of the carbon nanofiber. A battery anode composition can be formed from a plurality of carbon nanofibers each including a plurality of crystalline whiskers.
Kalb, Paul D.; Colombo, Peter
1999-07-20
The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogenous molten matrix. The molten matrix may be directed in a "clean" polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment.
Kalb, Paul D.; Colombo, Peter
1998-03-24
The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogenous molten matrix. The molten matrix may be directed in a "clean" polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment.
Kalb, Paul D.; Colombo, Peter
1997-01-01
The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogenous molten matrix. The molten matrix may be directed in a "clean" polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment.
Amorphous and Crystalline Particulates: Challenges and Perspectives in Drug Delivery.
Al-Obaidi, Hisham; Majumder, Mridul; Bari, Fiza
2017-01-01
Crystalline and amorphous dispersions have been the focus of academic and industrial research due to their potential role in formulating poorly water-soluble drugs. This review looks at the progress made starting with crystalline carriers in the form of eutectics moving towards more complex crystalline mixtures. It also covers using glassy polymers to maintain the drug as amorphous exhibiting higher energy and entropy. However, the amorphous form tends to recrystallize on storage, which limits the benefits of this approach. Specific interactions between the drug and the polymer may retard this spontaneous conversion of the amorphous drug. Some studies have shown that it is possible to maintain the drug in the amorphous form for extended periods of time. For the drug and the polymer to form a stable mixture they have to be miscible on a molecular basis. Another form of solid dispersions is pharmaceutical co-crystals, for which research has focused on understanding the chemistry, crystal engineering and physico-chemical properties. USFDA has issued a guidance in April 2013 suggesting that the co-crystals as a pharmaceutical product may be a reality; but just not yet! While some of the research is still oriented towards application of these carriers, understanding the mechanism by which drug-carrier miscibility occurs is also covered. Within this context is the use of thermodynamic models such as Flory-Huggins model with some examples of studies used to predict miscibility. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.
Liquid crystalline order in mucus
NASA Technical Reports Server (NTRS)
Viney, C.; Huber, A. E.; Verdugo, P.
1993-01-01
Mucus plays an exceptionally wide range of important biological roles. It operates as a protective, exchange, and transport medium in the digestive, respiratory, and reproductive systems of humans and other vertebrates. Mucus is a polymer hydrogel. It is secreted as discrete packages (secretory granules) by specialized secretory cells. Mucus hydrogel is stored in a condensed state inside the secretory granules. Depending upon the architecture of their constituent macromolecules and on the composition of the solvent, polymer gels can form liquid crystalline microstructures, with orientational order being exhibited over optically resolvable distances. Individual mucin molecules consist of alternating rigid segments (heavily glycosylated; hydrophilic) and flexible segments (nonglycosylated; hydrophobic). Polymer molecules consisting of rigid units linked by flexible spacers are frequently associated with liquid crystalline behavior, which again raises the possibility that mucus could form anisotropic fluid phases. Suggestions that mucins may be self-associating in dilute solution have previously been challenged on the basis of sedimentation-equilibrium studies performed on mucus in which potential sites of association were competitively blocked with inhibitors. However, the formation of stable liquid crystalline phases does not depend on the existence of inter- or intramolecular associations; these phases can form on the basis of steric considerations alone.
Characterization of thin film CO2 ice through the infrared ν1 + ν3 combination mode
NASA Astrophysics Data System (ADS)
He, Jiao; Vidali, Gianfranco
2018-01-01
Carbon dioxide is abundant in ice mantles of dust grains; some is found in the pure crystalline form as inferred from the double peak splitting of the bending profile at about 650 cm-1. To study how CO2 segregates into the pure form from water-rich mixtures of ice mantles and how it then crystallizes, we used Reflection Absorption InfraRed Spectroscopy to study the structural change of pure CO2 ice as a function of both ice thickness and temperature. We found that the ν1 + ν3 combination mode absorption profile at 3708 cm-1 provides an excellent probe to quantify the degree of crystallinity in CO2 ice. We also found that between 20 and 30 K, there is an ordering transition that we attribute to reorientation of CO2 molecules, while the diffusion of CO2 becomes significant at much higher temperatures. In the formation of pure crystalline CO2 in interstellar medium ices, the rate limiting process is the diffusion/segregation of CO2 molecules in the ice instead of the phase transition from amorphous to crystalline after clusters/islands of CO2 are formed.
Closed Fuel Cycle Waste Treatment Strategy
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vienna, J. D.; Collins, E. D.; Crum, J. V.
This study is aimed at evaluating the existing waste management approaches for nuclear fuel cycle facilities in comparison to the objectives of implementing an advanced fuel cycle in the U.S. under current legal, regulatory, and logistical constructs. The study begins with the Global Nuclear Energy Partnership (GNEP) Integrated Waste Management Strategy (IWMS) (Gombert et al. 2008) as a general strategy and associated Waste Treatment Baseline Study (WTBS) (Gombert et al. 2007). The tenets of the IWMS are equally valid to the current waste management study. However, the flowsheet details have changed significantly from those considered under GNEP. In addition, significantmore » additional waste management technology development has occurred since the GNEP waste management studies were performed. This study updates the information found in the WTBS, summarizes the results of more recent technology development efforts, and describes waste management approaches as they apply to a representative full recycle reprocessing flowsheet. Many of the waste management technologies discussed also apply to other potential flowsheets that involve reprocessing. These applications are occasionally discussed where the data are more readily available. The report summarizes the waste arising from aqueous reprocessing of a typical light-water reactor (LWR) fuel to separate actinides for use in fabricating metal sodium fast reactor (SFR) fuel and from electrochemical reprocessing of the metal SFR fuel to separate actinides for recycle back into the SFR in the form of metal fuel. The primary streams considered and the recommended waste forms include; Tritium in low-water cement in high integrity containers (HICs); Iodine-129: As a reference case, a glass composite material (GCM) formed by the encapsulation of the silver Mordenite (AgZ) getter material in a low-temperature glass is assumed. A number of alternatives with distinct advantages are also considered including a fused silica waste form with encapsulated nano-sized AgI crystals; Carbon-14 immobilized as a CaCO3 in a cement waste form; Krypton-85 stored as a compressed gas; An aqueous reprocessing high-level waste (HLW) raffinate waste immobilized by the vitrification process; An undissolved solids (UDS) fraction from aqueous reprocessing of LWR fuel either included in the borosilicate HLW glass or immobilized in the form of a metal alloy or titanate ceramics; Zirconium-based LWR fuel cladding hulls and stainless steel (SS) fuel assembly hardware super-compacted for disposal or purified for reuse (or disposal as low-level waste, LLW) of Zr by reactive gas separations; Electrochemical process salt HLW incorporated into a glass bonded Sodalite waste form; and Electrochemical process UDS and SS cladding hulls melted into an iron based alloy waste form. Mass and volume estimates for each of the recommended waste forms based on the source terms from a representative flowsheet are reported. In addition to the above listed primary waste streams, a range of secondary process wastes are generated by aqueous reprocessing of LWR fuel, metal SFR fuel fabrication, and electrochemical reprocessing of SFR fuel. These secondary wastes have been summarized and volumes estimated by type and classification. The important waste management data gaps and research needs have been summarized for each primary waste stream and selected waste process.« less
Glasses for immobilization of low- and intermediate-level radioactive waste
NASA Astrophysics Data System (ADS)
Laverov, N. P.; Omel'yanenko, B. I.; Yudintsev, S. V.; Stefanovsky, S. V.; Nikonov, B. S.
2013-03-01
Reprocessing of spent nuclear fuel (SNF) for recovery of fissionable elements is a precondition of long-term development of nuclear energetics. Solution of this problem is hindered by the production of a great amount of liquid waste; 99% of its volume is low- and intermediate-level radioactive waste (LILW). The volume of high-level radioactive waste (HLW), which is characterized by high heat release, does not exceed a fraction of a percent. Solubility of glasses at an elevated temperature makes them unfit for immobilization of HLW, the insulation of which is ensured only by mineral-like matrices. At the same time, glasses are a perfect matrix for LILW, which are distinguished by low heat release. The solubility of borosilicate glass at a low temperature is so low that even a glass with relatively low resistance enables them to retain safety of under-ground LILW depositories without additional engineering barriers. The optimal technology of liquid confinement is their concentration and immobilization in borosilicate glasses, which are disposed in shallow-seated geological repositories. The vitrification of 1 m3 liquid LILW with a salt concentration of ˜300 kg/m3 leaves behind only 0.2 m3 waste, that is, 4-6 times less than by bitumen impregnation and 10 times less than by cementation. Environmental and economic advantages of LILW vitrification result from (1) low solubility of the vitrified LILW in natural water; (2) significant reduction of LILW volume; (3) possibility to dispose the vitrified waste without additional engineering barriers under shallow conditions and in diverse geological media; (4) the strength of glass makes its transportation and storage possible; and finally (5) reliable longterm safety of repositories. When the composition of the glass matrix for LILW is being chosen, attention should be paid to the factors that ensure high technological and economic efficiency of vitrification. The study of vitrified LILW from the Kursk nuclear power plant with high-power channel reactors (HPCR; equivalent Russian acronym, RBMK) and the Kalinin nuclear power plant with pressurized water reactors (PWR; equivalent Russian acronym VVER) after their 14-yr storage in the shallow-seated repository at the MosNPO Radon testing ground has confirmed the safety of repositories ensured by confinement properties of borosilicate matrix. The most efficient vitrification technology is based on cold crucible induction melting. If the content of a chemical element in waste exceeds its solubility in glass, a crystalline phase is formed in the course of vitrification, so that the glass ceramics become a matrix for such waste. Vitrified waste with high Fe; Na and Al; Na, Fe, and Al; Na and B is characterized. The composition of frit and its proportion to waste depends on waste composition. This procedure requires careful laboratory testing.
Final report on cermet high-level waste forms
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kobisk, E.H.; Quinby, T.C.; Aaron, W.S.
1981-08-01
Cermets are being developed as an alternate method for the fixation of defense and commercial high level radioactive waste in a terminal disposal form. Following initial feasibility assessments of this waste form, consisting of ceramic particles dispersed in an iron-nickel base alloy, significantly improved processing methods were developed. The characterization of cermets has continued through property determinations on samples prepared by various methods from a variety of simulated and actual high-level wastes. This report describes the status of development of the cermet waste form as it has evolved since 1977. 6 tables, 18 figures.
Radionuclide and contaminant immobilization in the fluidized bed steam reforming waste products
DOE Office of Scientific and Technical Information (OSTI.GOV)
Neeway, James J.; Qafoku, Nikolla; Westsik, Joseph H.
2012-05-01
The goal of this chapter is to introduce the reader to the Fluidized Bed Steam Reforming (FBSR) process and resulting waste form. The first section of the chapter gives an overview of the potential need for FBSR processing in nuclear waste remediation followed by an overview of the engineering involved in the process itself. This is followed by a description of waste form production at a chemical level followed by a section describing different process streams that have undergone the FBSR process. The third section describes the resulting mineral product in terms of phases that are present and the abilitymore » of the waste form to encapsulate hazardous and radioactive wastes from several sources. Following this description is a presentation of the physical properties of the granular and monolith waste form product including and contaminant release mechanisms. The last section gives a brief summary of this chapter and includes a section on the strengths associated with this waste form and the needs for additional data and remaining questions yet to be answered. The reader is directed elsewhere for more information on other waste forms such as Cast Stone (Lockrem, 2005), Ceramicrete (Singh et al., 1997, Wagh et al., 1999) and geopolymers (Kyritsis et al., 2009; Russell et al., 2006).« less
Austrian Mirrors: Development of Ultra-Low-Loss Cryogenic Crystalline Coatings (DARPA)
2016-07-13
AFRL-AFOSR-UK-TR-2016-0013 Austrian Mirrors: Development of ultra-low- loss cryogenic crystalline coatings (DARPA) Garrett Cole Crystalline Mirror...REPORT DOCUMENTATION PAGE Form ApprovedOMB No . 0704-0188 The public reporting burden for this collection of information is estimated to average 1 hour...that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if
Structure and hydrogen bonds of γS-crystallin and γS-G18V studied by molecular dynamics simulation
NASA Astrophysics Data System (ADS)
Ozawa, A.; Yamada, H.; Mori, S.; Noguchi, Y.; Miyakawa, T.; Morikawa, R.; Takasu, M.
2017-11-01
The γS-crystallin protein maintains transparency and increases the reflection index of the eye lens. Here, γS-G18V, a mutant of γS-crystallin, was studied, in which the 18th residue, glycine, is replaced by valine. This mutation is associated with childhood-onset cortical cataract. Mutated γS-crystallin forms cross-links with other proteins in the eye lens and leads to aggregation at a temperature lower than that for γS-crystallin. In this study, structural analysis of γS-crystallin and γS-G18V was performed by molecular dynamics simulation. It was found that cysteine residues around the area where the mutation is introduced are arranged at the solvent side with less hydrogen bonds than in the case of γS-WT.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Reigel, M.; Johnson, F.; Crawford, C.
2011-09-20
The U.S. Department of Energy (DOE), Office of River Protection (ORP), is responsible for the remediation and stabilization of the Hanford Site tank farms, including 53 million gallons of highly radioactive mixed wasted waste contained in 177 underground tanks. The plan calls for all waste retrieved from the tanks to be transferred to the Waste Treatment Plant (WTP). The WTP will consist of three primary facilities including pretreatment facilities for Low Activity Waste (LAW) to remove aluminum, chromium and other solids and radioisotopes that are undesirable in the High Level Waste (HLW) stream. Removal of aluminum from HLW sludge canmore » be accomplished through continuous sludge leaching of the aluminum from the HLW sludge as sodium aluminate; however, this process will introduce a significant amount of sodium hydroxide into the waste stream and consequently will increase the volume of waste to be dispositioned. A sodium recovery process is needed to remove the sodium hydroxide and recycle it back to the aluminum dissolution process. The resulting LAW waste stream has a high concentration of aluminum and sodium and will require alternative immobilization methods. Five waste forms were evaluated for immobilization of LAW at Hanford after the sodium recovery process. The waste forms considered for these two waste streams include low temperature processes (Saltstone/Cast stone and geopolymers), intermediate temperature processes (steam reforming and phosphate glasses) and high temperature processes (vitrification). These immobilization methods and the waste forms produced were evaluated for (1) compliance with the Performance Assessment (PA) requirements for disposal at the IDF, (2) waste form volume (waste loading), and (3) compatibility with the tank farms and systems. The iron phosphate glasses tested using the product consistency test had normalized release rates lower than the waste form requirements although the CCC glasses had higher release rates than the quenched glasses. However, the waste form failed to meet the vapor hydration test criteria listed in the WTP contract. In addition, the waste loading in the phosphate glasses were not as high as other candidate waste forms. Vitrification of HLW waste as borosilicate glass is a proven process; however the HLW and LAW streams at Hanford can vary significantly from waste currently being immobilized. The ccc glasses show lower release rates for B and Na than the quenched glasses and all glasses meet the acceptance criterion of < 4 g/L. Glass samples spiked with Re{sub 2}O{sub 7} also passed the PCT test. However, further vapor hydration testing must be performed since all the samples cracked and the test could not be performed. The waste loading of the iron phosphate and borosilicate glasses are approximately 20 and 25% respectively. The steam reforming process produced the predicted waste form for both the high and low aluminate waste streams. The predicted waste loadings for the monolithic samples is approximately 39%, which is higher than the glass waste forms; however, at the time of this report, no monolithic samples were made and therefore compliance with the PA cannot be determined. The waste loading in the geopolymer is approximately 40% but can vary with the sodium hydroxide content in the waste stream. Initial geopolymer mixes revealed compressive strengths that are greater than 500 psi for the low aluminate mixes and less than 500 psi for the high aluminate mixes. Further work testing needs to be performed to formulate a geopolymer waste form made using a high aluminate salt solution. A cementitious waste form has the advantage that the process is performed at ambient conditions and is a proven process currently in use for LAW disposal. The Saltstone/Cast Stone formulated using low and high aluminate salt solutions retained at least 97% of the Re that was added to the mix as a dopant. While this data is promising, additional leaching testing must be performed to show compliance with the PA. Compressive strength tests must also be performed on the Cast Stone monoliths to verify PA compliance. Based on testing performed for this report, the borosilicate glass and Cast Stone are the recommended waste forms for further testing. Both are proven technologies for radioactive waste disposal and the initial testing using simulated Hanford LAW waste shows compliance with the PA. Both are resistant to leaching and have greater than 25% waste loading.« less
Phase-Equilibria and Nanostructure Formation in Charged Rigid-Rod Polymers and Carbon Nanotubes
2002-11-10
or liquid crystalline) and the crystalline polymer state. The form-I crystal solvate, identi- fied as a cocrystal of the protonated polymer and the...dissolution temperature, below 100 °C.12,13 The form-II crystal solvate, considered a polymer-solvent cocrystal in which the polymer is deprotonated,11,12...solvate that is a cocrystal of protonated PBZT and PPA anions. As previously mentioned, the fact that these two extreme cases result in similar
EXAFS/XANES studies of plutonium-loaded sodalite/glass waste forms
NASA Astrophysics Data System (ADS)
Richmann, Michael K.; Reed, Donald T.; Kropf, A. Jeremy; Aase, Scott B.; Lewis, Michele A.
2001-09-01
A sodalite/glass ceramic waste form is being developed to immobilize highly radioactive nuclear wastes in chloride form, as part of an electrochemical cleanup process. Two types of simulated waste forms were studied: where the plutonium was alone in an LiCl/KCl matrix and where simulated fission-product elements were added representative of the electrometallurgical treatment process used to recover uranium from spent nuclear fuel also containing plutonium and a variety of fission products. Extended X-ray absorption fine structure spectroscopy (EXAFS) and X-ray absorption near-edge spectroscopy (XANES) studies were performed to determine the location, oxidation state, and particle size of the plutonium within these waste form samples. Plutonium was found to segregate as plutonium(IV) oxide with a crystallite size of at least 4.8 nm in the non-fission-element case and 1.3 nm with fission elements present. No plutonium was observed within the sodalite in the waste form made from the plutonium-loaded LiCl/KCl eutectic salt. Up to 35% of the plutonium in the waste form made from the plutonium-loaded simulated fission-product salt may be segregated with a heavy-element nearest neighbor other than plutonium or occluded internally within the sodalite lattice.
40 CFR 761.345 - Form of the waste to be sampled.
Code of Federal Regulations, 2010 CFR
2010-07-01
... Characterization for PCB Disposal in Accordance With § 761.62, and Sampling PCB Remediation Waste Destined for Off... waste and PCB remediation waste destined for off-site disposal must be in the form of either flattened...
Kalb, P.D.; Colombo, P.
1997-07-15
The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogeneous molten matrix. The molten matrix may be directed in a ``clean`` polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment. 2 figs.
Kalb, P.D.; Colombo, P.
1998-03-24
The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogeneous molten matrix. The molten matrix may be directed in a ``clean`` polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment. 2 figs.
Kalb, P.D.; Colombo, P.
1999-07-20
The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogeneous molten matrix. The molten matrix may be directed in a clean'' polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment. 2 figs.
Low-temperature crystallization of silicate dust in circumstellar disks.
Molster, F J; Yamamura, I; Waters, L B; Tielens, A G; de Graauw, T; de Jong, T; de Koter, A; Malfait, K; van den Ancker, M E; van Winckel, H; Voors, R H; Waelkens, C
1999-10-07
Silicate dust in the interstellar medium is observed to be amorphous, yet silicate dust in comets and interplanetary dust particles is sometimes partially crystalline. The dust in disks that are thought to be forming planets around some young stars also appears to be partially crystalline. These observations suggest that as the dust goes from the precursor clouds to a planetary system, it must undergo some processing, but the nature and extent of this processing remain unknown. Here we report observations of highly crystalline silicate dust in the disks surrounding binary red-giant stars. The dust was created in amorphous form in the outer atmospheres of the red giants, and therefore must be processed in the disks to become crystalline. The temperatures in these disks are too low for the grains to anneal; therefore, some low-temperature process must be responsible. As the physical properties of the disks around young stars and red giants are similar, our results suggest that low-temperature crystallization of silicate grains also can occur in protoplanetary systems.
DOE Office of Scientific and Technical Information (OSTI.GOV)
N. R. Mann; T. A. Todd; K. N. Brewer
1999-04-01
Development of waste treatment processes for the remediation of radioactive wastes is currently underway. A number of experiments were performed at the Idaho Nuclear Technology and Environmental Center (INTEC) located at the Idaho National Engineering and Environmental Laboratory (INEEL) with the commercially available sorbent material, IONSIV IE-911, crystalline silicotitanate (CST), manufactured by UOP LLC. The purpose of this work was to evaluate the removal efficiency, sorbent capacity and selectivity of CST for removing Cs-137 from actual and simulated acidic tank waste in addition to dissolved pilot-plant calcine solutions. The scope of this work included batch contact tests performed with non-radioactivemore » dissolved Al and Run-64 pilot plant calcines in addition to simulants representing the average composition of tank waste. Small-scale column tests were performed with actual INEEL tank WM-183 waste, tank waste simulant, dissolved Al and Run-64 pilot plant calcine solutions. Small-scale column experiments using actual WM-183 tank waste resulted in fifty-percent Cs-137 breakthrough at approximately 589 bed volumes. Small-scale column experiments using the tank waste simulant displayed fifty-percent Cs-137 breakthrough at approximately 700 bed volumes. Small-scale column experiments using dissolved Al calcine simulant displayed fifty-percent Cs-137 breakthrough at approximately 795 bed volumes. Column experiments with dissolved Run-64, pilot plant calcine did not reach fifty-percent breakthrough throughout the test.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mattigod, Shas V.; Wellman, Dawn M.; Bovaird, Chase C.
2011-08-31
One of the methods being considered for safely disposing of Category 3 low-level radioactive wastes is to encase the waste in concrete. Such concrete encasement would contain and isolate the waste packages from the hydrologic environment and would act as an intrusion barrier. The current plan for waste isolation consists of stacking low-level waste packages on a trench floor, surrounding the stacks with reinforced steel, and encasing these packages in concrete. These concrete-encased waste stacks are expected to vary in size with maximum dimensions of 6.4 m long, 2.7 m wide, and 4 m high. The waste stacks are expectedmore » to have a surrounding minimum thickness of 15 cm of concrete encasement. These concrete-encased waste packages are expected to withstand environmental exposure (solar radiation, temperature variations, and precipitation) until an interim soil cover or permanent closure cover is installed, and to remain largely intact thereafter. Any failure of concrete encasement may result in water intrusion and consequent mobilization of radionuclides from the waste packages. The mobilized radionuclides may escape from the encased concrete by mass flow and/or diffusion and move into the surrounding subsurface environment. Therefore, it is necessary to assess the performance of the concrete encasement structure and the ability of the surrounding soil to retard radionuclide migration. The retardation factors for radionuclides contained in the waste packages can be determined from measurements of diffusion coefficients for these contaminants through concrete and fill material. Some of the mobilization scenarios include (1) potential leaching of waste form before permanent closure cover is installed; (2) after the cover installation, long-term diffusion of radionuclides from concrete waste form into surrounding fill material; (3) diffusion of radionuclides from contaminated soils into adjoining concrete encasement and clean fill material. Additionally, the rate of diffusion of radionuclides may be affected by the formation of structural cracks in concrete, the carbonation of the buried waste form, and any potential effect of metallic iron (in the form of rebars) on the mobility of radionuclides. The radionuclides iodine-129 ({sup 129}I), technetium-99 ({sup 99}Tc), and uranium-238 ({sup 238}U) are identified as long-term dose contributors in Category 3 waste (Mann et al. 2001; Wood et al. 1995). Because of their anionic nature in aqueous solutions, {sup 129}I, {sup 99}Tc, and carbonate-complexed {sup 238}U may readily leach into the subsurface environment (Serne et al. 1989, 1992a, b, 1993, and 1995). The leachability and/or diffusion of radionuclide species must be measured to assess the long-term performance of waste grouts when contacted with vadose-zone pore water or groundwater. Although significant research has been conducted on the design and performance of cementitious waste forms, the current protocol conducted to assess radionuclide stability within these waste forms has been limited to the Toxicity Characteristic Leaching Procedure, Method 1311 Federal Registry (EPA 1992) and ANSI/ANS-16.1 leach test (ANSI 1986). These tests evaluate the performance under water-saturated conditions and do not evaluate the performance of cementitious waste forms within the context of waste repositories which are located within water-deficient vadose zones. Moreover, these tests assess only the diffusion of radionuclides from concrete waste forms and neglect evaluating the mechanisms of retention, stability of the waste form, and formation of secondary phases during weathering, which may serve as long-term secondary hosts for immobilization of radionuclides. The results of recent investigations conducted under arid and semi-arid conditions (Al-Khayat et al. 2002; Garrabrants et al. 2002; Garrabrants and Kosson 2003; Garrabrants et al. 2004; Gervais et al. 2004; Sanchez et al. 2002; Sanchez et al. 2003) provide valuable information suggesting structural and chemical changes to concrete waste forms which may affect contaminant containment and waste form performance. However, continued research is necessitated by the need to understand: the mechanism of contaminant release; the significance of contaminant release pathways; how waste form performance is affected by the full range of environmental conditions within the disposal facility; the process of waste form aging under conditions that are representative of processes occurring in response to changing environmental conditions within the disposal facility; the effect of waste form aging on chemical, physical, and radiological properties, and the associated impact on contaminant release. Recent reviews conducted by the National Academies of Science recognized the efficacy of cementitious materials for waste isolation, but further noted the significant shortcomings in our current understanding and testing protocol for evaluating the performance of various formulations.« less
Immobilization of organic radioactive and non-radioactive liquid waste in a composite matrix
DOE Office of Scientific and Technical Information (OSTI.GOV)
Galkin, Anatoliy; Gelis, Artem V.; Castiglioni, Andrew J.
A method for immobilizing liquid radioactive waste is provided, the method having the steps of mixing waste with polymer to form a non-liquid waste; contacting the non-liquid waste with a solidifying agent to create a mixture, heating the mixture to cause the polymer, waste, and filler to irreversibly bind in a solid phase, and compressing the solid phase into a monolith. The invention also provides a method for immobilizing liquid radioactive waste containing tritium, the method having the steps of mixing liquid waste with polymer to convert the liquid waste to a non-liquid waste, contacting the non-liquid waste with amore » solidifying agent to create a mixture, heating the mixture to form homogeneous, chemically stable solid phase, and compressing the chemically stable solid phase into a final waste form, wherein the polymer comprises approximately a 9:1 weight ratio mixture of styrene block co-polymers and cross linked co-polymers of acrylamides.« less
Secondary Waste Simulant Development for Cast Stone Formulation Testing
DOE Office of Scientific and Technical Information (OSTI.GOV)
Russell, Renee L.; Westsik, Joseph H.; Rinehart, Donald E.
Washington River Protection Solutions, LLC (WRPS) funded Pacific Northwest National Laboratory (PNNL) to conduct a waste form testing program to implement aspects of the Secondary Liquid Waste Treatment Cast Stone Technology Development Plan (Ashley 2012) and the Hanford Site Secondary Waste Roadmap (PNNL 2009) related to the development and qualification of Cast Stone as a potential waste form for the solidification of aqueous wastes from the Hanford Site after the aqueous wastes are treated at the Effluent Treatment Facility (ETF). The current baseline is that the resultant Cast Stone (or grout) solid waste forms would be disposed at the Integratedmore » Disposal Facility (IDF). Data and results of this testing program will be used in the upcoming performance assessment of the IDF and in the design and operation of a solidification treatment unit planned to be added to the ETF. The purpose of the work described in this report is to 1) develop simulants for the waste streams that are currently being fed and future WTP secondary waste streams also to be fed into the ETF and 2) prepare simulants to use for preparation of grout or Cast Stone solid waste forms for testing.« less
NASA Astrophysics Data System (ADS)
Riley, Brian J.; Peterson, Jacob A.; Kroll, Jared O.; Frank, Steven M.
2018-04-01
In this study, hydrothermal and salt-occlusion processes were used to make chlorosodalite through reactions with a high-LiCl salt simulating a waste stream generated from pyrochemical treatment of oxide-based used nuclear fuel. Some products were reacted with glass binders to increase chlorosodalite yield through alkali ion exchange and to aid in densification. Hydrothermal processes included reaction of the salt simulant in an autoclave with either zeolite 4A or sodium aluminate and colloidal silica. Chlorosodalite yields in the crystalline products were nearly complete in the glass-bonded materials at values of 100 mass% for the salt-occlusion method, up to 99.0 mass% for the hydrothermal synthesis with zeolite 4A, and up to 96 mass% for the hydrothermal synthesis with sodium aluminate and colloidal silica. These results show promise for using chemically stable chlorosodalite to immobilize oxide reduction salt wastes.
High ion-exchange properties of hybrid materials from X-type zeolite and ground glass powder
NASA Astrophysics Data System (ADS)
Taira, Nobuyuki; Yoshida, Kohei
2017-10-01
Zeolites are crystalline aluminosilicates with a homogeneous distribution of micropores with a superior cation-exchange capacity. Because they have especially excellent selective exchange properties, a considerable number of studies have been conducted on treating water containing radioisotopes using the zeolites. When using artificial zeolites, they have inferior sinterability; in addition, it is quite hard for them to remove from polluted liquid since these artificial zeolites are principally synthesized as a form of powder, which is a disadvantage. In this study, hybrid materials were prepared from X-type zeolite and waste glass powder. Their ion-removal effect and mechanical strength were investigated. The zeolite and waste glass were ground in an agate mortar in several ratios. 0.5 g of the mixture was pressure-molded into pellets having a diameter of 7 mm. These pellets were slowly heated at the speed of 240°C/h to 700°C and maintained at 700°C for 2 h. The removal rate of Sr2+ ions increased as the amount of X-type zeolite in the hybrid materials increased; the former increased up to 100% when the content of latter exceeded 50%. The mechanical strength increased by increasing the amount of glass in the hybrid materials. This is attributed to the fact that the glass powder acts as a binder that improves the densification and consequently the mechanical strength of the hybrid materials.
Natural polymer biocomposites produced from processing raw wood flour by severe shear deformation.
Zhang, Xiaoqing; Wu, Xiaolin; Haryono, Hengky; Xia, Kenong
2014-11-26
Wood flour (WF) based natural polymer biocomposites were produced using the equal channel angular pressing (ECAP) technique. The wood particle structures were disrupted and the cellulose crystallinity was decreased while bulk materials were formed with continuous phase structures by the severe shear-deformation during ECAP. The mechanical properties of the processed WF materials were enhanced when the processing temperature was increased due to enhanced intermolecular interactions and thermal crosslinking reactions among WF components. The processing capability was improved by using wheat gluten (WG) as additives, leading to significantly reduced processing temperature. Effective chain penetration and strong intermolecular interactions in conjunction with chemical crosslinking occurred between WG and the amorphous components in WF. However, the thermal decomposition of the WG component also occurred at increased temperatures, resulting in a decrease in the mechanical strength of the WF/WG composites. The result has demonstrated that ECAP is a promising methodology to produce renewable and degradable biocomposites from wood waste. Copyright © 2014 Elsevier Ltd. All rights reserved.
Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments
Perdrial, Nicolas; Vázquez-Ortega, Angélica; Wang, Guohui; ...
2017-12-05
Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. Here, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO 4-reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K 2(UO 2) 6O 4(OH) 6·8H 2O]- and becquerelite [Ca(UO 2) 6O 4(OH) 6·8H 2O]-like species.more » Subsequent further removal of uranium coincided with that of Si and accumulation of boltwoodite, [(K, Na)(UO 2) 2O 4(HSiO 4) 2•0.5(H 2O)]-like species of uranium at 180 and 365 days. When present, PO 4 exerted a direct and strong control over U speciation. Furthermore, the detection of meta-ankoleite, [K 2(UO 2) 2O 4(PO 4) 2·6H 2O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO 4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO 4 present, nearly all uranium would have precipitated in the upper soil.« less
Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments
DOE Office of Scientific and Technical Information (OSTI.GOV)
Perdrial, Nicolas; Vázquez-Ortega, Angélica; Wang, Guohui
Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. In this study, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO(4)(-)reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K-2(UO2)(6)O-4(OH)(6)center dot 8H(2)O]-and becquerelite [Ca(UO2)(6)O-4(OH)(6)center dot 8H(2)O]-like species. Subsequent further removal of uranium coincided withmore » that of Si and accumulation of boltwoodite, [(K, Na)(UO2)(2)O-4(HSiO4)(2)center dot 0.5(H2O)]-like species of uranium at 180 and 365 days. When present, PO4 exerted a direct and strong control over U speciation. The detection of meta-ankoleite, [K-2(UO2)(2)O-4(PO4)(2)center dot 6H(2)O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO4 present, nearly all uranium would have precipitated in the upper soil.« less
Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments
DOE Office of Scientific and Technical Information (OSTI.GOV)
Perdrial, Nicolas; Vázquez-Ortega, Angélica; Wang, Guohui
Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. Here, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO 4-reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K 2(UO 2) 6O 4(OH) 6·8H 2O]- and becquerelite [Ca(UO 2) 6O 4(OH) 6·8H 2O]-like species.more » Subsequent further removal of uranium coincided with that of Si and accumulation of boltwoodite, [(K, Na)(UO 2) 2O 4(HSiO 4) 2•0.5(H 2O)]-like species of uranium at 180 and 365 days. When present, PO 4 exerted a direct and strong control over U speciation. Furthermore, the detection of meta-ankoleite, [K 2(UO 2) 2O 4(PO 4) 2·6H 2O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO 4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO 4 present, nearly all uranium would have precipitated in the upper soil.« less
Environmentally-Friendly Geopolymeric Binders Made with Silica
NASA Astrophysics Data System (ADS)
Erdogan, S. T.
2013-12-01
Portland cement (PC) is the ubiquitous binding material for constructions works. It is a big contributor to global warming and climate change since its production is responsible for 5-10 % of all anthropogenic CO2 emissions. Half of this emission arises from the calcination of calcareous raw materials and half from kiln fuel burning and cement clinker grinding. Recently there have been efforts to develop alternative binders with lower greenhouse gas emissions. One such class of binders is geopolymers, formed by activating natural or waste materials with suitable alkaline or acidic solutions. These binders use natural or industrial waste raw materials with a very low CO2 footprint from grinding of the starting materials, and some from the production of the activating chemicals. The total CO2 emissions from carefully formulated mixtures can be as low as 1/10th - 1/5th of those of PC concrete mixtures with comparable properties. While use of industrial wastes as raw materials is environmentally preferable, the variability of their chemical compositions over time renders their use difficult. Use of natural materials depletes resources but can have more consistent properties and can be more easily accepted. Silica sand is a natural material containing very high amounts of quartz. Silica fume is a very fine waste from silicon metal production that is mostly non-crystalline silica. This study describes the use of sodium hydroxide and sodium silicate solutions to yield mortars with mechanical properties comparable to those of portland cement mortars and with better chemical and thermal durability. Strength gain is slower than with PC mixtures at room temperature but adequate ultimate strength can be achieved with curing at slightly elevated temperatures in less than 24 h. The consistency of the chemical compositions of these materials and their abundance in several large, developing countries makes silica attractive for producing sustainable concretes with reduced carbon footprints.
Liquid Secondary Waste Grout Formulation and Waste Form Qualification
DOE Office of Scientific and Technical Information (OSTI.GOV)
Um, Wooyong; Williams, B. D.; Snyder, Michelle M. V.
This report describes the results from liquid secondary waste (LSW) grout formulation and waste form qualification tests performed at Pacific Northwest National Laboratory (PNNL) for Washington River Protection Solutions (WRPS) to evaluate new formulations for preparing a grout waste form with high-sulfate secondary waste simulants and the release of key constituents from these grout monoliths. Specific objectives of the LSW grout formulation and waste form qualification tests described in this report focused on five activities: 1.preparing new formulations for the LSW grout waste form with high-sulfate LSW simulants and solid characterization of the cured LSW grout waste form; 2.conducting themore » U.S. Environmental Protection Agency (EPA) Method 1313 leach test (EPA 2012) on the grout prepared with the new formulations, which solidify sulfate-rich Hanford Tank Waste Treatment and Immobilization Plant (WTP) off-gas condensate secondary waste simulant, using deionized water (DIW); 3.conducting the EPA Method 1315 leach tests (EPA 2013) on the grout monoliths made with the new dry blend formulations and three LSW simulants (242-A evaporator condensate, Environmental Restoration Disposal Facility (ERDF) leachate, and WTP off-gas condensate) using two leachants, DIW and simulated Hanford Integrated Disposal Facility (IDF) Site vadose zone pore water (VZPW); 4.estimating the 99Tc desorption K d (distribution coefficient) values for 99Tc transport in oxidizing conditions to support the IDF performance assessment (PA); 5.estimating the solubility of 99Tc(IV)-bearing solid phases for 99Tc transport in reducing conditions to support the IDF PA.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Serdar, Marijana; Meral, Cagla; Kunz, Martin
2015-05-15
The mineralogy and spatial distribution of nano-crystalline corrosion products that form in the steel/concrete interface were characterized using synchrotron X-ray micro-diffraction (μ-XRD). Two types of low-nickel high-chromium reinforcing steels embedded into mortar and exposed to NaCl solution were investigated. Corrosion in the samples was confirmed by electrochemical impedance spectroscopy (EIS). μ-XRD revealed that goethite (α-FeOOH) and akaganeite (β-FeOOH) are the main iron oxide–hydroxides formed during the chloride-induced corrosion of stainless steel in concrete. Goethite is formed closer to the surface of the steel due to the presence of chromium in the steel, while akaganeite is formed further away from themore » surface due to the presence of chloride ions. Detailed microstructural analysis is shown and discussed on one sample of each type of steel. - Highlights: • Synchrotron micro-diffraction used to map the distribution of crystalline phases. • Goethite and akaganeite are the main corrosion products during chloride induced corrosion in mortar. • Layers of goethite and akaganeite are negatively correlated. • EDS showed Cr present in corrosion products identified by SEM.« less
NASA Astrophysics Data System (ADS)
Figueiredo, Bruno; Tsang, Chin-Fu; Niemi, Auli; Lindgren, Georg
2016-11-01
Laboratory and field experiments done on fractured rock show that flow and solute transport often occur along flow channels. `Sparse channels' refers to the case where these channels are characterised by flow in long flow paths separated from each other by large spacings relative to the size of flow domain. A literature study is presented that brings together information useful to assess whether a sparse-channel network concept is an appropriate representation of the flow system in tight fractured rock of low transmissivity, such as that around a nuclear waste repository in deep crystalline rocks. A number of observations are made in this review. First, conventional fracture network models may lead to inaccurate results for flow and solute transport in tight fractured rocks. Secondly, a flow dimension of 1, as determined by the analysis of pressure data in well testing, may be indicative of channelised flow, but such interpretation is not unique or definitive. Thirdly, in sparse channels, the percolation may be more influenced by the fracture shape than the fracture size and orientation but further studies are needed. Fourthly, the migration of radionuclides from a waste canister in a repository to the biosphere may be strongly influenced by the type of model used (e.g. discrete fracture network, channel model). Fifthly, the determination of appropriateness of representing an in situ flow system by a sparse-channel network model needs parameters usually neglected in site characterisation, such as the density of channels or fracture intersections.
Method for calcining radioactive wastes
Bjorklund, William J.; McElroy, Jack L.; Mendel, John E.
1979-01-01
This invention relates to a method for the preparation of radioactive wastes in a low leachability form by calcining the radioactive waste on a fluidized bed of glass frit, removing the calcined waste to melter to form a homogeneous melt of the glass and the calcined waste, and then solidifying the melt to encapsulate the radioactive calcine in a glass matrix.
Effect of drying conditions on crystallinity of amylose nanoparticles prepared by nanoprecipitation.
Yan, Xiaoxia; Chang, Yanjiao; Wang, Qian; Fu, Youjia; Zhou, Jiang
2017-04-01
In this study, amylose nanoparticles prepared by nanoprecipitation were dried at different conditions. The crystalline structure, crystallinity, re-dispersibility and morphological characteristic of the amylose nanoparticles after drying were investigated. X-ray diffraction analysis revealed that the V-type crystalline structure of the amylose nanoparticles formed in the drying process instead of the precipitation process, and drying condition significantly affects the crystallinity. The temperature cycles drying at 4°C and 40°C considerably increased crystallinity of the amylose nanoparticles, 24h (4/40°C, 12h/12h) drying under 11% relative humidity could give rise to a crystallinity up to 50.05%. The applied drying procedures had no obvious effect on the appearance of the amylose nanoparticles. The Z average-size (d. nm) and polydispersity index (PDI) obtained from dynamic light scattering analysis suggested that the drying processes caused some aggregates, but the dried amylose nanoparticles could be well dispersed in water. Copyright © 2017 Elsevier B.V. All rights reserved.
Li, Guiwei; Zhao, Ji; Wu, Wenzheng; Jiang, Jili; Wang, Bofan; Jiang, Hao
2018-01-01
Fused deposition modeling 3D printing has become the most widely used additive manufacturing technology because of its low manufacturing cost and simple manufacturing process. However, the mechanical properties of the 3D printing parts are not satisfactory. Certain pressure and ultrasonic vibration were applied to 3D printed samples to study the effect on the mechanical properties of 3D printed non-crystalline and semi-crystalline polymers. The tensile strength of the semi-crystalline polymer polylactic acid was increased by 22.83% and the bending strength was increased by 49.05%, which were almost twice the percentage increase in the tensile strength and five times the percentage increase in the bending strength of the non-crystalline polymer acrylonitrile butadiene styrene with ultrasonic strengthening. The dynamic mechanical properties of the non-crystalline and semi-crystalline polymers were both improved after ultrasonic enhancement. Employing ultrasonic energy can significantly improve the mechanical properties of samples without modifying the 3D printed material or adjusting the forming process parameters. PMID:29772802
A method for the quantitative determination of crystalline phases by X-ray
NASA Technical Reports Server (NTRS)
Petzenhauser, I.; Jaeger, P.
1988-01-01
A mineral analysis method is described for rapid quantitative determination of crystalline substances in those cases in which the sample is present in pure form or in a mixture of known composition. With this method there is no need for prior chemical analysis.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Perry, Frank Vinton; Kelley, Richard E.
The DOE Spent Fuel and Waste Technology (SWFT) R&D Campaign is supporting research on crystalline rock, shale (argillite) and salt as potential host rocks for disposal of HLW and SNF in a mined geologic repository. The distribution of these three potential repository host rocks is limited to specific regions of the US and to different geologic and hydrologic environments (Perry et al., 2014), many of which may be technically suitable as a site for mined geologic disposal. This report documents a regional geologic evaluation of the Pierre Shale, as an example of evaluating a potentially suitable shale for siting amore » geologic HLW repository. This report follows a similar report competed in 2016 on a regional evaluation of crystalline rock that focused on the Superior Province of the north-central US (Perry et al., 2016).« less
Study of crystallinity and thermal behavior of gamma irradiated luffa fiber
NASA Astrophysics Data System (ADS)
Patra, Subhashree; Mohanta, Kamal Lochan; Parida, Chhatrapati
2018-04-01
The purpose of this study is to examine the effect of high energy 6 MV X-ray photon beams on fiber of luffa cylindrica (LC), an agricultural waste of India. Techniques such as XRD, FTIR, SEM and TGA are used to study the structural changes and thermal behavior of fiber after physical modification by X-ray photon. Results illustrated that the crystallinity of cellulose in modified fibers was destroyed. High reactivity of modified LC fiber was ascertained from the presence of carboxylic group in the FT-IR spectrum. TGA study revealed increase in hydrophobicity of the modified fiber. The variation of these properties was analyzed with variation in dose of irradiation. Before treatment, the LC fibers are modified with Ca salts in order to explore their applications in biomedical terrain.
The molecular refractive function of lens γ-crystallins
Zhao, Huaying; Brown, Patrick H.; Magone, M. Teresa; Schuck, Peter
2011-01-01
γ-crystallins constitute the major protein component in the nucleus of the vertebrate eye lens. Present at very high concentrations, they exhibit extreme solubility and thermodynamic stability to prevent scattering of light and the formation of cataracts. However, functions beyond this structural role have remained mostly unclear. Here, we calculate molecular refractive index increments of crystallins. We show that all lens γ-crystallins have evolved a significantly elevated molecular refractive index increment, which is far above those of most proteins, including non-lens members of the βγ-crystallin family from different species. The same trait has evolved in parallel in crystallins of different phyla, including in the S-crystallins of cephalopods. A high refractive index increment can lower the crystallin concentration required to achieve a suitable refractive power of the lens, and thereby reduce their propensity to aggregate and form cataract. To produce a significant increase of the refractive index increment, a substantial global shift in the amino acid composition is required, which can naturally explain the highly unusual amino acid composition of γ-crystallins and their functional homologues. This function provides a new perspective for interpreting their molecular structure. PMID:21684289
The molecular refractive function of lens γ-Crystallins.
Zhao, Huaying; Brown, Patrick H; Magone, M Teresa; Schuck, Peter
2011-08-19
γ-Crystallins constitute the major protein component in the nucleus of the vertebrate eye lens. Present at very high concentrations, they exhibit extreme solubility and thermodynamic stability to prevent scattering of light and formation of cataracts. However, functions beyond this structural role have remained mostly unclear. Here, we calculate molecular refractive index increments of crystallins. We show that all lens γ-crystallins have evolved a significantly elevated molecular refractive index increment, which is far above those of most proteins, including nonlens members of the βγ-crystallin family from different species. The same trait has evolved in parallel in crystallins of different phyla, including S-crystallins of cephalopods. A high refractive index increment can lower the crystallin concentration required to achieve a suitable refractive power of the lens and thereby reduce their propensity to aggregate and form cataracts. To produce a significant increase in the refractive index increment, a substantial global shift in amino acid composition is required, which can naturally explain the highly unusual amino acid composition of γ-crystallins and their functional homologues. This function provides a new perspective for interpreting their molecular structure. Copyright © 2011. Published by Elsevier Ltd.
Glass binder development for a glass-bonded sodalite ceramic waste form
DOE Office of Scientific and Technical Information (OSTI.GOV)
Riley, Brian J.; Vienna, John D.; Frank, Steven M.
This paper discusses work to develop Na2O-B2O3-SiO2 glass binders for immobilizing LiCl-KCl eutectic salt waste in a glass-bonded sodalite waste form following electrochemical reprocessing of used metallic nuclear fuel. Here, five new glasses with high Na2O contents were designed to generate waste forms having higher sodalite contents and fewer stress fractures. The structural, mechanical, and thermal properties of the new glasses were measured using variety of analytical techniques. The glasses were then used to produce ceramic waste forms with surrogate salt waste. The materials made using the glasses developed during this study were formulated to generate more sodalite than materialsmore » made with previous baseline glasses used. The coefficients of thermal expansion for the glass phase in the glass-bonded sodalite waste forms made with the new binder glasses were closer to the sodalite phase in the critical temperature region near and below the glass transition temperature. These improvements should result in lower probability of cracking in the full-scale monolithic ceramic waste form, leading to better long-term chemical durability. Additionally, a model generated during this study for predicting softening temperature of silicate binder glasses is presented.« less
LEACHING BOUNDARY MOVEMENT IN SOLIDIFIED/STABILIZED WASTE FORMS
Investigation of the leaching of cement-based waste forms in acetic acid solutions found that acids attacked the waste form from the surface toward the center. A sharp leaching boundary was identified in every leached sample, using pH color indica- tors. The movement of the leach...
Pajander, Jari; Rensonnet, Alexia; Hietala, Sami; Rantanen, Jukka; Baldursdottir, Stefania
2017-02-25
The effect of product design parameters on the formation and properties of an injection molded solid dosage form consisting of poly(ethylene oxide)s (PEO) and two different active pharmaceutical ingredients (APIs) was studied. The product design parameters explored were melting temperature and the duration of melting, API loading degree and the molecular weight (M w ) of PEO. The solid form composition of the model APIs, theophylline and carbamazepine, was of specific interest, and its possible impact on the in vitro drug release behavior. M w of PEO had the greatest impact on the release rate of both APIs. High M w resulted in slower API release rate. Process temperature had two-fold effect with PEO 300,000g/mol. Firstly, higher process temperature transformed the crystalline part of the polymer into metastable folded form (more folded crystalline regions) and less into the more stable extended form (more extended crystalline regions), which lead to enhanced theophylline release rate. Secondly, the higher process temperature seemed to induce carbamazepine polymorphic transformation from p-monoclinic form III (carbamazepine (M)) into trigonal form II (carbamazepine (T)). The results indicated that the actual content of carbamazepine (T) affected drug release behavior more than the magnitude of transformation. Copyright © 2016 Elsevier B.V. All rights reserved.
Nanowires, nanostructures and devices fabricated therefrom
Majumdar, Arun; Shakouri, Ali; Sands, Timothy D.; Yang, Peidong; Mao, Samuel S.; Russo, Richard E.; Feick, Henning; Weber, Eicke R.; Kind, Hannes; Huang, Michael; Yan, Haoquan; Wu, Yiying; Fan, Rong
2005-04-19
One-dimensional nanostructures having uniform diameters of less than approximately 200 nm. These inventive nanostructures, which we refer to as "nanowires", include single-crystalline homostructures as well as heterostructures of at least two single-crystalline materials having different chemical compositions. Because single-crystalline materials are used to form the heterostructure, the resultant heterostructure will be single-crystalline as well. The nanowire heterostructures are generally based on a semiconducting wire wherein the doping and composition are controlled in either the longitudinal or radial directions, or in both directions, to yield a wire that comprises different materials. Examples of resulting nanowire heterostructures include a longitudinal heterostructure nanowire (LOHN) and a coaxial heterostructure nanowire (COHN).
NASA Astrophysics Data System (ADS)
Ortega, Luis H.; Kaminski, Michael D.; Zeng, Zuotao; Cunnane, James
2013-07-01
In the pursuit of methods to improve nuclear waste form thermal properties and combine potential nuclear fuel cycle wastes, a bronze alloy was combined with an alkali, alkaline earth metal bearing ceramic to form a cermet. The alloy was prepared from copper and tin (10 mass%) powders. Pre-sintered ceramic consisting of cesium, strontium, barium and rubidium alumino-silicates was mixed with unalloyed bronze precursor powders and cold pressed to 300 × 103 kPa, then sintered at 600 °C and 800 °C under hydrogen. Cermets were also prepared that incorporated molybdenum, which has a limited solubility in glass, under similar conditions. The cermet thermal conductivities were seven times that of the ceramic alone. These improved thermal properties can reduce thermal gradients within the waste forms thus lowering internal temperature gradients and thermal stresses, allowing for larger waste forms and higher waste loadings. These benefits can reduce the total number of waste packages necessary to immobilize a given amount of high level waste and immobilize troublesome elements.
Civeira, Matheus S; Pinheiro, Rafael N; Gredilla, Ainara; de Vallejuelo, Silvia Fdez Ortiz; Oliveira, Marcos L S; Ramos, Claudete G; Taffarel, Silvio R; Kautzmann, Rubens M; Madariaga, Juan Manuel; Silva, Luis F O
2016-02-15
Brazilian coal area (South Brazil) impacted the environment by means of a large number of coal waste piles emplaced over the old mine sites and the adjacent areas of the Criciúma, Urussanga, and Siderópolis cities. The area studied here was abandoned and after almost 30 years (smokeless visual) some companies use the actual minerals derived from burning coal cleaning rejects (BCCRs) complied in the mentioned area for industry tiles or refractory bricks. Mineralogical and geochemical similarities between the BCCRs and non-anthropogenic geological environments are outlined here. Although no visible flames were observed, this study revealed that auto-combustion existed in the studied area for many years. The presence of amorphous phases, mullite, hematite and other Fe-minerals formed by high temperature was found. There is also pyrite, Fe-sulphates (eg. jarosite) and unburnt coal present, which are useful for comparison purposes. Bad disposal of coal-dump wastes represents significant environmental concerns due to their potential influence on atmosphere, river sediments, soils and as well as on the surface and groundwater in the surroundings of these areas. The present study using advanced analytical techniques were performed to provide an improved understanding of the complex processes related with sulphide-rich coal waste oxidation, spontaneous combustion and mineral formation. It is reporting huge numbers of rare minerals with alunite, montmorillonite, szomolnokite, halotrichite, coquimbite and copiapite at the BCCRs. The data showed the presence of abundant amorphous Si-Al-Fe-Ti as (oxy-)hydroxides and Fe-hydro/oxides with goethite and hematite with various degrees of crystallinity, containing hazardous elements, such as Cu, Cr, Hf, Hg, Mo, Ni, Se, Pb, Th, U, Zr, and others. By Principal Component Analysis (PCA), the mineralogical composition was related with the range of elemental concentration of each sample. Most of the nano-minerals and ultra-fine particles found in the burned coal-dump wastes are the same as those commonly associated with coal cleaning rejects, in which oxidation of sulphides plays an important role to environment and human health. Copyright © 2015 Elsevier B.V. All rights reserved.
Glass ceramic obtained by tailings and tin mine waste reprocessing from Llallagua, Bolivia
NASA Astrophysics Data System (ADS)
Arancibia, Jony Roger Hans; Villarino, Cecilia; Alfonso, Pura; Garcia-Valles, Maite; Martinez, Salvador; Parcerisa, David
2014-05-01
In Bolivia Sn mining activity produces large tailings of SiO2-rich residues. These tailings contain potentially toxic elements that can be removed into the surface water and produce a high environmental pollution. This study determines the thermal behaviour and the viability of the manufacture of glass-ceramics from glass. The glass has been obtained from raw materials representative of the Sn mining activities from Llallagua (Bolivia). Temperatures of maximum nucleation rate (Tn) and crystallization (Tcr) were calculated from the differential thermal analyses. The final mineral phases were determined by X-ray diffraction and textures were observed by scanning electron microscopy. Crystalline phases are nefeline occurring with wollastonite or plagioclase. Tn for nepheline is between 680 ºC and 700 ºC, for wollastonite, 730 ºC and for plagioclase, 740 ºC. Tcr for nefeline is between 837 and 965 ºC; for wollastonite, 807 ºC and for plagioclase, 977 ºC. In order to establish the mechanical characteristics and efficiency of the vitrification process in the fixation of potentially toxic elements the resistance to leaching and micro-hardness were determined. The obtained contents of the elements leached from the glass ceramic are well below the limits established by the European legislation. So, these analyses confirm that potentially toxic elements remain fixed in the structure of mineral phases formed in the glass-ceramic process. Regarding the values of micro-hardness results show that they are above those of a commercial glass. The manufacture of glass-ceramics from mining waste reduces the volume of tailings produced for the mining industry and, in turn enhances the waste, transforming it into a product with industrial application. Acknowledgements: This work was partly financed by the project AECID: A3/042750/11, and the SGR 2009SGR-00444.
Temperature-package power correlations for open-mode geologic disposal concepts.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hardin, Ernest.
2013-02-01
Logistical simulation of spent nuclear fuel (SNF) management in the U.S. combines storage, transportation and disposal elements to evaluate schedule, cost and other resources needed for all major operations leading to final geologic disposal. Geologic repository reference options are associated with limits on waste package thermal power output at emplacement, in order to meet limits on peak temperature for certain key engineered and natural barriers. These package power limits are used in logistical simulation software such as CALVIN, as threshold requirements that must be met by means of decay storage or SNF blending in waste packages, before emplacement in amore » repository. Geologic repository reference options include enclosed modes developed for crystalline rock, clay or shale, and salt. In addition, a further need has been addressed for open modes in which SNF can be emplaced in a repository, then ventilated for decades or longer to remove heat, prior to permanent repository closure. For each open mode disposal concept there are specified durations for surface decay storage (prior to emplacement), repository ventilation, and repository closure operations. This study simulates those steps for several timing cases, and for SNF with three fuel-burnup characteristics, to develop package power limits at which waste packages can be emplaced without exceeding specified temperature limits many years later after permanent closure. The results are presented in the form of correlations that span a range of package power and peak postclosure temperature, for each open-mode disposal concept, and for each timing case. Given a particular temperature limit value, the corresponding package power limit for each case can be selected for use in CALVIN and similar tools.« less
Cast Stone Formulation for Nuclear Waste Immobilization at Higher Sodium Concentrations
Fox, Kevin; Cozzi, Alex; Roberts, Kimberly; ...
2014-11-01
Low activity radioactive waste at U.S. Department of Energy sites can be immobilized for permanent disposal using cementitious waste forms. This study evaluated waste forms produced with simulated wastes at concentrations up to twice that of currently operating processes. The simulated materials were evaluated for their fresh properties, which determine processability, and cured properties, which determine waste form performance. The results show potential for greatly reducing the volume of material. Fresh properties were sufficient to allow for processing via current practices. Cured properties such as compressive strength meet disposal requirements. Leachability indices provide an indication of expected long-term performance.
Crystalline coats or hollow crystals as tools for product design in pharmaceutical industry
NASA Astrophysics Data System (ADS)
Ulrich, J.; Schuster, A.; Stelzer, T.
2013-01-01
The coating of pharmaceutical compounds is a field of high interest. As most of the coating materials form an amorphous layer around the material, the studies on crystalline coatings are rare. In this work the progress in this domain should be summarized and innovative results concerning crystalline hollow needles as coating material are presented. Since the first reports on needles formed via a solvent-mediated phase transition from solvates to hydrates, the field could be widened to hydrate-to-anhydrate and anhydrate-to-hydrate transformations. Novel investigations on hollow theophylline monohydrate and carbamazepine dihydrate needles are presented. It is shown that the inclusion of substances into the hollow needle crystals is feasible by simple means, which enable an application in industry as coating for sensitive materials.
Methods and system for subsurface stabilization using jet grouting
Loomis, Guy G.; Weidner, Jerry R.; Farnsworth, Richard K.; Gardner, Bradley M.; Jessmore, James J.
1999-01-01
Methods and systems are provided for stabilizing a subsurface area such as a buried waste pit for either long term storage, or interim storage and retrieval. A plurality of holes are drilled into the subsurface area with a high pressure drilling system provided with a drill stem having jet grouting nozzles. A grouting material is injected at high pressure through the jet grouting nozzles into a formed hole while the drill stem is withdrawn from the hole at a predetermined rate of rotation and translation. A grout-filled column is thereby formed with minimal grout returns, which when overlapped with other adjacent grout-filled columns encapsulates and binds the entire waste pit area to form a subsurface agglomeration or monolith of grout, soil, and waste. The formed monolith stabilizes the buried waste site against subsidence while simultaneously providing a barrier against contaminate migration. The stabilized monolith can be left permanently in place or can be retrieved if desired by using appropriate excavation equipment. The jet grouting technique can also be utilized in a pretreatment approach prior to in situ vitrification of a buried waste site. The waste encapsulation methods and systems are applicable to buried waste materials such as mixed waste, hazardous waste, or radioactive waste.
Conceptual uncertainty in crystalline bedrock: Is simple evaluation the only practical approach?
Geier, J.; Voss, C.I.; Dverstorp, B.
2002-01-01
A simple evaluation can be used to characterize the capacity of crystalline bedrock to act as a barrier to release radionuclides from a nuclear waste repository. Physically plausible bounds on groundwater flow and an effective transport-resistance parameter are estimated based on fundamental principles and idealized models of pore geometry. Application to an intensively characterized site in Sweden shows that, due to high spatial variability and uncertainty regarding properties of transport paths, the uncertainty associated with the geological barrier is too high to allow meaningful discrimination between good and poor performance. Application of more complex (stochastic-continuum and discrete-fracture-network) models does not yield a significant improvement in the resolution of geological barrier performance. Comparison with seven other less intensively characterized crystalline study sites in Sweden leads to similar results, raising a question as to what extent the geological barrier function can be characterized by state-of-the art site investigation methods prior to repository construction. A simple evaluation provides a simple and robust practical approach for inclusion in performance assessment.
Conceptual uncertainty in crystalline bedrock: Is simple evaluation the only practical approach?
Geier, J.; Voss, C.I.; Dverstorp, B.
2002-01-01
A simple evaluation can be used to characterise the capacity of crystalline bedrock to act as a barrier to releases of radionuclides from a nuclear waste repository. Physically plausible bounds on groundwater flow and an effective transport-resistance parameter are estimated based on fundamental principles and idealised models of pore geometry. Application to an intensively characterised site in Sweden shows that, due to high spatial variability and uncertainty regarding properties of transport paths, the uncertainty associated with the geological barrier is too high to allow meaningful discrimination between good and poor performance. Application of more complex (stochastic-continuum and discrete-fracture-network) models does not yield a significant improvement in the resolution of geologic-barrier performance. Comparison with seven other less intensively characterised crystalline study sites in Sweden leads to similar results, raising a question as to what extent the geological barrier function can be characterised by state-of-the art site investigation methods prior to repository construction. A simple evaluation provides a simple and robust practical approach for inclusion in performance assessment.
Controlling Crystal Microstructure to Minimize Loss in Polymer Dielectrics
NASA Astrophysics Data System (ADS)
Miranda, Daniel; Iacob, Ciprian; Zhang, Shihai; Runt, James
Polymer dielectric films are of great importance for high performance capacitors. For these films it is critical to reduce dielectric loss, as it diminishes efficiency and contributes to waste heat generation during device operation. Here, a model semi-crystalline polymer, poly(ethylene naphthalate) (PEN), was used to examine how morphological factors inhibit chain relaxations responsible for loss. This was achieved by manipulating the extent of crystallization and the crystalline microstructure through a combination of annealing and uniaxial drawing, and investigating their effects on dielectric performance. Varying crystallization conditions influenced the dynamic Tg and extent of rigid amorphous fraction formation, but had a limited effect on loss magnitude. Film orientation however greatly reduced loss, through strain-induced crystallization and development of oriented amorphous mesophasic regions. Post-drawing annealing conditions were capable of further refining the crystal microstructure and, in turn, the dielectric properties. These findings demonstrate that semi-crystalline polymer morphology has a very strong influence on amorphous chain relaxations, and understanding how processing conditions affect morphology is critical to the rational design of polymer dielectrics. Office of Naval Research.
NASA Astrophysics Data System (ADS)
Chaudhury, Susmitnarayan; Dutta, Anirudha; Bag, Sudipta; Biswas, Pranandita; Das, Amit Kumar; Dasgupta, Swagata
2018-03-01
Aggregation of human ocular lens proteins, the crystallins is believed to be one of the key reasons for age-onset cataract. Previous studies have shown that human γD-crystallin forms amyloid like fibres under conditions of low pH and elevated temperature. In this article, we have investigated the aggregation propensity of human γB-crystallin in absence and presence of epigallocatechin gallate (EGCG), in vitro, when exposed to stressful conditions. We have used different spectroscopic and microscopic techniques to elucidate the inhibitory effect of EGCG towards aggregation. The experimental results have been substantiated by molecular dynamics simulation studies. We have shown that EGCG possesses inhibitory potency against the aggregation of human γB-crystallin at low pH and elevated temperature.
Development of Alternative Technetium Waste Forms
DOE Office of Scientific and Technical Information (OSTI.GOV)
Czerwinski, Kenneth
2013-09-13
The UREX+1 process is under consideration for the separation of transuranic elements from spent nuclear fuel. The first steps of this process extract the fission product technicium-99 ({sup 99}Tc) into an organic phase containing tributylphosphate together with uranium. Treatment of this stream requires the separation of Tc from U and placement into a suitable waste storage form. A potential candidate waste form involves immobilizing the Tc as an alloy with either excess metallic zirconium or stainless steel. Although Tc-Zr alloys seem to be promising waste forms, alternative materials must be investigated. Innovative studies related to the synthesis and behavior ofmore » a different class of Tc materials will increase the scientific knowledge related to development of Tc waste forms. These studies will also provide a better understanding of the behavior of {sup 99}Tc in repository conditions. A literature survey has selected promising alternative waste forms for further study: technetium metallic alloys, nitrides, oxides, sulfides, and pertechnetate salts. The goals of this project are to 1) synthesize and structurally characterize relevant technetium materials that may be considered as waste forms, 2) investigate material behavior in solution under different conditions of temperature, electrochemical potential, and radiation, and 3) predict the long-term behavior of these materials.« less
Methods of vitrifying waste with low melting high lithia glass compositions
Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.
2001-01-01
The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.
Epsilon Metal Waste Form for Immobilization of Noble Metals from Used Nuclear Fuel
DOE Office of Scientific and Technical Information (OSTI.GOV)
Crum, Jarrod V.; Strachan, Denis M.; Rohatgi, Aashish
2013-10-01
Epsilon metal (ε-metal), an alloy of Mo, Pd, Rh, Ru, and Tc, is being developed as a waste form to treat and immobilize the undissolved solids and dissolved noble metals from aqueous reprocessing of commercial used nuclear fuel. Epsilon metal is an attractive waste form for several reasons: increased durability relative to borosilicate glass, it can be fabricated without additives (100% waste loading), and in addition it also benefits borosilicate glass waste loading by eliminating noble metals from the glass and thus the processing problems related there insolubility in glass. This work focused on the processing aspects of the epsilonmore » metal waste form development. Epsilon metal is comprised of refractory metals resulting in high reaction temperatures to form the alloy, expected to be 1500 - 2000°C making it a non-trivial phase to fabricate by traditional methods. Three commercially available advanced technologies were identified: spark-plasma sintering, microwave sintering, and hot isostatic pressing, and investigated as potential methods to fabricate this waste form. Results of these investigations are reported and compared in terms of bulk density, phase assemblage (X-ray diffraction and elemental analysis), and microstructure (scanning electron microscopy).« less
Federal Register 2010, 2011, 2012, 2013, 2014
2010-01-29
... suspension for the treatment of lower respiratory tract infections in horses. DATES: This rule is effective... ceftiofur crystalline free acid injectable suspension for the treatment of lower respiratory tract... of lower respiratory tract infections in horses caused by susceptible strains of Streptococcus equi...
Method for forming porous platinum films
Maya, Leon
2000-01-01
A method for forming a platinum film includes providing a substrate, sputtering a crystalline platinum oxide layer over at least a portion of the substrate, and reducing the crystalline platinum oxide layer to form the platinum film. A device includes a non-conductive substrate and a platinum layer having a density of between about 2 and 5 g/cm.sup.3 formed over at least a portion of the non-conductive substrate. The platinum films produced in accordance with the present invention provide porous films suitable for use as electrodes, yet require few processing steps. Thus, such films are less costly. Such films may be formed on both conductive and non-conductive substrates. While the invention has been illustrated with platinum, other metals, such as noble metals, that form a low density oxide when reactively sputtered may also be used.
Ciszek, Theodore F.
1994-01-01
An elongated, flexible superconductive wire or strip is fabricated by pulling it through and out of a melt of metal oxide material at a rate conducive to forming a crystalline coating of superconductive metal oxide material on an elongated, flexible substrate wire or strip. A coating of crystalline superconductive material, such as Bi.sub.2 Sr.sub.2 CaCu.sub.2 O.sub.8, is annealed to effect conductive contact between adjacent crystalline structures in the coating material, which is then cooled to room temperature. The container for the melt can accommodate continuous passage of the substrate through the melt. Also, a second pass-through container can be used to simultaneously anneal and overcoat the superconductive coating with a hot metallic material, such as silver or silver alloy. A hollow, elongated tube casting method of forming an elongated, flexible superconductive wire includes drawing the melt by differential pressure into a heated tubular substrate.
Apparatus for electrohydrodynamically assembling patterned colloidal structures
NASA Technical Reports Server (NTRS)
Trau, Mathias (Inventor); Aksay, Ilhan A. (Inventor); Saville, Dudley A. (Inventor)
2000-01-01
A method apparatus is provided for electrophoretically depositing particles onto an electrode, and electrohydrodynamically assembling the particles into crystalline structures. Specifically, the present method and apparatus creates a current flowing through a solution to cause identically charged electrophoretically deposited colloidal particles to attract each other over very large distances (<5 particle diameters) on the surface of electrodes to form two-dimensional colloidal crystals. The attractive force can be created with both DC and AC fields and can modulated by adjusting either the field strength or frequency of the current. Modulating this lateral attraction between the particles causes the reversible formation of two-dimensional fluid and crystalline colloidal states on the electrode surface. Further manipulation allows for the formation of two or three-dimensional colloidal crystals, as well as more complex designed structures. Once the required structures are formed, these three-dimension colloidal crystals can be permanently frozen or glued by controlled coagulation induced by to the applied field to form a stable crystalline structure.
NASA Astrophysics Data System (ADS)
Boatz, Jennifer C.; Whitley, Matthew J.; Li, Mingyue; Gronenborn, Angela M.; van der Wel, Patrick C. A.
2017-05-01
Cataracts cause vision loss through the large-scale aggregation of eye lens proteins as a result of ageing or congenital mutations. The development of new treatments is hindered by uncertainty about the nature of the aggregates and their mechanism of formation. We describe the structure and morphology of aggregates formed by the P23T human γD-crystallin mutant associated with congenital cataracts. At physiological pH, the protein forms aggregates that look amorphous and disordered by electron microscopy, reminiscent of the reported formation of amorphous deposits by other crystallin mutants. Surprisingly, solid-state NMR reveals that these amorphous deposits have a high degree of structural homogeneity at the atomic level and that the aggregated protein retains a native-like conformation, with no evidence for large-scale misfolding. Non-physiological destabilizing conditions used in many in vitro aggregation studies are shown to yield qualitatively different, highly misfolded amyloid-like fibrils.
Vibrational characterisation of a crystallised oligoaniline: a model compound of polyaniline
NASA Astrophysics Data System (ADS)
Quillard, Sophie; Corraze, Benoı̂t; Boyer, Marie Isabelle; Fayad, Elias; Louarn, Guy; Froyer, Gérard
2001-09-01
We present a detailed study on the vibrational properties of N,N‧-diphenyl-1,4-phenylenediamine in different crystalline forms. A new triclinic form of the molecule has been obtained through appropriate recrystallization procedure. This polymorphism of the crystalline state was associated to different vibrational features. These results are discussed with regards to the possible conformations of the molecule. In order to complete the study, thin solid films of these materials were also elaborated by vacuum sublimation of the molecule, upon selected conditions of rate, deposition and thickness. Spectroscopic measurements of these layers are showed and compared to those obtained on the crystalline solid forms. We performed convenient oxidation processes of this neutral N,N‧-diphenyl-1,4-phenylenediamine (powder and thin solid film) leading to the formation of the correspondent radical cation species. A comparison with radical cation generated in solution by electrochemical oxidative method is done. Vibrational characterisations of this doped oligomer were achieved in each case and finally, the observed differences are discussed in terms of conformation.
Method for electrohydrodynamically assembling patterned colloidal structures
NASA Technical Reports Server (NTRS)
Trau, Mathias (Inventor); Aksay, Ilhan A. (Inventor); Saville, Dudley A. (Inventor)
1999-01-01
A method apparatus is provided for electrophoretically depositing particles onto an electrode, and electrohydrodynamically assembling the particles into crystalline structures. Specifically, the present method and apparatus creates a current flowing through a solution to cause identically charged electrophoretically deposited colloidal particles to attract each other over very large distances (<5 particle diameters) on the surface of electrodes to form two-dimensional colloidal crystals. The attractive force can be created with both DC and AC fields and can modulated by adjusting either the field strength or frequency of the current. Modulating this lateral attraction between the particles causes the reversible formation of two-dimensional fluid and crystalline colloidal states on the electrode surface. Further manipulation allows for the formation of two or three-dimensional colloidal crystals, as well as more complex designed structures. Once the required structures are formed, these three-dimension colloidal crystals can be permanently frozen or glued by controlled coagulation induced by to the applied field to form a stable crystalline structure.
Ciszek, T.F.
1994-04-19
An elongated, flexible superconductive wire or strip is fabricated by pulling it through and out of a melt of metal oxide material at a rate conducive to forming a crystalline coating of superconductive metal oxide material on an elongated, flexible substrate wire or strip. A coating of crystalline superconductive material, such as Bi[sub 2]Sr[sub 2]CaCu[sub 2]O[sub 8], is annealed to effect conductive contact between adjacent crystalline structures in the coating material, which is then cooled to room temperature. The container for the melt can accommodate continuous passage of the substrate through the melt. Also, a second pass-through container can be used to simultaneously anneal and overcoat the superconductive coating with a hot metallic material, such as silver or silver alloy. A hollow, elongated tube casting method of forming an elongated, flexible superconductive wire includes drawing the melt by differential pressure into a heated tubular substrate. 8 figures.
Structural aspects of fish skin collagen which forms ordered arrays via liquid crystalline states.
Giraud-Guille, M M; Besseau, L; Chopin, C; Durand, P; Herbage, D
2000-05-01
The ability of acid-soluble type I collagen extracts from Soleidae flat fish to form ordered arrays in condensed phases has been compared with data for calf skin collagen. Liquid crystalline assemblies in vitro are optimized by preliminary treatment of the molecular population with ultrasounds. This treatment requires the stability of the fish collagen triple helicity to be controlled by X-ray diffraction and differential scanning calorimetry and the effect of sonication to be evaluated by viscosity measurements and gel electrophoresis. The collagen solution in concentrations of at least 40 mg ml(-1) showed in polarized light microscopy birefringent patterns typical of precholesteric phases indicating long-range order within the fluid collagen phase. Ultrastructural data, obtained after stabilization of the liquid crystalline collagen into a gelated matrix, showed that neutralized acid-soluble fish collagen forms cross-striated fibrils, typical of type I collagen, following sine wave-like undulations in precholesteric domains. These ordered geometries, approximating in vivo situations, give interesting mechanical properties to the material.
On the use of bismuth as a neutron filter
NASA Astrophysics Data System (ADS)
Adib, M.; Kilany, M.
2003-02-01
A formula is given which, for neutron energies in the range 10 -4< E<10 eV, permits calculation of the nuclear capture, thermal diffuse and Bragg scattering cross-sections as a function of bismuth temperature and crystalline form. Computer programs have been developed which allow calculations for the Bi rhombohedral structure in its poly-crystalline form and its equivalent hexagonal close-packed structure. The calculated total neutron cross-sections for poly-crystalline Bi at different temperatures were compared with the measured values. An overall agreement is indicated between the formula fits and experimental data. Agreement was also obtained for values of Bi-single crystals, at room and liquid nitrogen temperatures. A feasibility study for use of Bi in powdered form, as a cold neutron filter, is detailed in terms of the optimum Bi-single crystal thickness, mosaic spread, temperature and cutting plane for efficient transmission of thermal-reactor neutrons, and also for rejection of the accompanying fast neutrons and gamma rays.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wall, Nathalie A.; Neeway, James J.; Qafoku, Nikolla P.
2015-09-30
Assessments of waste form and disposal options start with the degradation of the waste forms and consequent mobilization of radionuclides. Long-term static tests, single-pass flow-through tests, and the pressurized unsaturated flow test are often employed to study the durability of potential waste forms and to help create models that predict their durability throughout the lifespan of the disposal site. These tests involve the corrosion of the material in the presence of various leachants, with different experimental designs yielding desired information about the behavior of the material. Though these tests have proved instrumental in elucidating various mechanisms responsible for material corrosion,more » the chemical environment to which the material is subject is often not representative of a potential radioactive waste repository where factors such as pH and leachant composition will be controlled by the near-field environment. Near-field materials include, but are not limited to, the original engineered barriers, their resulting corrosion products, backfill materials, and the natural host rock. For an accurate performance assessment of a nuclear waste repository, realistic waste corrosion experimental data ought to be modeled to allow for a better understanding of waste form corrosion mechanisms and the effect of immediate geochemical environment on these mechanisms. Additionally, the migration of radionuclides in the resulting chemical environment during and after waste form corrosion must be quantified and mechanisms responsible for migrations understood. The goal of this research was to understand the mechanisms responsible for waste form corrosion in the presence of relevant repository sediments to allow for accurate radionuclide migration quantifications. The rationale for this work is that a better understanding of waste form corrosion in relevant systems will enable increased reliance on waste form performance in repository environments and potentially decrease the need for expensive engineered barriers.Our current work aims are 1) quantifying and understanding the processes associated with glass alteration in contact with Fe-bearing materials; 2) quantifying and understanding the processes associated with glass alteration in presence of MgO (example of engineered barrier used in WIPP); 3) identifying glass alteration suppressants and the processes involved to reach glass alteration suppression; 4) quantifying and understanding the processes associated with Saltstone and Cast Stone (SRS and Hanford cementitious waste forms) in various representative groundwaters; 5) investigating positron annihilation as a new tool for the study of glass alteration; and 6) quantifying and understanding the processes associated with glass alteration under gamma irradiation.« less
Bogush, Anna; Stegemann, Julia A; Wood, Ian; Roy, Amitava
2015-02-01
Air pollution control (APC) residues from energy-from-waste (EfW) are alkaline (corrosive) and contain high concentrations of metals, such as zinc and lead, and soluble salts, such as chlorides and sulphates. The EPA 3050B-extractable concentrations of 66 elements, including critical elements of strategic importance for advanced electronics and energy technologies, were determined in eight APC residues from six UK EfW facilities. The concentrations of Ag (6-15 mg/kg) and In (1-13 mg/kg), as well as potential pollutants, especially Zn (0.26-0.73 wt.%), Pb (0.05-0.2 wt.%), As, Cd, Cu, Mo, Sb, Sn and Se were found to be enriched in all APC residues compared to average crustal abundances. Results from a combination of scanning electron microscopy with energy dispersive X-ray spectroscopy and also powder X-ray diffraction, thermal analysis and Fourier transform infrared spectroscopy give an exceptionally full understanding of the mineralogy of these residues, which is discussed in the context of other results in the literature. The present work has shown that the bulk of the crystalline phases present in the investigated APC residues include Ca-based phases, such as CaCl(x)OH(2-x), CaCO3, Ca(OH)2, CaSO4, and CaO, as well as soluble salts, such as NaCl and KCl. Poorly-crystalline aragonite was identified by FTIR. Sulphur appears to have complex redox speciation, presenting as both anhydrite and hannebachite in some UK EfW APC residues. Hazardous elements (Zn and Pb) were widely associated with soluble Ca- and Cl-bearing phases (e.g. CaCl(x)OH(2-x) and sylvite), as well as unburnt organic matter and aluminosilicates. Specific metal-bearing minerals were also detected in some samples: e.g., Pb present as cerussite; Zn in gahnite, zincowoodwardite and copper nickel zinc oxide; Cu in tenorite, copper nickel zinc oxide and fedotovite. Aluminium foil pieces were present and abundantly covered by fine phases, particularly in any cracks, probably in the form of Friedel's salt. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.
10 CFR 60.17 - Contents of site characterization plan.
Code of Federal Regulations, 2012 CFR
2012-01-01
... assurance to data collection, recording, and retention. (3) Plans for the decontamination and... rule or order, requires. (b) A description of the possible waste form or waste package for the high... practicable) of the relationship between such waste form or waste package and the host rock at such area, and...
10 CFR 60.17 - Contents of site characterization plan.
Code of Federal Regulations, 2013 CFR
2013-01-01
... assurance to data collection, recording, and retention. (3) Plans for the decontamination and... rule or order, requires. (b) A description of the possible waste form or waste package for the high... practicable) of the relationship between such waste form or waste package and the host rock at such area, and...
10 CFR 60.17 - Contents of site characterization plan.
Code of Federal Regulations, 2014 CFR
2014-01-01
... assurance to data collection, recording, and retention. (3) Plans for the decontamination and... rule or order, requires. (b) A description of the possible waste form or waste package for the high... practicable) of the relationship between such waste form or waste package and the host rock at such area, and...
10 CFR 60.17 - Contents of site characterization plan.
Code of Federal Regulations, 2011 CFR
2011-01-01
... assurance to data collection, recording, and retention. (3) Plans for the decontamination and... rule or order, requires. (b) A description of the possible waste form or waste package for the high... practicable) of the relationship between such waste form or waste package and the host rock at such area, and...
Selective oxoanion separation using a tripodal ligand
Custelcean, Radu; Moyer, Bruce A.; Rajbanshi, Arbin
2016-02-16
The present invention relates to urea-functionalized crystalline capsules self-assembled by sodium or potassium cation coordination and by hydrogen-bonding water bridges to selectively encapsulate tetrahedral divalent oxoanions from highly competitive aqueous alkaline solutions and methods using this system for selective anion separations from industrial solutions. The method involves competitive crystallizations using a tripodal tris(urea) functionalized ligand and, in particular, provides a viable approach to sulfate separation from nuclear wastes.
Trace concentration - Huge impact: Nitrate in the calcite/Eu(III) system
NASA Astrophysics Data System (ADS)
Hofmann, Sascha; Voïtchovsky, Kislon; Schmidt, Moritz; Stumpf, Thorsten
2014-01-01
The interactions of trivalent lanthanides and actinides with secondary mineral phases such as calcite is of high importance for the safety assessment of deep geological repositories for high level nuclear waste (HLW). Due to similar ionic radii, calcium-bearing mineral phases are suitable host minerals for Ln(III) and An(III) ions. Especially calcite has been proven to retain these metal ions effectively by both surface complexation and bulk incorporation. Since anionic ligands (e.g., nitrate) are omnipresent in the geological environment and due to their coordinating properties, their influence on retentive processes should not be underestimated. Nitrate is a common contaminant in most HLW forms as a result of using nitric acid in fuel reprocessing. It is also formed by microbial activity under aerobic conditions. In this study, atomic force microscopy investigations revealed a major influence of nitrate upon the surface of calcite crystals. NaNO3 causes serious modifications even in trace amounts (<10-7 M) and forms a soft surface layer of low crystallinity on top of the calcite crystal. Time-resolved laser fluorescence spectroscopy of Eu(III) showed that, within this layer, Eu(III) ions are incorporated, while losing most of their hydration shell. The results show that solid solution modelling for actinides in calcite must take into account the presence of nitrate in pore and ground waters.
Felipe-Sotelo, M; Hinchliff, J; Field, L P; Milodowski, A E; Preedy, O; Read, D
2017-07-01
The solubility of uranium and thorium has been measured under the conditions anticipated in a cementitious, geological disposal facility for low and intermediate level radioactive waste. Similar solubilities were obtained for thorium in all media, comprising NaOH, Ca(OH) 2 and water equilibrated with a cement designed as repository backfill (NRVB, Nirex Reference Vault Backfill). In contrast, the solubility of U(VI) was one order of magnitude higher in NaOH than in the remaining solutions. The presence of cellulose degradation products (CDP) results in a comparable solubility increase for both elements. Extended X-ray Absorption Fine Structure (EXAFS) data suggest that the solubility-limiting phase for uranium corresponds to a becquerelite-type solid whereas thermodynamic modelling predicts a poorly crystalline, hydrated calcium uranate phase. The solubility-limiting phase for thorium was ThO 2 of intermediate crystallinity. No breakthrough of either uranium or thorium was observed in diffusion experiments involving NRVB after three years. Nevertheless, backscattering electron microscopy and microfocus X-ray fluorescence confirmed that uranium had penetrated about 40 μm into the cement, implying active diffusion governed by slow dissolution-precipitation kinetics. Precise identification of the uranium solid proved difficult, displaying characteristics of both calcium uranate and becquerelite. Copyright © 2017 Elsevier Ltd. All rights reserved.
Experimental investigation to evaluate the potential environmental hazards of photovoltaic panels.
Tammaro, Marco; Salluzzo, Antonio; Rimauro, Juri; Schiavo, Simona; Manzo, Sonia
2016-04-05
Recently the potential environmental hazard of photovoltaic modules together with their management as waste has attracted the attention of scientists. Particular concern is aroused by the several metals contained in photovoltaic panels whose potential release in the environment were scarcely investigated. Here, for the first time, the potential environmental hazard of panels produced in the last 30 years was investigated through the assessment of up to 18 releasable metals. Besides, the corresponding ecotoxicological effects were also evaluated. Experimental data were compared with the current European and Italian law limits for drinking water, discharge on soil and landfill inert disposal in order to understand the actual pollution load. Results showed that less than 3% of the samples respected all law limits and around 21% was not ecotoxic. By considering the technological evolutions in manufacturing, we have shown that during the years crystalline silicon panels have lower tendency to release hazardous metals with respect to thin film panels. In addition, a prediction of the amounts of lead, chromium, cadmium and nickel releasable from next photovoltaic waste was performed. The prevision up to 2050 showed high amounts of lead (30t) and cadmium (2.9t) releasable from crystalline and thin film panels respectively. Copyright © 2015 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Hosseini, Tahereh A.
Rising rates of the energy consumption and growing concerns over the climate change worldwide have made energy efficiency an urgent problem to address. Nowadays, almost two-thirds of the energy produced by burning fossil fuels to generate electrical power is lost in the form of the heat. On this front, increasing electrical power generation through a waste heat recovery remains one of the highly promising venues of the energy research. Thermo-electric generators (TEGs) directly convert thermal energy into electrical and are the prime candidates for application in low-grade thermal energy/ waste heat recovery. The key commercial TE materials, e.g. PbTe and Bi2Te 3, have room temperature ZT of less than 1, whereas ZT exceeding 3 is required for a TEG to be economically viable. With the thermoelectric efficiency typically within a few percent range and a low efficiency-to-cost ratio of TEGs, there has been a resurgence in the search for new class of thermo-electric materials for developing high efficiency thermo-to-electric energy conversion systems, with phonon-glass electron-crystal materials holding the most promise. Herein, we focus on synthesis, characterization and investigation of electrical, thermo-electrical and thermal characteristics of crystalline Cd 3As2, a high performance 3D topological Dirac semimetal with Dirac fermions dispersing linearly in k3-space and possessing one of the largest electron mobilities known for crystalline materials, i.e. 104-105cm2V-1 s-1. Suppression of carrier backscattering, ultra-high charge carrier mobility, and inherently low thermal conductivity make this semimetal a key candidate for demonstrating high, device-favorable S and in turn ZT. In this work, a low-temperature vapor-based crystallization pathway was developed and optimized to produce free standing 2D cm-size crystals in Cd 3As2. Compared to the bulk crystals produced in previous studies, e.g. Piper-Polich, Bridgman, or flux method, Cd3As 2 samples were synthesized over a considerably shorter time ( only a few hours), were single crystals and highly stochiometric. A high thermopower of up to 613 microV K-1 and the electrical conductivity of 105 S/m were registered within the temperature range of 300-400 K. A 1o-method based on the transfer function was applied to probe a thermal conductivity, k of Cd3As2 platelets. The results yield k of 2.4 W/m.K in the confirmation that the thermal conductivity of Cd3As2 crystals is to approach the amorphous limit at the room temperature. With its peak thermopower attained at the low temperature range of 300-400 K, high electrical conductivity and amorphous limit thermal conductivity, crystalline Cd3As2 grown via a low-T vapor based method demonstrates ZT > 3; the results confirm that as-produced Cd 3As2 platelets hold a high promise and is another phonon-glass electron-crystal TE material for the development of next generation, high efficiency thermo-electric generators and refrigerators operating under normal conditions.
Spray Drying as a Reliable Route to Produce Metastable Carbamazepine Form IV.
Halliwell, Rebecca A; Bhardwaj, Rajni M; Brown, Cameron J; Briggs, Naomi E B; Dunn, Jaclyn; Robertson, John; Nordon, Alison; Florence, Alastair J
2017-07-01
Carbamazepine (CBZ) is an active pharmaceutical ingredient used in the treatment of epilepsy that can form at least 5 polymorphic forms. Metastable form IV was originally discovered from crystallization with polymer additives; however, it has not been observed from subsequent solvent-only crystallization efforts. This work reports the reproducible formation of phase pure crystalline form IV by spray drying of methanolic CBZ solution. Characterization of the material was carried out using diffraction, scanning electron microscopy, and differential scanning calorimetry. In situ Raman spectroscopy was used to monitor the spray-dried product during the spray drying process. This work demonstrates that spray drying provides a robust method for the production of form IV CBZ, and the combination of high supersaturation and rapid solid isolation from solution overcomes the apparent limitation of more traditional solution crystallization approaches to produce metastable crystalline forms. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.
Structure of the cellulose synthase complex of Gluconacetobacter hansenii at 23.4 Å resolution
Du, Juan; Vepachedu, Venkata; Cho, Sung Hyun; ...
2016-05-23
Bacterial crystalline cellulose is used in biomedical and industrial applications, but the molecular mechanisms of synthesis are unclear. Unlike most bacteria, which make non-crystalline cellulose, Gluconacetobacter hansenii extrudes profuse amounts of crystalline cellulose. Its cellulose synthase (AcsA) exists as a complex with accessory protein AcsB, forming a 'terminal complex' (TC) that has been visualized by freeze-fracture TEM at the base of ribbons of crystalline cellulose. The catalytic AcsAB complex is embedded in the cytoplasmic membrane. The C-terminal portion of AcsC is predicted to form a translocation channel in the outer membrane, with the rest of AcsC possibly interacting with AcsDmore » in the periplasm. It is thus believed that synthesis from an organized array of TCs coordinated with extrusion by AcsC and AcsD enable this bacterium to make crystalline cellulose. The only structural data that exist for this system are the above mentioned freeze-fracture TEM images, fluorescence microscopy images revealing that TCs align in a row, a crystal structure of AcsD bound to cellopentaose, and a crystal structure of PilZ domain of AcsA. Here we advance our understanding of the structural basis for crystalline cellulose production by bacterial cellulose synthase by determining a negative stain structure resolved to 23.4 angstrom for highly purified AcsAB complex that catalyzed incorporation of UDP-glucose into β-1,4-glucan chains, and responded to the presence of allosteric activator cyclic diguanylate. Although the AcsAB complex was functional in vitro, the synthesized cellulose was not visible in TEM. The negative stain structure revealed that AcsAB is very similar to that of the BcsAB synthase of Rhodobacter sphaeroides, a non-crystalline cellulose producing bacterium. Furthermore, the results indicate that the crystalline cellulose producing and non-crystalline cellulose producing bacteria share conserved catalytic and membrane translocation components, and support the hypothesis that it is the extrusion mechanism and order in linearly arrayed TCs that enables production of crystalline cellulose.« less
Structure of the cellulose synthase complex of Gluconacetobacter hansenii at 23.4 Å resolution
DOE Office of Scientific and Technical Information (OSTI.GOV)
Du, Juan; Vepachedu, Venkata; Cho, Sung Hyun
Bacterial crystalline cellulose is used in biomedical and industrial applications, but the molecular mechanisms of synthesis are unclear. Unlike most bacteria, which make non-crystalline cellulose, Gluconacetobacter hansenii extrudes profuse amounts of crystalline cellulose. Its cellulose synthase (AcsA) exists as a complex with accessory protein AcsB, forming a 'terminal complex' (TC) that has been visualized by freeze-fracture TEM at the base of ribbons of crystalline cellulose. The catalytic AcsAB complex is embedded in the cytoplasmic membrane. The C-terminal portion of AcsC is predicted to form a translocation channel in the outer membrane, with the rest of AcsC possibly interacting with AcsDmore » in the periplasm. It is thus believed that synthesis from an organized array of TCs coordinated with extrusion by AcsC and AcsD enable this bacterium to make crystalline cellulose. The only structural data that exist for this system are the above mentioned freeze-fracture TEM images, fluorescence microscopy images revealing that TCs align in a row, a crystal structure of AcsD bound to cellopentaose, and a crystal structure of PilZ domain of AcsA. Here we advance our understanding of the structural basis for crystalline cellulose production by bacterial cellulose synthase by determining a negative stain structure resolved to 23.4 angstrom for highly purified AcsAB complex that catalyzed incorporation of UDP-glucose into β-1,4-glucan chains, and responded to the presence of allosteric activator cyclic diguanylate. Although the AcsAB complex was functional in vitro, the synthesized cellulose was not visible in TEM. The negative stain structure revealed that AcsAB is very similar to that of the BcsAB synthase of Rhodobacter sphaeroides, a non-crystalline cellulose producing bacterium. Furthermore, the results indicate that the crystalline cellulose producing and non-crystalline cellulose producing bacteria share conserved catalytic and membrane translocation components, and support the hypothesis that it is the extrusion mechanism and order in linearly arrayed TCs that enables production of crystalline cellulose.« less
Structure of the Cellulose Synthase Complex of Gluconacetobacter hansenii at 23.4 Å Resolution
Du, Juan; Vepachedu, Venkata; Cho, Sung Hyun; Kumar, Manish; Nixon, B. Tracy
2016-01-01
Bacterial crystalline cellulose is used in biomedical and industrial applications, but the molecular mechanisms of synthesis are unclear. Unlike most bacteria, which make non-crystalline cellulose, Gluconacetobacter hansenii extrudes profuse amounts of crystalline cellulose. Its cellulose synthase (AcsA) exists as a complex with accessory protein AcsB, forming a 'terminal complex' (TC) that has been visualized by freeze-fracture TEM at the base of ribbons of crystalline cellulose. The catalytic AcsAB complex is embedded in the cytoplasmic membrane. The C-terminal portion of AcsC is predicted to form a translocation channel in the outer membrane, with the rest of AcsC possibly interacting with AcsD in the periplasm. It is thus believed that synthesis from an organized array of TCs coordinated with extrusion by AcsC and AcsD enable this bacterium to make crystalline cellulose. The only structural data that exist for this system are the above mentioned freeze-fracture TEM images, fluorescence microscopy images revealing that TCs align in a row, a crystal structure of AcsD bound to cellopentaose, and a crystal structure of PilZ domain of AcsA. Here we advance our understanding of the structural basis for crystalline cellulose production by bacterial cellulose synthase by determining a negative stain structure resolved to 23.4 Å for highly purified AcsAB complex that catalyzed incorporation of UDP-glucose into β-1,4-glucan chains, and responded to the presence of allosteric activator cyclic diguanylate. Although the AcsAB complex was functional in vitro, the synthesized cellulose was not visible in TEM. The negative stain structure revealed that AcsAB is very similar to that of the BcsAB synthase of Rhodobacter sphaeroides, a non-crystalline cellulose producing bacterium. The results indicate that the crystalline cellulose producing and non-crystalline cellulose producing bacteria share conserved catalytic and membrane translocation components, and support the hypothesis that it is the extrusion mechanism and order in linearly arrayed TCs that enables production of crystalline cellulose. PMID:27214134
Thermal investigation of nuclear waste disposal in space
NASA Technical Reports Server (NTRS)
Wilkinson, C. L.
1981-01-01
A thermal analysis has been conducted to determine the allowable size and response of bare and shielded nuclear waste forms in both low earth orbit and at 0.85 astronomical units. Contingency conditions of re-entry with a 45 deg and 60 deg aeroshell are examined as well as re-entry of a spherical shielded waste form. A variety of shielded schemes were examined and the waste form thermal response for each determined. Two optimum configurations were selected. The thermal response of these two shielded waste configurations to indefinite exposure to ground conditions following controlled and uncontrolled re-entry is determined. In all cases the prime criterion is that waste containment must be maintained.
Aubert, J E; Husson, B; Sarramone, N
2006-08-25
This paper is the first of a series of two articles dealing with the processes applied to MSWI fly ash with a view to reusing it safely in cement-based materials. Part 1 presents two stabilization processes and Part 2 deals with the use of the two treated fly ashes (TFA) in mortars. Two types of binder were used: an Ordinary Portland Cement (OPC) containing more than 95% clinker (CEM I 52.5R) and a binary blend cement composed of 70% ground granulated blast furnace slag and 30% clinker (CEM III-B 42.5N). In this first part, two stabilization processes are presented: the conventional process, called "A", based on the washing, phosphation and calcination of the ash, and a modified process, called "B", intended to eliminate metallic aluminum and sulfate contained in the ash. The physical, chemical and mineralogical characteristics of the two TFA were comparable. The main differences observed were those expected, i.e. TFA-B was free of metallic aluminum and sulfate. The mineralogical characterization of the two TFAs highlighted the presence of large amounts of a calcium aluminosilicate phase taking two forms, a crystalline form (gehlenite) and an amorphous form. Hydration studies on pastes containing mixed TFA and calcium hydroxide showed that this phase reacted with calcium hydroxide to form calcium aluminate hydrates. This formation of hydrates was accompanied by a hardening of the pastes. These results are very encouraging for the reuse of such TFA in cement-based materials because they can be considered as pozzolanic additions and could advantageously replace a part of the cement in cement-based materials. Finally, leaching tests were carried out to evaluate the environmental impact of the two TFAs. The elements which were less efficiently stabilized by process A were zinc, cadmium and antimony but, when the results of the leaching tests were compared with the thresholds of the European landfill directive, TFA-A could nevertheless be accepted at landfills for non-hazardous waste. The modifications of the process led to a significant reduction in the stabilization of chromium, selenium and antimony.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rigali, Mark J.; Pye, Steven; Hardin, Ernest
This study considers the feasibility of large diameter deep boreholes for waste disposal. The conceptual approach considers examples of deep large diameter boreholes that have been successfully drilled, and also other deep borehole designs proposed in the literature. The objective for large diameter boreholes would be disposal of waste packages with diameters of 22 to 29 inches, which could enable disposal of waste forms such as existing vitrified high level waste. A large-diameter deep borehole design option would also be amenable to other waste forms including calcine waste, treated Na-bonded and Na-bearing waste, and Cs and Sr capsules.
Crystalline and amorphous cellulose in the secondary walls of Arabidopsis.
Ruel, Katia; Nishiyama, Yoshiharu; Joseleau, Jean-Paul
2012-09-01
In the cell walls of higher plants, cellulose chains are present in crystalline microfibril, with an amorphous part at the surface, or present as amorphous material. To assess the distribution and relative occurrence of the two forms of cellulose in the inflorescence stem of Arabidopsis, we used two carbohydrate-binding modules, CBM3a and CBM28, specific for crystalline and amorphous cellulose, respectively, with immunogold detection in TEM. The binding of the two CBMs displayed specific patterns suggesting that the synthesis of cellulose leads to variable nanodomains of cellulose structures according to cell type. In developing cell walls, only CBM3a bound significantly to the incipient primary walls, indicating that at the onset of its deposition cellulose is in a crystalline structure. As the secondary wall develops, the labeling with both CBMs becomes more intense. The variation of the labeling pattern by CBM3a between transverse and longitudinal sections appeared related to microfibril orientation and differed between fibers and vessels. Although the two CBMs do not allow the description of the complete status of cellulose microstructures, they revealed the dynamics of the deposition of crystalline and amorphous forms of cellulose during wall formation and between cell types adapting cellulose microstructures to the cell function. Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.
40 CFR 761.345 - Form of the waste to be sampled.
Code of Federal Regulations, 2012 CFR
2012-07-01
....345 Section 761.345 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Characterization for PCB Disposal in Accordance With § 761.62, and Sampling PCB Remediation Waste Destined for Off... waste and PCB remediation waste destined for off-site disposal must be in the form of either flattened...
40 CFR 761.345 - Form of the waste to be sampled.
Code of Federal Regulations, 2011 CFR
2011-07-01
....345 Section 761.345 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Characterization for PCB Disposal in Accordance With § 761.62, and Sampling PCB Remediation Waste Destined for Off... waste and PCB remediation waste destined for off-site disposal must be in the form of either flattened...
40 CFR 761.345 - Form of the waste to be sampled.
Code of Federal Regulations, 2014 CFR
2014-07-01
....345 Section 761.345 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Characterization for PCB Disposal in Accordance With § 761.62, and Sampling PCB Remediation Waste Destined for Off... waste and PCB remediation waste destined for off-site disposal must be in the form of either flattened...
Methods of fabricating nanostructures and nanowires and devices fabricated therefrom
Majumdar, Arun [Orinda, CA; Shakouri, Ali [Santa Cruz, CA; Sands, Timothy D [Moraga, CA; Yang, Peidong [Berkeley, CA; Mao, Samuel S [Berkeley, CA; Russo, Richard E [Walnut Creek, CA; Feick, Henning [Kensington, CA; Weber, Eicke R [Oakland, CA; Kind, Hannes [Schaffhausen, CH; Huang, Michael [Los Angeles, CA; Yan, Haoquan [Albany, CA; Wu, Yiying [Albany, CA; Fan, Rong [El Cerrito, CA
2009-08-04
One-dimensional nanostructures having uniform diameters of less than approximately 200 nm. These inventive nanostructures, which we refer to as "nanowires", include single-crystalline homostructures as well as heterostructures of at least two single-crystalline materials having different chemical compositions. Because single-crystalline materials are used to form the heterostructure, the resultant heterostructure will be single-crystalline as well. The nanowire heterostructures are generally based on a semiconducting wire wherein the doping and composition are controlled in either the longitudinal or radial directions, or in both directions, to yield a wire that comprises different materials. Examples of resulting nanowire heterostructures include a longitudinal heterostructure nanowire (LOHN) and a coaxial heterostructure nanowire (COHN).
Methods Of Fabricating Nanosturctures And Nanowires And Devices Fabricated Therefrom
Majumdar, Arun; Shakouri, Ali; Sands, Timothy D.; Yang, Peidong; Mao, Samuel S.; Russo, Richard E.; Feick, Henning; Weber, Eicke R.; Kind, Hannes; Huang, Michael; Yan, Haoquan; Wu, Yiying; Fan, Rong
2006-02-07
One-dimensional nanostructures having uniform diameters of less than approximately 200 nm. These inventive nanostructures, which we refer to as "nanowires", include single-crystalline homostructures as well as heterostructures of at least two single-crystalline materials having different chemical compositions. Because single-crystalline materials are used to form the heterostructure, the resultant heterostructure will be single-crystalline as well. The nanowire heterostructures are generally based on a semiconducting wire wherein the doping and composition are controlled in either the longitudinal or radial directions, or in both directions, to yield a wire that comprises different materials. Examples of resulting nanowire heterostructures include a longitudinal heterostructure nanowire (LOHN) and a coaxial heterostructure nanowire (COHN).
Methods of fabricating nanostructures and nanowires and devices fabricated therefrom
Majumdar, Arun; Shakouri, Ali; Sands, Timothy D.; Yang, Peidong; Mao, Samuel S.; Russo, Richard E.; Feick, Henning; Weber, Eicke R.; Kind, Hannes; Huang, Michael; Yan, Haoquan; Wu, Yiying; Fan, Rong
2010-11-16
One-dimensional nanostructures having uniform diameters of less than approximately 200 nm. These inventive nanostructures, which we refer to as "nanowires", include single-crystalline homostructures as well as heterostructures of at least two single-crystalline materials having different chemical compositions. Because single-crystalline materials are used to form the heterostructure, the resultant heterostructure will be single-crystalline as well. The nanowire heterostructures are generally based on a semiconducting wire wherein the doping and composition are controlled in either the longitudinal or radial directions, or in both directions, to yield a wire that comprises different materials. Examples of resulting nanowire heterostructures include a longitudinal heterostructure nanowire (LOHN) and a coaxial heterostructure nanowire (COHN).
Methods of fabricating nanostructures and nanowires and devices fabricated therefrom
Majumdar, Arun; Shakouri, Ali; Sands, Timothy D.; Yang, Peidong; Mao, Samuel S.; Russo, Richard E.; Feick, Henning; Weber, Eicke R.; Kind, Hannes; Huang, Michael; Yan, Haoquan; Wu, Yiying; Fan, Rong
2018-01-30
One-dimensional nanostructures having uniform diameters of less than approximately 200 nm. These inventive nanostructures, which we refer to as "nanowires", include single-crystalline homostructures as well as heterostructures of at least two single-crystalline materials having different chemical compositions. Because single-crystalline materials are used to form the heterostructure, the resultant heterostructure will be single-crystalline as well. The nanowire heterostructures are generally based on a semiconducting wire wherein the doping and composition are controlled in either the longitudinal or radial directions, or in both directions, to yield a wire that comprises different materials. Examples of resulting nanowire heterostructures include a longitudinal heterostructure nanowire (LOHN) and a coaxial heterostructure nanowire (COHN).
NASA Astrophysics Data System (ADS)
Oka, Hiroshi; Amamoto, Takashi; Koyama, Masahiro; Imai, Yasuhiko; Kimura, Shigeru; Hosoi, Takuji; Shimura, Takayoshi; Watanabe, Heiji
2017-01-01
We developed a method of forming single-crystalline germanium-tin (GeSn) alloy on transparent substrates that is based on liquid-phase crystallization. By controlling and designing nucleation during the melting growth process, a highly tensile-strained single-crystalline GeSn layer was grown on a quartz substrate without using any crystal-seeds or catalysts. The peak field-effect hole mobility of 423 cm2/V s was obtained for a top-gate single-crystalline GeSn MOSFET on a quartz substrate with a Sn content of 2.6%, indicating excellent crystal quality and mobility enhancement due to Sn incorporation and tensile strain.
Identification of hydrogen peroxide oxidation sites of alpha A- and alpha B-crystallins.
Smith, J B; Jiang, X; Abraham, E C
1997-02-01
The alpha-crystallins are the most abundant structural proteins of the lens and, because of their chaperone activity, contribute to the solubility of the other crystallins. With aging, the lens crystallins undergo a variety of modifications which correlate with a loss of solubility and the development of cataract. A recent study demonstrating that alpha-crystallins exposed in vitro to FeCl3 and H2O2 exhibit decreased chaperone activity, implicates metal catalyzed oxidations of alpha-crystallins in this loss of solubility. The present study has determined that alpha-crystallins incubated with FeCl3 and H2O2 are modified by the nearly complete oxidation of all methionine residues to methionine sulfoxide, with no other detectable reaction products. The modifications were identified from the molecular weights of peptides formed by enzymatic digestion of the alpha-crystallins and located by tandem mass spectrometric analysis of the fragmentation pattern of the mass spectra of the fragments from peptides with oxidized methionine is loss of 64 Da, which corresponds to loss of CH3SOH from the methionine sulfoxide. These fragments are useful in identifying peptides that include oxidized methionine residues.
Fundamental Aspects of Zeolite Waste Form Production by Hot Isostatic Pressing
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jubin, Robert Thomas; Bruffey, Stephanie H.; Jordan, Jacob A.
The direct conversion of iodine-bearing sorbents into a stable waste form is a research topic of interest to the US Department of Energy. The removal of volatile radioactive 129I from the off-gas of a nuclear fuel reprocessing facility will be necessary in order to comply with the regulatory requirements that apply to facilities sited within the United States (Jubin et al., 2012a), and any iodine-containing media or solid sorbents generated by this process would contain 129I and would be destined for eventual geological disposal. While recovery of iodine from some sorbents is possible, a method to directly convert iodineloaded sorbentsmore » to a durable waste form with little or no additional waste materials being formed and a potentially reduced volume would be beneficial. To this end, recent studies have investigated the conversion of iodine-loaded silver mordenite (I-AgZ) directly to a waste form by hot isostatic pressing (HIPing) (Bruffey and Jubin, 2015). Silver mordenite (AgZ), of the zeolite class of minerals, is under consideration for use in adsorbing iodine from nuclear reprocessing off-gas streams. Direct conversion of I-AgZ by HIPing may provide the following benefits: (1) a waste form of high density that is tolerant to high temperatures, (2) a waste form that is not significantly chemically hazardous, and (3) a robust conversion process that requires no pretreatment.« less
Fujiki, Sadahiro; Watanabe, Narumi; Iwao, Yasunori; Noguchi, Shuji; Mizoguchi, Midori; Iwamura, Takeru; Itai, Shigeru
2015-08-01
The pharmaceutical properties of clarithromycin (CAM) tablets containing the metastable form I of crystalline CAM were investigated. Although the dissolution rate of form I was higher than that of stable form II, the release of CAM from form I tablet was delayed. Disintegration test and liquid penetration test showed that the disintegration of the tablet delayed because of the slow penetration of an external solution into form I tablet. Investigation by scanning electron microscopy revealed that the surface of form I tablet was covered with fine needle-shaped crystals following an exposure to the external solution. These crystals were identified as form IV crystals by powder X-ray diffraction. The phenomenon that CAM releases from tablet was inhibited by fine crystals spontaneously formed on the tablet surface could be applied to the design of sustained-release formulation systems with high CAM contents by minimizing the amount of functional excipients. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.
Phase transitions of antibiotic clarithromycin forms I, IV and new form VII crystals.
Ito, Masataka; Shiba, Rika; Watanabe, Miteki; Iwao, Yasunori; Itai, Shigeru; Noguchi, Shuji
2018-06-01
Metastable crystal form I of the antibiotic clarithromycin has a pharmaceutically valuable characteristic that its crystalline phase transition can be applied for its sustained release from tablets. The phase transition of form I was investigated in detail by single crystal and powder X-ray analyses, dynamic vapor sorption analysis and thermal analysis. The single crystal structure of form I revealed that form I was not an anhydrate crystal but contained a partially occupied water molecule in the channel-like void space. Dynamic vapor sorption (DVS) analysis demonstrated that form I crystals reversibly sorbed water molecules in two steps when the relative humidity (RH) increased and finally transited to hydrate form IV at 95% RH. DVS analysis also showed that when the RH decreased form IV crystals lost water molecules at 40% RH and transited to the newly identified anhydrate crystal form VII. Form VII reversibly transited to form IV at lower RH than form I, suggesting that form I is more suitable for manufacturing a sustained-release tablet of CAM utilizing the crystalline phase transition. Copyright © 2018 Elsevier B.V. All rights reserved.
A green emissive amorphous fac-Alq3 solid generated by grinding crystalline blue fac-Alq3 powder.
Bi, Hai; Chen, Dong; Li, Di; Yuan, Yang; Xia, Dandan; Zhang, Zuolun; Zhang, Hongyu; Wang, Yue
2011-04-14
A novel green emissive Alq(3) solid with a facial isomeric form has been obtained by grinding the typical blue luminescent fac-Alq(3) crystalline powder. This is the first report, to the best of our knowledge, that a fac-Alq(3) isomer emits green light.
Fabrication and characterization of bioactive glass-ceramic using soda-lime-silica waste glass.
Abbasi, Mojtaba; Hashemi, Babak
2014-04-01
Soda-lime-silica waste glass was used to synthesize a bioactive glass-ceramic through solid-state reactions. In comparison with the conventional route, that is, the melt-quenching and subsequent heat treatment, the present work is an economical technique. Structural and thermal properties of the samples were examined by X-ray diffraction (XRD) and differential thermal analysis (DTA). The in vitro test was utilized to assess the bioactivity level of the samples by Hanks' solution as simulated body fluid (SBF). Bioactivity assessment by atomic absorption spectroscopy (AAS) and scanning electron microscopy (SEM) was revealed that the samples with smaller amount of crystalline phase had a higher level of bioactivity. Copyright © 2014 Elsevier B.V. All rights reserved.
Research on the Treatment of Wastewater by Waste Ceramic Adsorption
NASA Astrophysics Data System (ADS)
He, Lingfeng; Zhang, Yongli; Shi, Liang
2018-03-01
The process of preparing porous ceramic with waste porcelain powder as aggregate was researched. The affect of assimilate time on cuprum removal efficiency in wastewater containing copper was investigated. The results show the water copper removal rate increased along with the augment of assimilate time, and the assimilate time is suitable for 35 min; XRD characterizations show the porous ceramic catalyst before and after calcination in active components of X ray diffraction peak position almost had no changes, and the diffraction intensity slightly changed with calcination and absorption, and diffraction peaks became sharper, and its crystallinity was improved. Baking leads to the growth of crystal particles, and the performance of porous ceramics is stable before and after adsorption.
Boring and Sealing Rock with Directed Energy Millimeter-Waves
NASA Astrophysics Data System (ADS)
Woskov, P.; Einstein, H. H.; Oglesby, K.
2015-12-01
Millimeter-wave directed energy is being investigated to penetrate into deep crystalline basement rock formations to lower well costs and to melt rocks, metals, and other additives to seal wells for applications that include nuclear waste storage and geothermal energy. Laboratory tests have established that intense millimeter-wave (MMW) beams > 1 kW/cm2 can melt and/ or vaporize hard crystalline rocks. In principle this will make it possible to create open boreholes and a method to seal them with a glass/ceramic liner and plug formed from the original rock or with other materials. A 10 kW, 28 GHz commercial (CPI) gyrotron system with a launched beam diameter of about 32 mm was used to heat basalt, granite, limestone, and sandstone specimens to temperatures over 2500 °C to create melts and holes. A calibrated 137 GHz radiometer view, collinear with the heating beam, monitored real time peak rock temperature. A water load surrounding the rock test specimen primarily monitored unabsorbed power at 28 GHz. Power balance analysis of the laboratory observations shows that the temperature rise is limited by radiative heat loss, which would be expected to be trapped in a borehole. The analysis also indicates that the emissivity (absorption efficiency) in the radiated infrared range is lower than the emissivity at 28 GHz, giving the MMW frequency range an important advantage for rock melting. Strength tests on one granite type indicated that heating the rock initially weakens it, but with exposure to higher temperatures the resolidified black glassy product regains strength. Basalt was the easiest to melt and penetrate, if a melt leak path was provided, because of its low viscosity. Full beam holes up to about 50 mm diameter (diffraction increased beam size) were achieved through 30 mm thick basalt and granite specimens. Laboratory experiments to form a seal in an existing hole have also been carried out by melting rock and a simulated steel casing.
Reaction of amorphous/crystalline SiOC/Fe interfaces by thermal annealing
Su, Qing; Zhernenkov, Mikhail; Ding, Hepeng; ...
2017-06-12
The development of revolutionary new alloys and composites is crucial to meeting materials requirements for next generation nuclear reactors. The newly developed amorphous silicon oxycarbide (SiOC) and crystalline Fe composite system has shown radiation tolerance over a wide range of temperatures. To advance understanding of this new composite, we investigate the structure and thermal stability of the interface between amorphous SiOC and crystalline Fe by combining various experimental techniques and simulation methods. We show that the SiOC/Fe interface is thermally stable up to at least 400 °C. When the annealing temperature reaches 600 °C, an intermixed region forms at thismore » interface. This region appears to be a crystalline phase that forms an incoherent interface with the Fe layer. Density functional theory (DFT) Molecular dynamics (MD) is performed on the homogeneous SiFeOC phase to study the early stages of 2 formation of the intermixed layer. Both experimental and simulation results suggest this phase has the fayalite crystal structure. As a result, the physical processes involved in the formation of the intermixed region are discussed.« less
Reductive capacity measurement of waste forms for secondary radioactive wastes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Um, Wooyong; Yang, Jung-Seok; Serne, R. Jeffrey
2015-12-01
The reductive capacities of dry ingredients and final solid waste forms were measured using both the Cr(VI) and Ce(IV) methods and the results were compared. Blast furnace slag (BFS), sodium sulfide, SnF2, and SnCl2 used as dry ingredients to make various waste forms showed significantly higher reductive capacities compared to other ingredients regardless of which method was used. Although the BFS exhibits appreciable reductive capacity, it requires greater amounts of time to fully react. In almost all cases, the Ce(IV) method yielded larger reductive capacity values than those from the Cr(VI) method and can be used as an upper boundmore » for the reductive capacity of the dry ingredients and waste forms, because the Ce(IV) method subjects the solids to a strong acid (low pH) condition that dissolves much more of the solids. Because the Cr(VI) method relies on a neutral pH condition, the Cr(VI) method can be used to estimate primarily the waste form surface-related and readily dissolvable reductive capacity. However, the Cr(VI) method does not measure the total reductive capacity of the waste form, the long-term reductive capacity afforded by very slowly dissolving solids, or the reductive capacity present in the interior pores and internal locations of the solids.« less
Potentiation of lymphocyte proliferative responses by nickel sulfide
NASA Technical Reports Server (NTRS)
Jaramillo, A.; Sonnenfeld, G.
1992-01-01
Crystalline nickel sulfide (NiS) induced a spleen cell proliferation that resembles a mixed lymphocyte reaction (MLR). It depended on cell-cell interaction, induced high levels of interleukin-1 (IL-1) and interleukin-2 (IL-2) and the responding cell subpopulation was composed of CD4+ T lymphocytes. Furthermore, the proliferation was inhibited in a dose-dependent manner by magnesium. Crystalline NiS also increased significantly the spleen cell proliferative response to concanavalin A (Con A) and lipopolysaccharide (LPS) with magnesium potentiating the combined effects of crystalline NiS and mitogens. Interestingly, crystalline NiS did not show any effect on the induction of IL-2 by Con A. The results described herein suggest that crystalline NiS can potentiate both antigenic (MLR) and mitogenic (Con A and LPS) proliferative responses in vitro. Crystalline NiS appears to potentiate these responses by acting in the form of ionic nickel on several intracellular targets for which magnesium ions have different noncompetitive interactions. The effects of magnesium on the potentiating action of crystalline NiS are different depending upon the type of primary stimulatory signal for proliferation (mitogenic or antigenic).
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ebert, W. L.; Snyder, C. T.; Frank, Steven
This report describes the scientific basis underlying the approach being followed to design and develop “advanced” glass-bonded sodalite ceramic waste form (ACWF) materials that can (1) accommodate higher salt waste loadings than the waste form developed in the 1990s for EBR-II waste salt and (2) provide greater flexibility for immobilizing extreme waste salt compositions. This is accomplished by using a binder glass having a much higher Na 2O content than glass compositions used previously to provide enough Na+ to react with all of the Cl– in the waste salt and generate the maximum amount of sodalite. The phase compositions andmore » degradation behaviors of prototype ACWF products that were made using five new binder glass formulations and with 11-14 mass% representative LiCl/KCl-based salt waste were evaluated and compared with results of similar tests run with CWF products made using the original binder glass with 8 mass% of the same salt to demonstrate the approach and select a composition for further studies. About twice the amount of sodalite was generated in all ACWF materials and the microstructures and degradation behaviors confirmed our understanding of the reactions occurring during waste form production and the efficacy of the approach. However, the porosities of the resulting ACWF materials were higher than is desired. These results indicate the capacity of these ACWF waste forms to accommodate LiCl/KCl-based salt wastes becomes limited by porosity due to the low glass-to-sodalite volume ratio. Three of the new binder glass compositions were acceptable and there is no benefit to further increasing the Na content as initially planned. Instead, further studies are needed to develop and evaluate alternative production methods to decrease the porosity, such as by increasing the amount of binder glass in the formulation or by processing waste forms in a hot isostatic press. Increasing the amount of binder glass to eliminate porosity will decrease the waste loading from about 12% to 10% on a mass basis, but this will not significantly impact the waste loading on a volume basis. It is likely that heat output will limit the amount of waste salt that can be accommodated in a waste canister rather than the salt loading in an ACWF, and that the increase from 8 mass% to about 10 mass% salt loadings in ACWF materials will be sufficient to optimize these waste forms. Although the waste salt composition used in this study contained a moderate amount of NaCl, the test results suggest waste salts with little or no NaCl can be accommodated in ACWF materials by using the new binder glass, albeit at waste loadings lower than 8 mass%. The higher glass contents that will be required for ACWF materials made with salt wastes that do not contain NaCl are expected to result in much lower porosities in those waste forms.« less
Characterization and Prebiotic Effect of the Resistant Starch from Purple Sweet Potato.
Zheng, Yafeng; Wang, Qi; Li, Baoyu; Lin, Liangmei; Tundis, Rosa; Loizzo, Monica R; Zheng, Baodong; Xiao, Jianbo
2016-07-19
Purple sweet potato starch is a potential resource for resistant starch production. The effects of heat-moisture treatment (HMT) and enzyme debranching combined heat-moisture treatment (EHMT) on the morphological, crystallinity and thermal properties of PSP starches were investigated. The results indicated that, after HMT or EHMT treatments, native starch granules with smooth surface was destroyed to form a more compact, irregular and sheet-like structure. The crystalline pattern was transformed from C-type to B-type with decreasing relative crystallinity. Due to stronger crystallites formed in modified starches, the swelling power and solubility of HMT and EHMT starch were decreased, while the transition temperatures and gelatinization enthalpy were significantly increased. In addition, HMT and EHMT exhibited greater effects on the proliferation of bifidobacteria compared with either glucose or high amylose maize starch.
NASA Astrophysics Data System (ADS)
Hu, Xiao; Kaplan, David; Cebe, Peggy
2007-03-01
We report a study of self-assembled beta pleated sheets in Bombyx mori silk fibroin films using thermal analysis and infrared spectroscopy. Crystallization of beta pleated sheets was effected either by heating the films above the glass transition temperature (Tg) and holding isothermally, or by exposure to methanol. The fractions of secondary structural components including random coils, alpha helices, beta pleated sheets, turns, and side chains, were evaluated using Fourier self-deconvolution (FSD) of the infrared absorbance spectra. As crystalline beta sheets form, the heat capacity increment from the TMDSC trace at Tg is systematically decreased and is linearly well correlated with beta sheet content determined from FSD. This analysis of beta sheet content can serve as an alternative to X-ray methods and may have wide applicability to other crystalline beta sheet forming proteins.
High-contrast observations of (136108) Haumea. A crystalline water-ice multiple system
NASA Astrophysics Data System (ADS)
Dumas, C.; Carry, B.; Hestroffer, D.; Merlin, F.
2011-04-01
Context. The trans-Neptunian region of the Solar System is populated by a wide variety of icy bodies showing great diversity in orbital behavior, size, surface color, and composition. One can also see there are dynamical families and binary systems. One surprising feature detected in the spectra of some of the largest trans-Neptunians is the presence of crystalline water-ice. This is the case for the large TNO (136 108) Haumea (2003 EL61). Aims: We seek to constrain the state of the water ice of Haumea and its satellites and to investigate possible energy sources that maintain the water ice in its crystalline form. Methods: Spectro-imaging observations in the near infrared were performed with the integral field spectrograph SINFONI mounted on UT4 at the ESO Very Large Telescope. The spectra of both Haumea and its larger satellite Hi'iaka were analyzed. Relative astrometry of the components was also measured, providing a check of the orbital solutions and equinox seasons. Results: We describe the physical characteristics of the crystalline water-ice present on the surface of Haumea and its largest satellite Hi'iaka and analyze possible sources of heating to maintain water in a crystalline state: tidal dissipation in the system components vs. radiogenic source. The surface of Hi'iaka appears to be covered by large grains of water ice, almost entirely in its crystalline form. Under some restricted conditions, both radiogenic heating and tidal forces between Haumea and Hi'iaka could provide the energy needed to maintain the ice in its crystalline state. Based on observations collected at the European Southern Observatory, Paranal, Chile - 60.A-9235.
Roadmap for disposal of Electrorefiner Salt as Transuranic Waste.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rechard, Robert P.; Trone, Janis R.; Kalinina, Elena Arkadievna
The experimental breeder reactor (EBR-II) used fuel with a layer of sodium surrounding the uranium-zirconium fuel to improve heat transfer. Disposing of EBR-II fuel in a geologic repository without treatment is not prudent because of the potentially energetic reaction of the sodium with water. In 2000, the US Department of Energy (DOE) decided to treat the sodium-bonded fuel with an electrorefiner (ER), which produces metallic uranium product, a metallic waste, mostly from the cladding, and the salt waste in the ER, which contains most of the actinides and fission products. Two waste forms were proposed for disposal in a minedmore » repository; the metallic waste, which was to be cast into ingots, and the ER salt waste, which was to be further treated to produce a ceramic waste form. However, alternative disposal pathways for metallic and salt waste streams may reduce the complexity. For example, performance assessments show that geologic repositories can easily accommodate the ER salt waste without treating it to form a ceramic waste form. Because EBR-II was used for atomic energy defense activities, the treated waste likely meets the definition of transuranic waste. Hence, disposal at the Waste Isolation Pilot Plant (WIPP) in southern New Mexico, may be feasible. This report reviews the direct disposal pathway for ER salt waste and describes eleven tasks necessary for implementing disposal at WIPP, provided space is available, DOE decides to use this alternative disposal pathway in an updated environmental impact statement, and the State of New Mexico grants permission.« less
Crystal genes in a marginal glass-forming system of Ni 50Zr 50
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wen, T. Q.; Tang, L.; Sun, Y.
Glass-forming motifs with B2 traits are found. A perfect Ni-centered B33 motif deteriorates the glass-forming ability of Ni 50Zr 50. The marginal glass-forming ability (GFA) of binary Ni-Zr system is an issue to be explained considering the numerous bulk metallic glasses (BMGs) found in the Cu-Zr system. Using molecular dynamics, the structures and dynamics of Ni 50Zr 50 metallic liquid and glass are investigated at the atomistic level. To achieve a well-relaxed glassy sample, sub-T g annealing method is applied and the final sample is closer to the experiments than the models prepared by continuous cooling. With the state-of-the-art structuralmore » analysis tools such as cluster alignment and pair-wise alignment methods, two glass-forming motifs with some mixed traits of the metastable B2 crystalline phase and the crystalline Ni-centered B33 motif are found to be dominant in the undercooled liquid and glass samples. A new chemical order characterization on each short-range order (SRO) structure is accomplished based on the cluster alignment method. The significant amount of the crystalline motif and the few icosahedra in the glassy sample deteriorate the GFA.« less
Crystal genes in a marginal glass-forming system of Ni 50Zr 50
Wen, T. Q.; Tang, L.; Sun, Y.; ...
2017-10-17
Glass-forming motifs with B2 traits are found. A perfect Ni-centered B33 motif deteriorates the glass-forming ability of Ni 50Zr 50. The marginal glass-forming ability (GFA) of binary Ni-Zr system is an issue to be explained considering the numerous bulk metallic glasses (BMGs) found in the Cu-Zr system. Using molecular dynamics, the structures and dynamics of Ni 50Zr 50 metallic liquid and glass are investigated at the atomistic level. To achieve a well-relaxed glassy sample, sub-T g annealing method is applied and the final sample is closer to the experiments than the models prepared by continuous cooling. With the state-of-the-art structuralmore » analysis tools such as cluster alignment and pair-wise alignment methods, two glass-forming motifs with some mixed traits of the metastable B2 crystalline phase and the crystalline Ni-centered B33 motif are found to be dominant in the undercooled liquid and glass samples. A new chemical order characterization on each short-range order (SRO) structure is accomplished based on the cluster alignment method. The significant amount of the crystalline motif and the few icosahedra in the glassy sample deteriorate the GFA.« less
Feasibility Study of Food Waste Co-Digestion at U.S. Army Installations
2017-03-01
sludge and food these, waste materials can create energy in the form of electric power for the plant. The extra heat and power generated from this... formed at Fort Huachuca provided detailed analyses of the waste stream, primary generators of each waste component, and a measured sample from the...tanks. The second tank will be the current first tank, where the majority of methane will be formed , and the last tank will remain as the final rest
Leaching boundary movement in solidified/stabilized waste forms
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kuang Ye Cheng; Bishop, P.L.
1992-02-01
Investigation of the leaching of cement-based waste forms in acetic acid solutions found that acids attacked the waste form from the surface toward the center. A sharp leaching boundary was identified in every leached sample, using pH color indicators. The movement of the leaching boundary was found to be a single diffusion-controlled process.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Xiong, Yongliang; Kirkes, Leslie Dawn; Marrs, Cassandra
In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH) 3(micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3(micro cr), avoiding the possibility of phase change.
NASA Astrophysics Data System (ADS)
Ferreira, F. V.; Mariano, M.; Rabelo, S. C.; Gouveia, R. F.; Lona, L. M. F.
2018-04-01
This work presents the isolation and functionalization of cellulose nanocrystals (CNCs) extracted from sugarcane bagasse (SCB). CNCs were obtained by acid hydrolysis of bleached bagasse pulp and functionalized with adipic acid. The results showed that unmodified CNCs exhibit both a high crystallinity index and a significant aspect ratio. Surface modification with adipic acid decreases the nanocrystal dimensions due to removal of the amorphous region between the crystalline domains and also changes the electrostatic repulsion and hydrophilic affinity of CNCs. Unmodified CNCs offer potential applications as reinforcing phase in hydrophilic polymeric matrices, while modified CNCs interact better with hydrophobic matrices. The use of CNCs as reinforcement in polymer nanocomposites expands the application of this renewable material and increases its added value, providing nonenergy-based markets for the main biomass of the sugarcane industry.
Xiong, Yongliang; Kirkes, Leslie Dawn; Marrs, Cassandra
2017-12-01
In this paper, the experimental results from long-term solubility experiments on micro crystalline neodymium hydroxide, Nd(OH) 3(micro cr), in high ionic strength solutions at 298.15 K under well-constrained conditions are presented. The starting material was synthesized according to a well-established method in the literature. In contrast with the previous studies in which hydrogen ion concentrations in experiments were adjusted with addition of either an acid or a base, the hydrogen ion concentrations in our experiments are controlled by the dissolution of Nd(OH) 3(micro cr), avoiding the possibility of phase change.
Catalytic crystallization of ices by small silicate smokes at temperatures less than 20K
NASA Technical Reports Server (NTRS)
Moore, M.; Ferrante, R.; Hudson, R.; Tanabe, T.; Nuth, J.
1993-01-01
Samples of methanol and water ices condensed from the vapor onto aluminum substrates at low temperatures (below approximately 80 K) form amorphous ices; annealing at temperatures in excess of 140-155 K is usually required to convert such amorphous samples to crystalline ices. However, we have found that when either methanol or water vapor is deposited on to aluminum substrates that have been coated with a thin (0.1-0.5 mm) layer of amorphous silicate smoke, the ices condense in crystalline form. We believe that crystalline ice forms as the result of energy liberated at the ice/silicate interface perhaps due to weak bonding of the ice at defect sites on the grains and the very high surface to volume ratio and defect density of these smokes. Annealing of amorphous water ice mixed with more volatile components such as methane, carbon monoxide, etc., has been suggested as an efficient way to produce clatherates in the outer solar nebula and thus explain the volatile content of comets and icy satellites of the outer planets. This hypothesis may need to be re-examined if amorphous ice does not form on cold silicate grains.
The origin, source, and cycling of methane in deep crystalline rock biosphere.
Kietäväinen, Riikka; Purkamo, Lotta
2015-01-01
The emerging interest in using stable bedrock formations for industrial purposes, e.g., nuclear waste disposal, has increased the need for understanding microbiological and geochemical processes in deep crystalline rock environments, including the carbon cycle. Considering the origin and evolution of life on Earth, these environments may also serve as windows to the past. Various geological, chemical, and biological processes can influence the deep carbon cycle. Conditions of CH4 formation, available substrates and time scales can be drastically different from surface environments. This paper reviews the origin, source, and cycling of methane in deep terrestrial crystalline bedrock with an emphasis on microbiology. In addition to potential formation pathways of CH4, microbial consumption of CH4 is also discussed. Recent studies on the origin of CH4 in continental bedrock environments have shown that the traditional separation of biotic and abiotic CH4 by the isotopic composition can be misleading in substrate-limited environments, such as the deep crystalline bedrock. Despite of similarities between Precambrian continental sites in Fennoscandia, South Africa and North America, where deep methane cycling has been studied, common physicochemical properties which could explain the variation in the amount of CH4 and presence or absence of CH4 cycling microbes were not found. However, based on their preferred carbon metabolism, methanogenic microbes appeared to have similar spatial distribution among the different sites.
The origin, source, and cycling of methane in deep crystalline rock biosphere
Kietäväinen, Riikka; Purkamo, Lotta
2015-01-01
The emerging interest in using stable bedrock formations for industrial purposes, e.g., nuclear waste disposal, has increased the need for understanding microbiological and geochemical processes in deep crystalline rock environments, including the carbon cycle. Considering the origin and evolution of life on Earth, these environments may also serve as windows to the past. Various geological, chemical, and biological processes can influence the deep carbon cycle. Conditions of CH4 formation, available substrates and time scales can be drastically different from surface environments. This paper reviews the origin, source, and cycling of methane in deep terrestrial crystalline bedrock with an emphasis on microbiology. In addition to potential formation pathways of CH4, microbial consumption of CH4 is also discussed. Recent studies on the origin of CH4 in continental bedrock environments have shown that the traditional separation of biotic and abiotic CH4 by the isotopic composition can be misleading in substrate-limited environments, such as the deep crystalline bedrock. Despite of similarities between Precambrian continental sites in Fennoscandia, South Africa and North America, where deep methane cycling has been studied, common physicochemical properties which could explain the variation in the amount of CH4 and presence or absence of CH4 cycling microbes were not found. However, based on their preferred carbon metabolism, methanogenic microbes appeared to have similar spatial distribution among the different sites. PMID:26236303
Test plan for formulation and evaluation of grouted waste forms with shine process wastes
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ebert, W. L.; Jerden, J. L.
2015-09-01
The objective of this experimental project is to demonstrate that waste streams generated during the production of Mo99 by the SHINE Medical Technologies (SHINE) process can be immobilized in cement-based grouted waste forms having physical, chemical, and radiological stabilities that meet regulatory requirements for handling, storage, transport, and disposal.
Final waste forms project: Performance criteria for phase I treatability studies
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gilliam, T.M.; Hutchins, D.A.; Chodak, P. III
1994-06-01
This document defines the product performance criteria to be used in Phase I of the Final Waste Forms Project. In Phase I, treatability studies will be performed to provide {open_quotes}proof-of-principle{close_quotes} data to establish the viability of stabilization/solidification (S/S) technologies. This information is required by March 1995. In Phase II, further treatability studies, some at the pilot scale, will be performed to provide sufficient data to allow treatment alternatives identified in Phase I to be more fully developed and evaluated, as well as to reduce performance uncertainties for those methods chosen to treat a specific waste. Three main factors influence themore » development and selection of an optimum waste form formulation and hence affect selection of performance criteria. These factors are regulatory, process-specific, and site-specific waste form standards or requirements. Clearly, the optimum waste form formulation will require consideration of performance criteria constraints from each of the three categories. Phase I will focus only on the regulatory criteria. These criteria may be considered the minimum criteria for an acceptable waste form. In other words, a S/S technology is considered viable only if it meet applicable regulatory criteria. The criteria to be utilized in the Phase I treatability studies were primarily taken from Environmental Protection Agency regulations addressed in 40 CFR 260 through 265 and 268; and Nuclear Regulatory Commission regulations addressed in 10 CFR 61. Thus the majority of the identified criteria are independent of waste form matrix composition (i.e., applicable to cement, glass, organic binders etc.).« less
Epsilon metal waste form for immobilization of noble metals from used nuclear fuel
NASA Astrophysics Data System (ADS)
Crum, Jarrod V.; Strachan, Denis; Rohatgi, Aashish; Zumhoff, Mac
2013-10-01
Epsilon metal (ɛ-metal), an alloy of Mo, Pd, Rh, Ru, and Tc, is being developed as a waste form to treat and immobilize the undissolved solids and dissolved noble metals from aqueous reprocessing of commercial used nuclear fuel. Epsilon metal is an attractive waste form for several reasons: increased durability relative to borosilicate glass, it can be fabricated without additives (100% waste loading), and in addition it also benefits borosilicate glass waste loading by eliminating noble metals from the glass, thus the processing problems related to their insolubility in glass. This work focused on the processing aspects of the epsilon metal waste form development. Epsilon metal is comprised of refractory metals resulting in high alloying temperatures, expected to be 1500-2000 °C, making it a non-trivial phase to fabricate by traditional methods. Three commercially available advanced technologies were identified: spark-plasma sintering, microwave sintering, and hot isostatic pressing, and investigated as potential methods to fabricate this waste form. Results of these investigations are reported and compared in terms of bulk density, phase assemblage (X-ray diffraction and elemental analysis), and microstructure (scanning electron microscopy).
IR spectra and properties of solid acetone, an interstellar and cometary molecule
NASA Astrophysics Data System (ADS)
Hudson, Reggie L.; Gerakines, Perry A.; Ferrante, Robert F.
2018-03-01
Mid-infrared spectra of amorphous and crystalline acetone are presented along with measurements of the refractive index and density for both forms of the compound. Infrared band strengths are reported for the first time for amorphous and crystalline acetone, along with IR optical constants. Vapor pressures and a sublimation enthalpy for crystalline acetone also are reported. Positions of 13C-labeled acetone are measured. Band strengths are compared to gas-phase values and to the results of a density-functional calculation. A 73% error in previous work is identified and corrected.
Mineral abundances of comet 17P/Holmes derived from the mid-infrared spectrum
NASA Astrophysics Data System (ADS)
Shinnaka, Yoshiharu; Yamaguchi, MItsuru; Ootsubo, Takafumi; Kawakita, Hideyo; Sakon, Itsuki; Honda, Mitsuhiko; Watanabe, Jun-ichi
2017-10-01
Dust grains of crystalline silicate, which is rarely presented in an interstellar space, were found in cometary nuclei (Messenger et al. 1996, LPI, 27, 867; Wooden et al. 1999, ApJ, 517, 1058, references therein). It is thought that these crystalline silicates had formed by annealing or condensations of amorphous grains near the Sun in the solar nebula, and incorporated into a cometary nucleus in a cold region (farther than formation regions of the crystalline silicates) by radial transportation in the solar nebula. It is considered that transportation mechanisms to outside of the solar nebula were turbulent and/or X-wind. An abundance of the crystalline dust grains was therefore expected to be smaller as far from the Sun (Gail, 2001, A&A, 378, 192; Bockelée-Morvan et al. 2002, A&A, 384, 1107). Namely, the abundance ratio of the crystalline silicate in cometary dust grains relates a degree of mass transportation and a distance from the Sun when cometary nucleus formed in the Solar nebula. The mass ratio of crystalline silicates of dust grains is determined from by Si-O stretching vibrational bands of silicate grains around 10 μm using difference of spectral band features between crystalline and amorphous grains. We present the crystalline-to-amorphous mass ratio of silicate grains in the comet 17P/Holmes by using the thermal emission mode of the dust grains (Ootsubo et al. 2007, P&SS, 55, 1044) applied to the mid-infrared spectra of the comet. These spectra were taken by the COMICS mounted on the Subaru Telescope on 2007 October 25, 26, 27 and 28 immediately after the great outburst of the comet (started on October 23). We discuss about formation conditions of the nucleus of the comet based on the derived mass ratio of silicate grains of the comet.
Riley, Brian J.; Pierce, David A.; Frank, Steven M.; ...
2015-04-01
This paper describes the various approaches attempted to make solution-derived sodalite with a LiCl-Li 2O oxide reduction salt used to dissolve used uranium oxide fuel so the uranium can be recovered and recycled. The approaches include modified sol-gel and solutionbased synthesis processes. As-made products were mixed with 5 and 10 mass% of a Na 2O-B 2O 3- SiO 2 glass binder and these, along with product without a binder, were heated using either a cold-press-and-sinter method or hot uniaxial pressing. The results demonstrate the limitation of sodalite yield due to the fast intermediate reactions between Na+ and Cl- to formmore » halite in solution and Li 2O and SiO 2 to form lithium silicates (e.g., Li 2SiO 3 or Li 2Si 2O 5) in the calcined and sintered pellets. The results show that pellets can be made with high sodalite fractions in the crystalline product (~92 mass%) and low porosities using a solution-based approach and this LiCl-Li 2O salt but that the incorporation of Li into the sodalite is low.« less
SEPARATIONS AND WASTE FORMS CAMPAIGN IMPLEMENTATION PLAN
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vienna, John D.; Todd, Terry A.; Peterson, Mary E.
2012-11-26
This Separations and Waste Forms Campaign Implementation Plan provides summary level detail describing how the Campaign will achieve the objectives set-forth by the Fuel Cycle Reasearch and Development (FCRD) Program. This implementation plan will be maintained as a living document and will be updated as needed in response to changes or progress in separations and waste forms research and the FCRD Program priorities.
Finite element analysis of ion transport in solid state nuclear waste form materials
NASA Astrophysics Data System (ADS)
Rabbi, F.; Brinkman, K.; Amoroso, J.; Reifsnider, K.
2017-09-01
Release of nuclear species from spent fuel ceramic waste form storage depends on the individual constituent properties as well as their internal morphology, heterogeneity and boundary conditions. Predicting the release rate is essential for designing a ceramic waste form, which is capable of effectively storing the spent fuel without contaminating the surrounding environment for a longer period of time. To predict the release rate, in the present work a conformal finite element model is developed based on the Nernst Planck Equation. The equation describes charged species transport through different media by convection, diffusion, or migration. And the transport can be driven by chemical/electrical potentials or velocity fields. The model calculates species flux in the waste form with different diffusion coefficient for each species in each constituent phase. In the work reported, a 2D approach is taken to investigate the contributions of different basic parameters in a waste form design, i.e., volume fraction, phase dispersion, phase surface area variation, phase diffusion co-efficient, boundary concentration etc. The analytical approach with preliminary results is discussed. The method is postulated to be a foundation for conformal analysis based design of heterogeneous waste form materials.
Low melting high lithia glass compositions and methods
Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.
2004-11-02
The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.
Low melting high lithia glass compositions and methods
Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.
2003-10-07
The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.
Low melting high lithia glass compositions and methods
Jantzen, Carol M.; Pickett, John B.; Cicero-Herman, Connie A.; Marra, James C.
2000-01-01
The invention relates to methods of vitrifying waste and for lowering the melting point of glass forming systems by including lithia formers in the glass forming composition in significant amounts, typically from about 0.16 wt % to about 11 wt %, based on the total glass forming oxides. The lithia is typically included as a replacement for alkali oxide glass formers that would normally be present in a particular glass forming system. Replacement can occur on a mole percent or weight percent basis, and typically results in a composition wherein lithia forms about 10 wt % to about 100 wt % of the alkali oxide glass formers present in the composition. The present invention also relates to the high lithia glass compositions formed by these methods. The invention is useful for stabilization of numerous types of waste materials, including aqueous waste streams, sludge solids, mixtures of aqueous supernate and sludge solids, combinations of spent filter aids from waste water treatment and waste sludges, supernate alone, incinerator ash, incinerator offgas blowdown, or combinations thereof, geological mine tailings and sludges, asbestos, inorganic filter media, cement waste forms in need of remediation, spent or partially spent ion exchange resins or zeolites, contaminated soils, lead paint, etc. The decrease in melting point achieved by the present invention desirably prevents volatilization of hazardous or radioactive species during vitrification.
Data Package for Secondary Waste Form Down-Selection—Cast Stone
DOE Office of Scientific and Technical Information (OSTI.GOV)
Serne, R. Jeffrey; Westsik, Joseph H.
2011-09-05
Available literature on Cast Stone and Saltstone was reviewed with an emphasis on determining how Cast Stone and related grout waste forms performed in relationship to various criteria that will be used to decide whether a specific type of waste form meets acceptance criteria for disposal in the Integrated Disposal Facility (IDF) at Hanford. After the critical review of the Cast Stone/Saltstone literature, we conclude that Cast Stone is a good candidate waste form for further consideration. Cast stone meets the target IDF acceptance criteria for compressive strength, no free liquids, TCLP leachate are below the UTS permissible concentrations andmore » leach rates for Na and Tc-99 are suiteably low. The cost of starting ingredients and equipment necessary to generate Cast Stone waste forms with secondary waste streams are low and the Cast Stone dry blend formulation can be tailored to accommodate variations in liquid waste stream compositions. The database for Cast Stone short-term performance is quite extensive compared to the other three candidate waste solidification processes. The solidification of liquid wastes in Cast Stone is a mature process in comparison to the other three candidates. Successful production of Cast Stone or Saltstone has been demonstrated from lab-scale monoliths with volumes of cm3 through m3 sized blocks to 210-liter sized drums all the way to the large pours into vaults at Savannah River. To date over 9 million gallons of low activity liquid waste has been solidified and disposed in concrete vaults at Savannah River.« less
Development of a Universal Canister for Disposal of High-Level Waste in Deep Boreholes.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Price, Laura L.; Gomberg, Steve
2015-11-01
The mission of the United States Department of Energy’s Office of Environmental Management is to complete the safe cleanup of the environmental legacy brought about from five decades of nuclear weapons development and government-sponsored nuclear energy research. Some of the wastes that must be managed have been identified as good candidates for disposal in a deep borehole in crystalline rock. In particular, wastes that can be disposed of in a small package are good candidates for this disposal concept. A canister-based system that can be used for handling these wastes during the disposition process (i.e., storage, transfer, transportation, and disposal)more » could facilitate the eventual disposal of these wastes. Development of specifications for the universal canister system will consider the regulatory requirements that apply to storage, transportation, and disposal of the capsules, as well as operational requirements and limits that could affect the design of the canister (e.g., deep borehole diameter). In addition, there are risks and technical challenges that need to be recognized and addressed as Universal Canister system specifications are developed. This paper provides an approach to developing specifications for such a canister system that is integrated with the overall efforts of the DOE’s Used Fuel Disposition Campaign's Deep Borehole Field Test and compatible with planned storage of potential borehole-candidate wastes.« less
Apparatus for the processing of solid mixed waste containing radioactive and hazardous materials
Gotovchikov, Vitaly T.; Ivanov, Alexander V.; Filippov, Eugene A.
1999-03-16
Apparatus for the continuous heating and melting of a solid mixed waste bearing radioactive and hazardous materials to form separate metallic, slag and gaseous phases for producing compact forms of the waste material to facilitate disposal includes a copper split water-cooled (cold) crucible as a reaction vessel for receiving the waste material. The waste material is heated by means of the combination oaf plasma torch directed into the open upper portion of the cold crucible and an electromagnetic flux produced by induction coils disposed about the crucible which is transparent to electromagnetic fields. A metallic phase of the waste material is formed in a lower portion of the crucible and is removed in the form of a compact ingot suitable for recycling and further processing. A glass-like, non-metallic slag phase containing radioactive elements is also formed in the crucible and flows out of the open upper portion of the crucible into a slag ingot mold for disposal. The decomposition products of the organic and toxic materials are incinerated and converted to environmentally safe gases in the melter.
Processing of solid mixed waste containing radioactive and hazardous materials
Gotovchikov, Vitaly T.; Ivanov, Alexander V.; Filippov, Eugene A.
1998-05-12
Apparatus for the continuous heating and melting of a solid mixed waste bearing radioactive and hazardous materials to form separate metallic, slag and gaseous phases for producing compact forms of the waste material to facilitate disposal includes a copper split water-cooled (cold) crucible as a reaction vessel for receiving the waste material. The waste material is heated by means of the combination of a plasma torch directed into the open upper portion of the cold crucible and an electromagnetic flux produced by induction coils disposed about the crucible which is transparent to electromagnetic fields. A metallic phase of the waste material is formed in a lower portion of the crucible and is removed in the form of a compact ingot suitable for recycling and further processing. A glass-like, non-metallic slag phase containing radioactive elements is also formed in the crucible and flows out of the open upper portion of the crucible into a slag ingot mold for disposal. The decomposition products of the organic and toxic materials are incinerated and converted to environmentally safe gases in the melter.
Apparatus for the processing of solid mixed waste containing radioactive and hazardous materials
Gotovchikov, V.T.; Ivanov, A.V.; Filippov, E.A.
1999-03-16
Apparatus for the continuous heating and melting of a solid mixed waste bearing radioactive and hazardous materials to form separate metallic, slag and gaseous phases for producing compact forms of the waste material to facilitate disposal includes a copper split water-cooled (cold) crucible as a reaction vessel for receiving the waste material. The waste material is heated by means of the combination of a plasma torch directed into the open upper portion of the cold crucible and an electromagnetic flux produced by induction coils disposed about the crucible which is transparent to electromagnetic fields. A metallic phase of the waste material is formed in a lower portion of the crucible and is removed in the form of a compact ingot suitable for recycling and further processing. A glass-like, non-metallic slag phase containing radioactive elements is also formed in the crucible and flows out of the open upper portion of the crucible into a slag ingot mold for disposal. The decomposition products of the organic and toxic materials are incinerated and converted to environmentally safe gases in the melter. 6 figs.
Processing of solid mixed waste containing radioactive and hazardous materials
Gotovchikov, V.T.; Ivanov, A.V.; Filippov, E.A.
1998-05-12
Apparatus for the continuous heating and melting of a solid mixed waste bearing radioactive and hazardous materials to form separate metallic, slag and gaseous phases for producing compact forms of the waste material to facilitate disposal includes a copper split water-cooled (cold) crucible as a reaction vessel for receiving the waste material. The waste material is heated by means of the combination of a plasma torch directed into the open upper portion of the cold crucible and an electromagnetic flux produced by induction coils disposed about the crucible which is transparent to electromagnetic fields. A metallic phase of the waste material is formed in a lower portion of the crucible and is removed in the form of a compact ingot suitable for recycling and further processing. A glass-like, non-metallic slag phase containing radioactive elements is also formed in the crucible and flows out of the open upper portion of the crucible into a slag ingot mold for disposal. The decomposition products of the organic and toxic materials are incinerated and converted to environmentally safe gases in the melter. 6 figs.
NASA Astrophysics Data System (ADS)
Hsu, Jen-Hsien; Bai, Jincheng; Kim, Cheol-Woon; Brow, Richard K.; Szabo, Joe; Zervos, Adam
2018-03-01
The effects of cooling rate on the chemical durability of iron phosphate waste forms containing up to 40 wt% of a high MoO3 Collins-CLT waste simulant were determined at 90 °C using the product consistency test (PCT). The waste form, designated 40wt%-5, meets appropriate Department of Energy (DOE) standards when rapidly quenched from the melt (as-cast) and after slow cooling following the CCC (canister centerline cooling)-protocol, although the quenched glass is more durable. The analysis of samples from the vapor hydration test (VHT) and the aqueous corrosion test (differential recession test) reveals that rare earth orthophosphate (monazite) and Zr-pyrophosphate crystals that form on cooling are more durable than the residual glass in the 40wt%-5 waste form. The residual glass in the CCC-treated samples has a greater average phosphate chain length and a lower Fe/P ratio, and those contribute to its faster corrosion kinetics.
Current induced polycrystalline-to-crystalline transformation in vanadium dioxide nanowires
Jeong, Junho; Yong, Zheng; Joushaghani, Arash; Tsukernik, Alexander; Paradis, Suzanne; Alain, David; Poon, Joyce K. S.
2016-01-01
Vanadium dioxide (VO2) exhibits a reversible insulator-metal phase transition that is of significant interest in energy-efficient nanoelectronic and nanophotonic devices. In these applications, crystalline materials are usually preferred for their superior electrical transport characteristics as well as spatial homogeneity and low surface roughness over the device area for reduced scattering. Here, we show applied electrical currents can induce a permanent reconfiguration of polycrystalline VO2 nanowires into crystalline nanowires, resulting in a dramatically reduced hysteresis across the phase transition and reduced resistivity. Low currents below 3 mA were sufficient to cause the local temperature in the VO2 to reach about 1780 K to activate the irreversible polycrystalline-to-crystalline transformation. The crystallinity was confirmed by electron microscopy and diffraction analyses. This simple yet localized post-processing of insulator-metal phase transition materials may enable new methods of studying and fabricating nanoscale structures and devices formed from these materials. PMID:27892519
Traffic jams reduce hydrolytic efficiency of cellulase on cellulose surface.
Igarashi, Kiyohiko; Uchihashi, Takayuki; Koivula, Anu; Wada, Masahisa; Kimura, Satoshi; Okamoto, Tetsuaki; Penttilä, Merja; Ando, Toshio; Samejima, Masahiro
2011-09-02
A deeper mechanistic understanding of the saccharification of cellulosic biomass could enhance the efficiency of biofuels development. We report here the real-time visualization of crystalline cellulose degradation by individual cellulase enzymes through use of an advanced version of high-speed atomic force microscopy. Trichoderma reesei cellobiohydrolase I (TrCel7A) molecules were observed to slide unidirectionally along the crystalline cellulose surface but at one point exhibited collective halting analogous to a traffic jam. Changing the crystalline polymorphic form of cellulose by means of an ammonia treatment increased the apparent number of accessible lanes on the crystalline surface and consequently the number of moving cellulase molecules. Treatment of this bulky crystalline cellulose simultaneously or separately with T. reesei cellobiohydrolase II (TrCel6A) resulted in a remarkable increase in the proportion of mobile enzyme molecules on the surface. Cellulose was completely degraded by the synergistic action between the two enzymes.
Skrdla, Peter J; Zhang, Dan
2014-03-01
The crystalline citrate salt (CS) of a developmental pharmaceutical compound, MK-Q, was investigated in this work from two different, but related, perspectives. In the first part of the paper, the apparent disproportionation kinetics were surveyed using two different slurry systems, one containing water and the other a pH 6.9 phosphate buffer, using time-dependent measurements of the solution pH or by acquiring online Raman spectra of the solids. While the CS is generally stable when stored as a solid under ambient conditions of temperature and humidity, its low pHmax (<3) facilitates rapid disproportionation in aqueous solution, particularly at higher pH values. The rate of disappearance of the CS was found to obey first-order (Noyes-Whitney/dissolution rate-limited) kinetics, however, the formation of the crystalline product form in the slurry system was observed to exhibit kinetics consistent with a heterogeneous nucleation-and-growth mechanism. In the second part of this paper, more sensitive offline measurements made using XRPD, DSC and FT-Raman spectroscopy were applied to the characterization of binary physical mixtures of the CS and free base (FB) crystalline forms of MK-Q to obtain a calibration curve for each technique. It was found that all calibration plots exhibited good linearity of response, with the limit of detection (LOD) for each technique estimated to be ≤7 wt% FB. While additional calibration curves would need to be constructed to allow for accurate quantitation in various slurry systems, the general feasibility of these techniques is demonstrated for detecting low levels of CS disproportionation. Copyright © 2013 Elsevier B.V. All rights reserved.
U.S. Food Loss and Waste 2030 Champions Activity Form
To join the U.S. Food Loss and Waste 2030 Champions, organizations complete and submit the 2030 Champions form, in which they commit to reduce food loss and waste in their own operations and periodically report their progress on their website.
High magnetic field processing of liquid crystalline polymers
Smith, M.E.; Benicewicz, B.C.; Douglas, E.P.
1998-11-24
A process of forming bulk articles of oriented liquid crystalline thermoset material, the material characterized as having an enhanced tensile modulus parallel to orientation of an applied magnetic field of at least 25 percent greater than said material processed in the absence of a magnetic field, by curing a liquid crystalline thermoset precursor within a high strength magnetic field of greater than about 2 Tesla, is provided, together with a resultant bulk article of a liquid crystalline thermoset material, said material processed in a high strength magnetic field whereby said material is characterized as having a tensile modulus parallel to orientation of said field of at least 25 percent greater than said material processed in the absence of a magnetic field.
High magnetic field processing of liquid crystalline polymers
Smith, Mark E.; Benicewicz, Brian C.; Douglas, Elliot P.
1998-01-01
A process of forming bulk articles of oriented liquid crystalline thermoset material, the material characterized as having an enhanced tensile modulus parallel to orientation of an applied magnetic field of at least 25 percent greater than said material processed in the absence of a magnetic field, by curing a liquid crystalline thermoset precursor within a high strength magnetic field of greater than about 2 Tesla, is provided, together with a resultant bulk article of a liquid crystalline thermoset material, said material processed in a high strength magnetic field whereby said material is characterized as having a tensile modulus parallel to orientation of said field of at least 25 percent greater than said material processed in the absence of a magnetic field.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Indacochea, J. E.; Gattu, V. K.; Chen, X.
The results of electrochemical corrosion tests and modeling activities performed collaboratively by researchers at the University of Illinois at Chicago and Argonne National Laboratory as part of workpackage NU-13-IL-UIC-0203-02 are summarized herein. The overall objective of the project was to develop and demonstrate testing and modeling approaches that could be used to evaluate the use of composite alloy/ceramic materials as high-level durable waste forms. Several prototypical composite waste form materials were made from stainless steels representing fuel cladding, reagent metals representing metallic fuel waste streams, and reagent oxides representing oxide fuel waste streams to study the microstructures and corrosion behaviorsmore » of the oxide and alloy phases. Microelectrodes fabricated from small specimens of the composite materials were used in a series of electrochemical tests to assess the corrosion behaviors of the constituent phases and phase boundaries in an aggressive acid brine solution at various imposed surface potentials. The microstructures were characterized in detail before and after the electrochemical tests to relate the electrochemical responses to changes in both the electrode surface and the solution composition. The results of microscopic, electrochemical, and solution analyses were used to develop equivalent circuit and physical models representing the measured corrosion behaviors of the different materials pertinent to long-term corrosion behavior. This report provides details regarding (1) the production of the composite materials, (2) the protocol for the electrochemical measurements and interpretations of the responses of multi-phase alloy and oxide composites, (3) relating corrosion behaviors to microstructures of multi-phase alloys based on 316L stainless steel and HT9 (410 stainless steel was used as a substitute) with added Mo, Ni, and/or Mn, and (4) modeling the corrosion behaviors and rates of several alloy/oxide composite materials made with added lanthanide and uranium oxides. These analyses show the corrosion behaviors of the alloy/ceramic composite materials are very similar to the corrosion behaviors of multi-phase alloy waste forms, and that the presence of oxide inclusions does not impact the corrosion behaviors of the alloy phases. Mixing with metallic waste streams is beneficial to lanthanide and uranium oxides in that they react with Zr in the fuel waste to form highly durable zirconates. The measured corrosion behaviors suggest properly formulated composite materials would be suitable waste forms for combined metallic and oxide waste streams generated during electrometallurgical reprocessing of spent nuclear fuel. Electrochemical methods are suitable for evaluating the durability and modeling long-term behavior of composite waste forms: the degradation model developed for metallic waste forms can be applied to the alloy phases formed in the composite and an affinity-based mineral dissolution model can be applied to the ceramic phases.« less
Pretreatment of Lignocellulosic Wastes to Improve Ethanol and Biogas Production: A Review
Taherzadeh, Mohammad J.; Karimi, Keikhosro
2008-01-01
Lignocelluloses are often a major or sometimes the sole components of different waste streams from various industries, forestry, agriculture and municipalities. Hydrolysis of these materials is the first step for either digestion to biogas (methane) or fermentation to ethanol. However, enzymatic hydrolysis of lignocelluloses with no pretreatment is usually not so effective because of high stability of the materials to enzymatic or bacterial attacks. The present work is dedicated to reviewing the methods that have been studied for pretreatment of lignocellulosic wastes for conversion to ethanol or biogas. Effective parameters in pretreatment of lignocelluloses, such as crystallinity, accessible surface area, and protection by lignin and hemicellulose are described first. Then, several pretreatment methods are discussed and their effects on improvement in ethanol and/or biogas production are described. They include milling, irradiation, microwave, steam explosion, ammonia fiber explosion (AFEX), supercritical CO2 and its explosion, alkaline hydrolysis, liquid hot-water pretreatment, organosolv processes, wet oxidation, ozonolysis, dilute-and concentrated-acid hydrolyses, and biological pretreatments. PMID:19325822
DOE Office of Scientific and Technical Information (OSTI.GOV)
Riley, Brian J.; Peterson, Jacob A.; Kroll, Jared O.
In this study, salt occlusion and hydrothermal processes were used to make chlorosodalite through reaction with a high-LiCl salt simulating a waste stream following pyrochemical treatment of oxide-based used nuclear fuel. Some products were reacted with glass binders to increase chlorosodalite yield through alkali ion exchange and aide in densification. Hydrothermal processes included reaction of the salt simulant in an acid digestion vessel with either zeolite 4A or sodium aluminate and colloidal silica. Chlorosodalite yields in the crystalline products were nearly complete in the glass-bonded materials at values of 100 mass% for the salt-occlusion method, up to 99.0 mass% formore » the hydrothermal synthesis with zeolite 4A, and up to 96 mass% for the hydrothermal synthesis with sodium aluminate and colloidal silica. These results show promise for using chemically stable chlorosodalite to immobilize oxide reduction salt wastes.« less
Benassi, L; Bosio, A; Dalipi, R; Borgese, L; Rodella, N; Pasquali, M; Depero, L E; Bergese, P; Bontempi, E
2015-08-15
The Stabilization of heavy metals from municipal solid waste incineration (MSWI) fly ash by rice husk ash (RHA) is under intense study as an effective strategy to recover and reuse industrial and agricultural waste together. We compare the metal entrapment performances of RHA from different Asian rice sources – namely from Japonica rice grown in Italy and Indica rice grown in India – Physicochemical and morphological characterization of the final stabilized material show that the same thermal treatment may result in marked structural differences in the silica contained in the two RHA. Remarkably, one of them displays a crystalline silica content, although obtained by a thermal treatment below 800 °C. We also find that the presence of an alkali metal ion (potassium) in the rice husk plays a crucial role in the attainment of the final silica phase. These physicochemical differences are mirrored by different stabilization yields by the two RHA. Copyright © 2015 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Roskosz, Mathieu; Leroux, Hugues
2015-03-01
Crystalline silica (SiO{sub 2}) is recurrently identified at the percent level in the infrared spectra of protoplanetary disks. By contrast, reports of crystalline silica in primitive meteorites are very unusual. This dichotomy illustrates the typical gap existing between astrophysical observations and meteoritical records of the first solids formed around young stars. The cometary samples returned by the Stardust mission in 2006 offer an opportunity to have a closer look at a silicate dust that experienced a very limited reprocessing since the accretion of the dust. Here, we provide the first extended study of silica materials in a large range ofmore » Stardust samples. We show that cristobalite is the dominant form. It was detected in 5 out of 25 samples. Crystalline silica is thus a common minor phase in Stardust samples. Furthermore, olivine is generally associated with this cristobalite, which put constraints on possible formation mechanisms. A low-temperature subsolidus solid–solid transformation of an amorphous precursor is most likely. This crystallization route favors the formation of olivine (at the expense of pyroxenes), and crystalline silica is the natural byproduct of this transformation. Conversely, direct condensation and partial melting are not expected to produce the observed mineral assemblages. Silica is preserved in cometary materials because they were less affected by thermal and aqueous alterations than their chondritic counterparts. The common occurrence of crystalline silica therefore makes the cometary material an important bridge between the IR-based mineralogy of distant protoplanetary disks and the mineralogy of the early solar system.« less
Microstructure of Sinter Deposit Formed at Hot Springs in West Sumatera
NASA Astrophysics Data System (ADS)
Putra, A.; Inanda, D. Y.; Buspa, F.; Salim, A. F.
2018-03-01
Sinter deposit emerged and spread at several hot springs in West Sumatera is divided into three types, they are full silica, half silica-carbonate and full carbonate. This work intends to investigate the characteristic of each type by its crystalline structure and morphology and its correlation to surface temperature. The research is focused on Sapan Maluluang hot spring (full silica), Garara hot spring (half silica-carbonate) and Bawah Kubang hot spring (full carbonate). Crystalline structure is analyzed by X-Ray Diffraction (XRD) methods, it showed that deposit from Sapan Maluluang has opal-A structure, Garara has opal-CT structure and Bawah Kubang has crystalline structure. The Scanning Electron Microscopy (SEM) methods is applied to describe its morphology surface, in which spherical, almost rounded and irregular textured was formed at each deposit, respectively. Surface temperature of hot spring also has given impact on deposit texture.
Preparing highly ordered glasses of discotic liquid crystalline systems by vapor deposition
NASA Astrophysics Data System (ADS)
Gujral, Ankit; Gomez, Jaritza; Bishop, Camille E.; Toney, Michael F.; Ediger, M. D.
Anisotropic molecular packing, particularly in highly ordered liquid-crystalline arrangements, has the potential for optimizing performance in organic electronic and optoelectronic applications. Here we show that physical vapor deposition can be used to prepare highly organized out-of-equilibrium (glassy) solids of discotic liquid-crystalline (LC) systems. Using grazing incidence x-ray scattering, we compare 3 systems: a rectangular columnar LC, a hexagonal columnar LC and a non-liquid crystal former. The packing motifs accessible by vapor deposition are highly organized and vary from face-on to edge-on columnar arrangements depending upon substrate temperature. A subset of these structures cannot be accessed under equilibrium conditions. The structures formed at a given substrate temperature can be understood as the result of the system partially equilibrating toward the structure of the free surface of the equilibrium liquid crystal. Consistent with this view, the structures formed are independent of the substrate material.
Sponge-like nanoporous single crystals of gold
Khristosov, Maria Koifman; Bloch, Leonid; Burghammer, Manfred; Kauffmann, Yaron; Katsman, Alex; Pokroy, Boaz
2015-01-01
Single crystals in nature often demonstrate fascinating intricate porous morphologies rather than classical faceted surfaces. We attempt to grow such crystals, drawing inspiration from biogenic porous single crystals. Here we show that nanoporous single crystals of gold can be grown with no need for any elaborate fabrication steps. These crystals are found to grow following solidification of a eutectic composition melt that forms as a result of the dewetting of nanometric thin films. We also present a kinetic model that shows how this nano-porous single-crystalline structure can be obtained, and which allows the potential size of the porous single crystal to be predicted. Retaining their single-crystalline nature is due to the fact that the full crystallization process is faster than the average period between two subsequent nucleation events. Our findings clearly demonstrate that it is possible to form single-crystalline nano porous metal crystals in a controlled manner. PMID:26554856
NASA Technical Reports Server (NTRS)
Pandey, Raghvendra K. (Inventor); Raina, Kanwal (Inventor); Solayappan, Narayanan (Inventor)
1994-01-01
A substantially single phase, single crystalline, highly epitaxial film of Bi.sub.2 CaSr.sub.2 Cu.sub.2 O.sub.8 superconductor which has a T.sub.c (zero resistance) of 83 K is provided on a lattice-matched substrate with no intergrowth. This film is produced by a Liquid Phase Epitaxy method which includes the steps of forming a dilute supercooled molten solution of a single phase superconducting mixture of oxides of Bi, Ca, Sr, and Cu having an atomic ratio of about 2:1:2:2 in a nonreactive flux such as KCl, introducing the substrate, e.g., NdGaO.sub.3, into the molten solution at 850.degree. C., cooling the solution from 850.degree. C. to 830.degree. C. to grow the film and rapidly cooling the substrate to room temperature to maintain the desired single phase, single crystalline film structure.
Crystallization Kinetics of Calcium-magnesium Aluminosilicate (CMAS) Glass
NASA Technical Reports Server (NTRS)
Wiesner, Valerie L.; Bansal, Narottam P.
2015-01-01
The crystallization kinetics of a calcium-magnesium aluminosilicate (CMAS) glass with composition relevant for aerospace applications, like air-breathing engines, were evaluated using differential thermal analysis (DTA) in powder and bulk forms. Activation energy and frequency factor values for crystallization of the glass were evaluated. X-ray diffraction (XRD) was used to investigate the onset of crystallization and the phases that developed after heat treating bulk glass at temperatures ranging from 690 to 960 deg for various times. Samples annealed at temperatures below 900 deg remained amorphous, while specimens heat treated at and above 900 deg exhibited crystallinity originating at the surface. The crystalline phases were identified as wollastonite (CaSiO3) and aluminum diopside (Ca(Mg,Al) (Si,Al)2O6). Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) were employed to examine the microstructure and chemical compositions of crystalline phases formed after heat treatment.
Shi, Jian; Li, Zhaodong; Kvit, Alexander; Krylyuk, Sergiy; Davydov, Albert V; Wang, Xudong
2013-01-01
Understanding the evolution of amorphous and crystalline phases during atomic layer deposition (ALD) is essential for creating high quality dielectrics, multifunctional films/coatings, and predictable surface functionalization. Through comprehensive atomistic electron microscopy study of ALD TiO2 nanostructures at designed growth cycles, we revealed the transformation process and sequence of atom arrangement during TiO2 ALD growth. Evolution of TiO2 nanostructures in ALD was found following a path from amorphous layers to amorphous particles to metastable crystallites and ultimately to stable crystalline forms. Such a phase evolution is a manifestation of the Ostwald-Lussac Law, which governs the advent sequence and amount ratio of different phases in high-temperature TiO2 ALD nanostructures. The amorphous-crystalline mixture also enables a unique anisotropic crystal growth behavior at high temperature forming TiO2 nanorods via the principle of vapor-phase oriented attachment.
Minimalistic Liquid-Assisted Route to Highly Crystalline α-Zirconium Phosphate.
Cheng, Yu; Wang, Xiaodong Tony; Jaenicke, Stephan; Chuah, Gaik-Khuan
2017-08-24
Zirconium phosphates have potential applications in areas of ion exchange, catalysis, photochemistry, and biotechnology. However, synthesis methodologies to form crystalline α-zirconium phosphate (Zr(HPO 4 ) 2 ⋅H 2 O) typically involve the use of excess phosphoric acid, addition of HF or oxalic acid and long reflux times or hydrothermal conditions. A minimalistic sustainable route to its synthesis has been developed by using only zirconium oxychloride and concentrated phosphoric acid to form highly crystalline α-zirconium phosphate within hours. The morphology can be changed from platelets to rod-shaped particles by fluoride addition. By varying the temperature and time, α-zirconium phosphate with particle sizes from nanometers to microns can be obtained. Key features of this minimal solvent synthesis are the excellent yields obtained with high atom economy under mild conditions and ease of scalability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Liquid Crystalline Thermosets from Ester, Ester-imide, and Ester-amide Oligomers
NASA Technical Reports Server (NTRS)
Dingemans, Theodorus J. (Inventor); Weiser, Erik S. (Inventor); St. Clair, Terry L. (Inventor)
2009-01-01
Main chain thermotropic liquid crystal esters, ester-imides, and ester-amides were prepared from AA, BB, and AB type monomeric materials and end-capped with phenylacetylene, phenylmaleimide, or nadimide reactive end-groups. The end-capped liquid crystal oligomers are thermotropic and have, preferably, molecular weights in the range of approximately 1000-15,000 grams per mole. The end-capped liquid crystaloligomers have broad liquid crystalline melting ranges and exhibit high melt stability and very low melt viscosities at accessible temperatures. The end-capped liquid crystal oli-gomers are stable forup to an hour in the melt phase. They are highly processable by a variety of melt process shape forming and blending techniques. Once processed and shaped, the end-capped liquid crystal oigomers were heated to further polymerize and form liquid crystalline thermosets (LCT). The fully cured products are rubbers above their glass transition temperatures.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dunn, Darrell; Poinssot, Christophe; Begg, Bruce
Management of nuclear waste remains an important international topic that includes reprocessing of commercial nuclear fuel, waste-form design and development, storage and disposal packaging, the process of repository site selection, system design, and performance assessment. Requirements to manage and dispose of materials from the production of nuclear weapons, and the renewed interest in nuclear power, in particular through the Generation IV Forum and the Advanced Fuel Cycle Initiative, can be expected to increase the need for scientific advances in waste management. A broad range of scientific and engineering disciplines is necessary to provide safe and effective solutions and address complexmore » issues. This volume offers an interdisciplinary perspective on materials-related issues associated with nuclear waste management programs. Invited and contributed papers cover a wide range of topics including studies on: spent fuel; performance assessment and models; waste forms for low- and intermediate-level waste; ceramic and glass waste forms for plutonium and high-level waste; radionuclides; containers and engineered barriers; disposal environments and site characteristics; and partitioning and transmutation.« less
NASA Astrophysics Data System (ADS)
Abdelbasir, S. M.; El-Sheikh, S. M.; Rashad, M. M.; Rayan, D. A.
2018-03-01
Cuprous oxide Cu2O nanopowders were purposefully synthesised from waste electric cables (WECs) via a simple precipitation route at room temperature using lactose as a reducing agent. In this regard, dimethyl sulfoxide (DMSO) was first applied as an organic solvent for the dissolution of the cable insulating materials. Several parameters were investigated during dissolution of WECs such as dissolution temperature, time and solid/liquid ratio to determine the dissolution percentage of the insulating materials in DMSO. The morphology and the optical properties of the formed Cu2O particles were investigated using X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), Fourier-transform infrared spectroscopy and UV-visible-near IR spectrophotometer. XRD data confirmed the presence of single crystalline phase of Cu2O nanoparticles. FE-SEM and TEM images revealed spherical, cubic and octahedral shapes with the various particle sizes ranged from 16 to 57 nm depending on the synthesis conditions. A possible mechanism explaining the Cu2O nanostructures formation was proposed. The band gap energies of the Cu2O nanostructures were estimated and the values were located between 1.5 and 2.08 eV. Photoluminescence spectroscopy analysis clearly showed a noticeably blue-shifted emission for the synthesized samples compared to spectrum of the bulk. Eventually, magnetic properties of the synthesized nanoparticles have been measured by vibrating sample magnetometer and the attained results implied that the synthesized particles are weakly ferromagnetic in nature at normal temperature.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Guohui; Um, Wooyong; Wang, Zheming
The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford’s cribs, USA. During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO2)(PO4)·3H2O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K2(UO2)6O4(OH)6·7H2O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitatedmore » as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67E-12 mol g-1 s-1. In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42E-10 mol g-1 s-1. The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.« less
Tommaseo, C E; Kersten, M
2002-07-01
Zinc oxide was added during hydration of alite (C3S) as an analogue for solidification/stabilization by cement of metal-bearing hazardous waste. Curing of samples was stopped at various intervals between 8 h and 100 d, and the reaction products were analyzed by both X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS at Zn, Ca, and Si K-edges). Calcium zincate hydrate (CaZn2(OH)6 x 2H2O) initially formed together with calcium silicate hydrate (CSH) vanishes from X-ray diffractograms after 14 d, and no other crystalline Zn-bearing phase could be detected thereafter. EXAFS Zn K-edge data analysis reveals that Zn(O,OH)4 tetrahedra continue to determine the first shell coordination. However, a new Zn-Si bond appears in the second coordination shell as indicated by both Zn K-edge and Si K-edge EXAFS. Together with the Ca-Zn and Ca-Ca shells derived from the Ca K-edge EXAFS spectra, a structural model for the site occupation of Zn in CSH is proposed, whereby the Zn(O,OH)4 tetrahedra are bound in layer rather than interlayer positions substituting for the silicate bridging tetrahedra and/or at terminal silicate chain sites. This structural model enables ultimately the formulation of a thermodyamic Lippmann model to predict the aqueous solubility of Zn in solid solution with a CSH phase of a Ca/Si ratio fixed to unity.
Wang, Guohui; Um, Wooyong; Wang, Zheming; Reinoso-Maset, Estela; Washton, Nancy M; Mueller, Karl T; Perdrial, Nicolas; O'Day, Peggy A; Chorover, Jon
2017-10-03
The reaction of acidic radioactive waste with sediments can induce mineral transformation reactions that, in turn, control contaminant fate. Here, sediment weathering by synthetic uranium-containing acid solutions was investigated using bench-scale experiments to simulate waste disposal conditions at Hanford's cribs (Hanford, WA). During acid weathering, the presence of phosphate exerted a strong influence over uranium mineralogy and a rapidly precipitated, crystalline uranium phosphate phase (meta-ankoleite [K(UO 2 )(PO 4 )·3H 2 O]) was identified using spectroscopic and diffraction-based techniques. In phosphate-free system, uranium oxyhydroxide minerals such as K-compreignacite [K 2 (UO 2 ) 6 O 4 (OH) 6 ·7H 2 O] were formed. Single-pass flow-through (SPFT) and column leaching experiments using synthetic Hanford pore water showed that uranium precipitated as meta-ankoleite during acid weathering was strongly retained in the sediments, with an average release rate of 2.67 × 10 -12 mol g -1 s -1 . In the absence of phosphate, uranium release was controlled by dissolution of uranium oxyhydroxide (compreignacite-type) mineral with a release rate of 1.05-2.42 × 10 -10 mol g -1 s -1 . The uranium mineralogy and release rates determined for both systems in this study support the development of accurate U-release models for the prediction of contaminant transport. These results suggest that phosphate minerals may be a good candidate for uranium remediation approaches at contaminated sites.
NASA Astrophysics Data System (ADS)
Gu, Xiaodan; Zhou, Yan; Gu, Kevin; Kurosawa, Tadanori; Yan, Hongping; Wang, Cheng; Toney, Micheal; Bao, Zhenan
The challenge of continuous printing in high efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution coated all-polymer bulk heterojunction (BHJ) solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, our results showed that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers. This methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. We were able to continuously roll-to-roll slot die print large area all-polymer solar cells with power conversion efficiencies of 5%, with combined cell area up to 10 cm2. This is among the highest efficiencies realized with R2R coated active layer organic materials on flexible substrate. DOE BRIDGE sunshot program. Office of Naval Research.
NASA Astrophysics Data System (ADS)
Puthirath, Anand B.; Methattel Raman, Shijeesh; Varma, Sreekanth J.; Jayalekshmi, S.
2016-04-01
Emeraldine salt form of polyaniline (PANI) was synthesized by chemical oxidative polymerisation method using ammonium persulfate as oxidant. Resultant emeraldine salt form of PANI was dedoped using ammonia solution and then re-doped with camphor sulphonic acid (CSA), naphthaline sulphonic acid (NSA), hydrochloric acid (HCl), and m-cresol. Thin films of these doped PANI samples were deposited on glass substrates using solution casting method with m-cresol as solvent. A level surface was employed to get homogeneous thin films of uniform thickness. Detailed X-ray diffraction studies have shown that the films are exceptionally crystalline. The crystalline peaks observed in the XRD spectra can be indexed to simple monoclinic structure. FTIR and Raman spectroscopy studies provide convincing explanation for the exceptional crystallinity observed in these polymer films. FESEM and AFM images give better details of surface morphology of doped PANI films. The DC electrical conductivity of the samples was measured using four point probe technique. It is seen that the samples also exhibit quite high DC electrical conductivity, about 287 S/cm for CSA doped PANI, 67 S/cm for NSA doped PANI 65 S/cm for HCl doped PANI, and just below 1 S/cm for m-cresol doped PANI. Effect of using the level surface for solution casting is studied and correlated with the observed crystallinity.
Lyotropic liquid crystal preconcentrates for the treatment of periodontal disease.
Fehér, A; Urbán, E; Eros, I; Szabó-Révész, P; Csányi, E
2008-06-24
The aim of our study was to develop water-free lyotropic liquid crystalline preconcentrates, which consist of oils and surfactants with good physiological tolerance and spontaneously form lyotropic liquid crystalline phase in aqueous environment. In this way these preconcentrates having low viscosity can be injected into the periodontal pocket, where they are transformed into highly viscous liquid crystalline phase, so that the preparation is prevented from flowing out of the pocket due to its great viscosity, while drug release is controlled by the liquid crystalline texture. In order to follow the structure alteration upon water absorption polarization microscopical and rheological examinations were performed. The water absorption mechanism of the samples was examined by the Enslin-method. Metronidazole-benzoate was used as active agent the release of which was characterized via in vitro investigations performed by means of modified Kirby-Bauer disk diffusion method. On the grounds of the results it can be stated that the 4:1 mixture of the investigated surfactants (Cremophor EL, Cremophor RH40) and oil (Miglyol 810) formed lyotopic liquid crystalline phases upon water addition. Polarization microscopic examinations showed that samples with 10-40% water content possessed anisotropic properties. On the basis of water absorption, rheological and drug release studies it can be concluded that the amount of absorbed water and stiffness of lyotropic structure influenced by the chemical entity of the surfactant exerted major effect on the drug release.
Narayan, Jagdish; Chen, Yok
1983-01-01
This invention is a new process for producing refractory crystalline oxides having improved or unusual properties. The process comprises the steps of forming a doped-metal crystal of the oxide; exposing the doped crystal in a bomb to a reducing atmosphere at superatmospheric pressure and a temperature effecting precipitation of the dopant metal in the crystal lattice of the oxide but insufficient to effect net diffusion of the metal out of the lattice; and then cooling the crystal. Preferably, the cooling step is effected by quenching. The process forms colloidal precipitates of the metal in the oxide lattice. The process may be used, for example, to produce thermally stable black MgO crystalline bodies containing magnetic colloidal precipitates consisting of about 99% Ni. The Ni-containing bodies are solar-selective absorbers, having a room-temperature absorptivity of about 0.96 over virtually all of the solar-energy spectrum and exhibiting an absorption edge in the region of 2 .mu.m. The process parameters can be varied to control the average size of the precipitates. The process can produce a black MgO crystalline body containing colloidal Ni precipitates, some of which have the face-centered-cubic structure and others of which have the body-centered cubic structure. The products of the process are metal-precipitate-containing refractory crystalline oxides which have improved or unique optical, mechanical, magnetic, and/or electronic properties.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gu, Xiaodan; Zhou, Yan; Gu, Kevin
The challenge of continuous printing in high-efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution-coated all-polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers.more » This particular methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small-scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. Large-area all-polymer solar cells are continuously roll-to-roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm 2. This is among the highest efficiencies realized with R2R-coated active layer organic materials on flexible substrate.« less
Gu, Xiaodan; Zhou, Yan; Gu, Kevin; ...
2017-03-07
The challenge of continuous printing in high-efficiency large-area organic solar cells is a key limiting factor for their widespread adoption. We present a materials design concept for achieving large-area, solution-coated all-polymer bulk heterojunction solar cells with stable phase separation morphology between the donor and acceptor. The key concept lies in inhibiting strong crystallization of donor and acceptor polymers, thus forming intermixed, low crystallinity, and mostly amorphous blends. Based on experiments using donors and acceptors with different degree of crystallinity, the results show that microphase separated donor and acceptor domain sizes are inversely proportional to the crystallinity of the conjugated polymers.more » This particular methodology of using low crystallinity donors and acceptors has the added benefit of forming a consistent and robust morphology that is insensitive to different processing conditions, allowing one to easily scale up the printing process from a small-scale solution shearing coater to a large-scale continuous roll-to-roll (R2R) printer. Large-area all-polymer solar cells are continuously roll-to-roll slot die printed with power conversion efficiencies of 5%, with combined cell area up to 10 cm 2. This is among the highest efficiencies realized with R2R-coated active layer organic materials on flexible substrate.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Puthirath, Anand B.; Varma, Sreekanth J.; Jayalekshmi, S., E-mail: jayalekshmi@cusat.ac.in
2016-04-18
Emeraldine salt form of polyaniline (PANI) was synthesized by chemical oxidative polymerisation method using ammonium persulfate as oxidant. Resultant emeraldine salt form of PANI was dedoped using ammonia solution and then re-doped with camphor sulphonic acid (CSA), naphthaline sulphonic acid (NSA), hydrochloric acid (HCl), and m-cresol. Thin films of these doped PANI samples were deposited on glass substrates using solution casting method with m-cresol as solvent. A level surface was employed to get homogeneous thin films of uniform thickness. Detailed X-ray diffraction studies have shown that the films are exceptionally crystalline. The crystalline peaks observed in the XRD spectra canmore » be indexed to simple monoclinic structure. FTIR and Raman spectroscopy studies provide convincing explanation for the exceptional crystallinity observed in these polymer films. FESEM and AFM images give better details of surface morphology of doped PANI films. The DC electrical conductivity of the samples was measured using four point probe technique. It is seen that the samples also exhibit quite high DC electrical conductivity, about 287 S/cm for CSA doped PANI, 67 S/cm for NSA doped PANI 65 S/cm for HCl doped PANI, and just below 1 S/cm for m-cresol doped PANI. Effect of using the level surface for solution casting is studied and correlated with the observed crystallinity.« less
Electrochemical synthesis of self-organized TiO2 crystalline nanotubes without annealing
NASA Astrophysics Data System (ADS)
Giorgi, Leonardo; Dikonimos, Theodoros; Giorgi, Rossella; Buonocore, Francesco; Faggio, Giuliana; Messina, Giacomo; Lisi, Nicola
2018-03-01
This work demonstrates that upon anodic polarization in an aqueous fluoride-containing electrolyte, TiO2 nanotube array films can be formed with a well-defined crystalline phase, rather than an amorphous one. The crystalline phase was obtained avoiding any high temperature annealing. We studied the formation of nanotubes in an HF/H2O medium and the development of crystalline grains on the nanotube wall, and we found a facile way to achieve crystalline TiO2 nanotube arrays through a one-step anodization. The crystallinity of the film was influenced by the synthesis parameters, and the optimization of the electrolyte composition and anodization conditions (applied voltage and time) were carried out. For comparison purposes, crystalline anatase TiO2 nanotubes were also prepared by thermal treatment of amorphous nanotubes grown in an organic bath (ethylene glycol/NH4F/H2O). The morphology and the crystallinity of the nanotubes were studied by field emission gun-scanning electron microscopy (FEG-SEM) and Raman spectroscopy, whereas the electrochemical and semiconducting properties were analyzed by means of linear sweep voltammetry, impedance spectroscopy, and Mott-Schottky plots. X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) allowed us to determine the surface composition and the electronic structure of the samples and to correlate them with the electrochemical data. The optimal conditions to achieve a crystalline phase with high donor concentration are defined.
NASA Astrophysics Data System (ADS)
Gong, Liang
Bacterially produced poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] (PHBHx) is a new type of bioplastic which not only inherits the excellent biodegradability and biocompatibility of its parent homopolymer, polyhydroxybutyrate (PHB), but also overcomes PHB’s brittleness and stiffness with the incorporation of 3-hydroxyhexanoate (Hx) comonomer units with medium-chain-length (mcl) side chains. The tough and ductile PHBHx, with a much lower crystallinity and melting temperature, is well-suited for many practical applications. Efforts have been made to broaden the application range of PHBHx by introducing the beta-form crystalline structure, where the molecular chains adopt a planar zig-zag conformation. However, it is extremely difficult to produce this beta-form in PHBHx due to its much lower crystallinity and much more flexible molecular chains. In this study, we report an approach using the technique of electrospinning. The strain-induced metastable β-form crystalline structure was successfully introduced in PHBHx by collecting the macroscopically aligned electrospun PHBHx nanofibers across the air gap on a piece of aluminum foil and on the tapered edge of a high-speed rotary disk. The presence of the β-form crystal structure in electrospun fiber mats was confirmed by wide-angle X-ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR), with molecular orientation of the polymer chains along the fiber axis revealed by polarized FTIR. Selected area electron diffraction (SAED) and AFM-IR were utilized to investigate the morphological and structural details of individual PHBHx nanofibers. The results demonstrated a coexistence of the thermodynamically stable α-form crystalline structure, where molecular chains adopt a left-handed 21 helical conformation, and the β-form in single fibers. The molecular orientation level and the relative amounts of the two crystalline polymorphs were found to be highly dependent on fiber collection methods and fiber diameter. Moreover, the α and β-form were revealed to be spatially distributed as a core-shell structure consisting of an α-form-rich core and a β-form-rich shell, with the thickness of the shell remaining constant despite the variation of fiber diameter. According to these observations, a possible mechanism for the generation of the β-form was proposed. The effects of electrospinning parameters on the formation of the beta-form were systematically investigated. The results indicated that more β-crystals can be produced when 1) a higher fiber take-up is used, so that the polymer chains are further stretched before fiber solidification; 2) an optimal solution concentration is chosen, so that a balance between polymer chain deformation and relaxation is maintained throughout the whole electrospinning process; and 3) a more volatile solvent is used, so that more planar zig-zag chains are kinetically frozen in the fibers without being converted to the helical conformation as the fibers solidify. These experimental results indicate that the β-content in PHBHx nanofibers can be easily regulated by modifying the electrospinning conditions. Finally, the influence of the presence of the β-form on the piezoelectric response of the electrospun PHBHx nanofibers was studied. It was observed that the fibers containing the β-form exhibited an obvious piezoelectric response to the applied pressure, possibly due to the planar zig-zag conformation of the chains which gives rise to a significant dipole moment change when subjected to mechanical deformation. In addition, the sensitivity of the piezoelectric PHBHx nanofibers to mechanical pressure was measured to be 7.46 mV/kPa. These preliminary investigations indicate that the piezoelectric performance of PHBHx can be largely improved by increasing the concentration of the piezoelectric-active β-form crystalline structure. The piezoelectric PHBHx distinguishes itself from all the other piezoelectric polymers with its excellent biodegradability and biocompatibility, environmental-friendliness and most importantly, low manufacturing cost. It is a promising piezoelectric polymer which can be applied in advanced areas including portable/foldable electronic devices, artificial electronic skins and implantable sensors.
Ripple structure of crystalline layers in ion-beam-induced Si wafers
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hazra, S.; Chini, T.K.; Sanyal, M.K.
Ion-beam-induced ripple formation in Si wafers was studied by two complementary surface sensitive techniques, namely atomic force microscopy (AFM) and depth-resolved x-ray grazing incidence diffraction (GID). The formation of ripple structure at high doses ({approx}7x10{sup 17} ions/cm{sup 2}), starting from initiation at low doses ({approx}1x10{sup 17} ions/cm{sup 2}) of ion beam, is evident from AFM, while that in the buried crystalline region below a partially crystalline top layer is evident from GID study. Such ripple structure of crystalline layers in a large area formed in the subsurface region of Si wafers is probed through a nondestructive technique. The GID techniquemore » reveals that these periodically modulated wavelike buried crystalline features become highly regular and strongly correlated as one increases the Ar ion-beam energy from 60 to 100 keV. The vertical density profile obtained from the analysis of a Vineyard profile shows that the density in the upper top part of ripples is decreased to about 15% of the crystalline density. The partially crystalline top layer at low dose transforms to a completely amorphous layer for high doses, and the top morphology was found to be conformal with the underlying crystalline ripple.« less
Method for the removal of ultrafine particulates from an aqueous suspension
Chaiko, David J.; Kopasz, John P.; Ellison, Adam J. G.
2000-01-01
A method of separating ultra-fine particulates from an aqueous suspension such as a process stream or a waste stream. The method involves the addition of alkali silicate and an organic gelling agent to a volume of liquid, from the respective process or waste stream, to form a gel. The gel then undergoes syneresis to remove water and soluble salts from the gel containing the particulates, thus, forming a silica monolith. The silica monolith is then sintered to form a hard, nonporous waste form.
Method for the Removal of Ultrafine Particulates from an Aqueous Suspension
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chaiko, David J.; Kopasz, John P.; Ellison, Adam J.G.
1999-03-05
A method of separating ultra-fine particulate from an aqueous suspension such as a process stream or a waste stream. The method involves the addition of alkali silicate and an organic gelling agent to a volume of liquid, from the respective process or waste stream, to form a gel. The gel then undergoes syneresis to remove water and soluble salts from the gel-containing the particulate, thus, forming a silica monolith. The silica monolith is then sintered to form a hard, nonporous waste form.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Eun, H.C.; Cho, Y.Z.; Choi, J.H.
A regeneration process of LiCl-KCl eutectic waste salt generated from the pyrochemical process of spent nuclear fuel has been studied. This regeneration process is composed of a chemical conversion process and a vacuum distillation process. Through the regeneration process, a high efficiency of renewable salt recovery can be obtained from the waste salt and rare earth nuclides in the waste salt can be separated as oxide or phosphate forms. Thus, the regeneration process can contribute greatly to a reduction of the waste volume and a creation of durable final waste forms. (authors)
NASA Astrophysics Data System (ADS)
Blue, C. R.; Giuffre, A.; Mergelsberg, S.; Han, N.; De Yoreo, J. J.; Dove, P. M.
2017-01-01
Calcite and other crystalline polymorphs of CaCO3 can form by pathways involving amorphous calcium carbonate (ACC). Apparent inconsistencies in the literature indicate the relationships between ACC composition, local conditions, and the subsequent crystalline polymorphs are not yet established. This experimental study quantifies the control of solution composition on the transformation of ACC into crystalline polymorphs in the presence of magnesium. Using a mixed flow reactor to control solution chemistry, ACC was synthesized with variable Mg contents by tuning input pH, Mg/Ca, and total carbonate concentration. ACC products were allowed to transform within the output suspension under stirred or quiescent conditions while characterizing the evolving solutions and solids. As the ACC transforms into a crystalline phase, the solutions record a polymorph-specific evolution of pH and Mg/Ca. The data provide a quantitative framework for predicting the initial polymorph that forms from ACC based upon the solution aMg2+/aCa2+ and aCO32-/aCa2+ and stirring versus quiescent conditions. This model reconciles discrepancies among previous studies that report on the nature of the polymorphs produced from ACC and supports the previous claim that monohydrocalcite may be an important, but overlooked, transient phase on the way to forming some aragonite and calcite deposits. By this construct, organic additives and extreme pH are not required to tune the composition and nature of the polymorph that forms. Our measurements show that the Mg content of ACC is recorded in the resulting calcite with a ≈1:1 dependence. By correlating composition of these calcite products with the Mgtot/Catot of the initial solutions, we find a ≈3:1 dependence that is approximately linear and general to whether calcite is formed via an ACC pathway or by the classical step-propagation process. Comparisons to calcite grown in synthetic seawater show a ≈1:1 dependence. The relationships suggest that the local Mg2+/Ca2+ at the time of precipitation determines the calcite composition, independent of whether growth occurs via an amorphous intermediate or classical pathway for a range of supersaturations and pH conditions. The findings reiterate the need to revisit the traditional picture of chemical and physical controls on CaCO3 polymorph selection. Mineralization by pathways involving ACC can lead to the formation of crystalline phases whose polymorphs and compositions are out of equilibrium with local growth media. As such, classical thermodynamic equilibria may not provide a reliable predictor of observed compositions.
Permeability and seismic velocity anisotropy across a ductile-brittle fault zone in crystalline rock
NASA Astrophysics Data System (ADS)
Wenning, Quinn C.; Madonna, Claudio; de Haller, Antoine; Burg, Jean-Pierre
2018-05-01
This study characterizes the elastic and fluid flow properties systematically across a ductile-brittle fault zone in crystalline rock at the Grimsel Test Site underground research laboratory. Anisotropic seismic velocities and permeability measured every 0.1 m in the 0.7 m across the transition zone from the host Grimsel granodiorite to the mylonitic core show that foliation-parallel P- and S-wave velocities systematically increase from the host rock towards the mylonitic core, while permeability is reduced nearest to the mylonitic core. The results suggest that although brittle deformation has persisted in the recent evolution, antecedent ductile fabric continues to control the matrix elastic and fluid flow properties outside the mylonitic core. The juxtaposition of the ductile strain zone next to the brittle zone, which is bounded inside the two mylonitic cores, causes a significant elastic, mechanical, and fluid flow heterogeneity, which has important implications for crustal deformation and fluid flow and for the exploitation and use of geothermal energy and geologic waste storage. The results illustrate how physical characteristics of faults in crystalline rocks change in fault zones during the ductile to brittle transitions.
Secondary Waste Form Screening Test Results—Cast Stone and Alkali Alumino-Silicate Geopolymer
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pierce, Eric M.; Cantrell, Kirk J.; Westsik, Joseph H.
2010-06-28
PNNL is conducting screening tests on the candidate waste forms to provide a basis for comparison and to resolve the formulation and data needs identified in the literature review. This report documents the screening test results on the Cast Stone cementitious waste form and the Geopolymer waste form. Test results suggest that both the Cast Stone and Geopolymer appear to be viable waste forms for the solidification of the secondary liquid wastes to be treated in the ETF. The diffusivity for technetium from the Cast Stone monoliths was in the range of 1.2 × 10-11 to 2.3 × 10-13 cm2/smore » during the 63 days of testing. The diffusivity for technetium from the Geopolymer was in the range of 1.7 × 10-10 to 3.8 × 10-12 cm2/s through the 63 days of the test. These values compare with a target of 1 × 10-9 cm2/s or less. The Geopolymer continues to show some fabrication issues with the diffusivities ranging from 1.7 × 10-10 to 3.8 × 10-12 cm2/s for the better-performing batch to from 1.2 × 10-9 to 1.8 × 10-11 cm2/s for the poorer-performing batch. In the future more comprehensive and longer term performance testing will be conducted, to further evaluate whether or not these waste forms will meet the regulation and performance criteria needed to cost-effectively dispose of secondary wastes.« less
1986-12-01
composed of crystalline par- ticles for one or more types accepted and studies of clay organic intaractions gained momentum (7), with some of the...ammonium cations) lessens this effect as the water of hydratior is less strongly held creating a more hydrophobic environment between the layers and...soil (35) and the wate- solubility of the compounds influences the extent of adsorption (19,20), presumably by increasing the extent of hydrophobic
Custelcean, Radu; Sloop, Frederick V.; Rajbanshi, Arbin; ...
2014-12-04
We measured the thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions in the 15 55 C temperature range, with the goal of identifying the optimal conditions for efficient and quick sulfate removal from nuclear wastes. The use of radiolabeled Na 2 35SO 4 provided a practical way to monitor the sulfate concentration in solution by liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na 2SO 4(L1) 2(H 2O) 4 capsules. We foundmore » that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. Moreover, this corresponds to 77 91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increased 20-fold from 15 to 55 C, corresponding to an activation energy of 14.1 kcal/mol. At the highest measured temperature of 55 C, 63% and 75% of sulfate was removed from solution within 8 h and 24 h, respectively.« less
NASA Astrophysics Data System (ADS)
Harte, Philip T.; Ayotte, Joseph D.; Hoffman, Andrew; Révész, Kinga M.; Belaval, Marcel; Lamb, Steven; Böhlke, J. K.
2012-09-01
Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site in Raymond, New Hampshire, USA, showed evidence of locally enhanced As mobilization in relatively reducing (mixed oxic-anoxic to anoxic) conditions as determined by redox classification and other lines of evidence. Redox classification was determined from geochemical indicators based on threshold concentrations of dissolved oxygen (DO), nitrate (NO{3/-}), iron (Fe2+), manganese (Mn2+), and sulfate (SO{4/2-}). Redox conditions were evaluated also based on methane (CH4), excess nitrogen gas (N2) from denitrification, the oxidation state of dissolved As speciation (As(III) and As(V)), and several stable isotope ratios. Samples from the residential-supply wells primarily exhibit mixed redox conditions, as most have long open boreholes (typically 50-100 m) that receive water from multiple discrete fractures with contrasting groundwater chemistry and redox conditions. The methods employed in this study can be used at other sites to gauge redox conditions and the potential for As mobilization in complex fractured crystalline-rock aquifers where multiple lines of evidence are likely needed to understand As occurrence, mobility, and transport.
Harte, Philip T.; Ayotte, Joseph D.; Hoffman, Andrew; Revesz, Kinga M.; Belaval, Marcel; Lamb, Steven; Böhlke, J.K.
2012-01-01
Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site in Raymond, New Hampshire, USA, showed evidence of locally enhanced As mobilization in relatively reducing (mixed oxic-anoxic to anoxic) conditions as determined by redox classification and other lines of evidence. Redox classification was determined from geochemical indicators based on threshold concentrations of dissolved oxygen (DO), nitrate (NO3-), iron (Fe2+), manganese (Mn2+), and sulfate (SO42-). Redox conditions were evaluated also based on methane (CH4), excess nitrogen gas (N2) from denitrification, the oxidation state of dissolved As speciation (As(III) and As(V)), and several stable isotope ratios. Samples from the residential-supply wells primarily exhibit mixed redox conditions, as most have long open boreholes (typically 50–100 m) that receive water from multiple discrete fractures with contrasting groundwater chemistry and redox conditions. The methods employed in this study can be used at other sites to gauge redox conditions and the potential for As mobilization in complex fractured crystalline-rock aquifers where multiple lines of evidence are likely needed to understand As occurrence, mobility, and transport.
NASA Astrophysics Data System (ADS)
Arshad, Aqsa; Iqbal, Javed; Siddiq, M.; Mansoor, Qaisar; Ismail, M.; Mehmood, Faisal; Ajmal, M.; Abid, Zubia
2017-01-01
The synthesis, physical, photocatalytic, and antibacterial properties of MgO and graphene nanoplatelets (GNPs) nanocomposites are reported. The crystallinity, phase, morphology, chemical bonding, and vibrational modes of prepared nanomaterials are studied. The conductive nature of GNPs is tailored via photocatalysis and enhanced antibacterial activity. It is interestingly observed that the MgO/GNPs nanocomposites with optimized GNPs content show a significant photocatalytic activity (97.23% degradation) as compared to bare MgO (43%) which makes it the potential photocatalyst for purification of industrial waste water. In addition, the effect of increased amount of GNPs on antibacterial performance of nanocomposites against pathogenic micro-organisms is researched, suggesting them toxic. MgO/GNPs 25% nanocomposite may have potential applications in waste water treatment and nanomedicine due its multifunctionality.
Khan, Shadab Ali; Uddin, Imran; Moeez, Sana; Ahmad, Absar
2014-01-01
In this paper, we for the first time show the ability of the mesophilic fungus Fusarium oxysporum in the bioleaching of waste material such as Fly-ash for the extracellular production of highly crystalline and highly stable, protein capped, fluorescent and water soluble silica nanoparticles at ambient conditions. When the fungus Fusarium oxysporum is exposed to Fly-ash, it is capable of selectively leaching out silica nanoparticles of quasi-spherical morphology within 24 h of reaction. These silica nanoparticles have been completely characterized by UV-vis spectroscopy, Photoluminescence (PL), Transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Energy dispersive analysis of X-rays (EDAX). PMID:25244567
Koyama, Tadafumi
1994-01-01
A method for immobilizing waste chloride salts containing radionuclides such as cesium and strontium and hazardous materials such as barium. A sodalite intermediate is prepared by mixing appropriate amounts of silica, alumina and sodium hydroxide with respect to sodalite and heating the mixture to form the sodalite intermediate and water. Heating is continued to drive off the water to form a water-free intermediate. The water-free intermediate is mixed with either waste salt or waste salt which has been contacted with zeolite to concentrate the radionuclides and hazardous material. The waste salt-intermediate mixture is then compacted and heated under conditions of heat and pressure to form sodalite with the waste salt, radionuclides and hazardous material trapped within the sodalite cage structure. This provides a final product having excellent leach resistant capabilities.
Koyama, Tadafumi.
1994-08-23
A method is described for immobilizing waste chloride salts containing radionuclides such as cesium and strontium and hazardous materials such as barium. A sodalite intermediate is prepared by mixing appropriate amounts of silica, alumina and sodium hydroxide with respect to sodalite and heating the mixture to form the sodalite intermediate and water. Heating is continued to drive off the water to form a water-free intermediate. The water-free intermediate is mixed with either waste salt or waste salt which has been contacted with zeolite to concentrate the radionuclides and hazardous material. The waste salt-intermediate mixture is then compacted and heated under conditions of heat and pressure to form sodalite with the waste salt, radionuclides and hazardous material trapped within the sodalite cage structure. This provides a final product having excellent leach resistant capabilities.
Koyama, T.
1992-01-01
This report describes a method for immobilizing waste chloride salts containing radionuclides such as cesium and strontium and hazardous materials such as barium. A sodalite intermediate is prepared by mixing appropriate amounts of silica, alumina and sodium hydroxide with respect to sodalite and heating the mixture to form the sodalite intermediate and water. Heating is continued to drive off the water to form a water-free intermediate. The water-free intermediate is mixed with either waste salt or waste salt which has been contacted with zeolite to concentrate the radionuclides and hazardous material. The waste salt-intermediate mixture is then compacted and heated under conditions of heat and pressure to form sodalite with the waste salt, radionuclides and hazardous material trapped within the sodalite cage structure. This provides a final product having excellent leach resistant capabilities.
NASA Astrophysics Data System (ADS)
Wiewiórowski, M.; Alejska, M.; Malinowska, N.; Bratek-Wiewiórowska, M. D.
1997-12-01
It has been found that 2'deoxycytidine (dCyd) crystallizes in different forms, denoted dCyd A, dCyd B and dCyd C·H 2O. In the crystal lattice of the newly discovered form dCydC·H 2O there is a crystalline water molecule present. The monohydrate of dCydC, under suitable conditions (RT, over P 2O 5, 48h), undergoes transformation into the fully dehydrated form—dCydC anhydro. The whole process of de- and re-hydratation has been observed by FTIR-PAS spectroscopy. The nature of the differences and similarities between structural and functional properties of crystalline forms of 2'dCyd and Cyd molecules has been discussed.