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At least 199 records · Page 11

High Pressure Response of Siliceous Materials

Several siliceous (i.e., materials containing, resembling, relating to or consisting of silica or silicon dioxide) materials were examined in this study conducted by Oak Ridge National Laboratory and sponsored by the US Army TARDEC. Some were glasses (fused silica or fused quartz, Starphire soda lime silicate glass, hydrated Starphire, BOROFLOAT borosilicate glass, an iron-containing soda lime silicate glass, opal (a hydrated silicate glass), ROBAX glass ceramic, and others were single crystal (α-quartz) and polycrystalline (Coesite - a high pressure phase of crystalline quartz) ceramics. Some of these materials are presently used in transparent armor systems or are under consideration for such. The testing of these materials allowed for comparisons of glass types, glass versus glass ceramics, effect of water content, and comparison of amorphous versus crystalline materials of the same composition. The responses of these materials to high pressure loading were studied using spherical indentation testing, diamond anvil cell testing, and laser shock testing. So besides the focus of this study being on the siliceous materials, as much emphasis was placed on the efficacy of these three test methods to exploit high pressure responses. Each test is different and enables the study of different aspects of high pressure response as highlighted below. 1. Spherical indentation, when using small indenter diameters, produces both high pressure and shear, and the loading and unloading histories enabled quantification of apparent yield stress and semi-quantification of energy absorption capability (hysteresis) of the various siliceous materials. 2. Diamond anvil cell testing produces a hydrostatic stress, and when concurrently used with Raman Spectroscopy, enabled the potential identification of changes of state of material as a function of quantified pressure for the various siliceous materials. Permanent densification was also detectable. 3. Laser shock testing produces high pressures but under dynamic conditions (impact event less than 30 ns), so this enabled the study of the effect of rate on high pressure. A previously unobserved damage mechanism was revealed with this testing, and the ease or difficulty of laser-shock-induced damage initiation was deemed to be relatable to the native surface flaw population that exists on these materials.

Wereszczak, Andrew A.↗

Glass Striae and Laser Shock Damage

This study sought to examine if striae are preferential locations for damage initiation in vitreous silicate float glasses when they are subjected to shock. Striae are typically native to vitreous silicate float glasses and their formation is a consequence of incomplete or inhomogeneous mixing prior to glass solidification. Striae typically have a lamellar-like habit and their planar orientation is usually perpendicular to the glass tile thickness. F loat glass, such as BOROFLOATâ borosilicate glass, is often used in transparent protective systems and therefore can be subjected to shock in a ballistic impact. Previous work by the Authors indicated that shock-induced damage in such glasses could be co-located with striae, so the objective of this study was to more closely examine that potential relationship.

36 MATERIALS SCIENCE↗

Bubbling Behavior in a Waste Glass Melter

Legacy tank waste from five decades of plutonium production at the Hanford Site during the Cold War will be vitrified into a stable waste form for disposal. A Waste Treatment Plant, currently under construction, houses Joule heated ceramic-lined waste glass melters wherein radioactive waste will be combined with glass formers to produce borosilicate glass. Through testing conducted in pilot-scale melters with surrogate waste, as well as operational experience at other sites, it has been demonstrated that the use of bubblers can dramatically improve the glass production rate. However, knowledge of the bubble dynamics in the molten glass is necessary for prediction and design of improved melting processes. A computational fluid dynamics model of the melter has been developed to investigate the processes affecting feed melt rate. The model shows that the convection currents within the melt pool due to Joule heating supplied by the electrodes are enhanced by forced air bubbling. In this paper, parameters influencing the formation and rise of a bubble stream in a viscous liquid are investigated. Experimental data and observations from laboratory and pilot-scale testing are integrated with first principles to develop a set of equations that form a mechanistic bubbling model to be incorporated into the melter model.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Borosilicate glass-to-Kovar tube bonding

Two-micron-diameter inlet leak, useful in mass spectrometry applications, minimizes gas sample distortion that occurs between sample and leak, is easily joined to spectrometer inlet system, and withstands unusual gas pressures and temperatures.

Harris, R. F.↗

A low-cost solar-cell front contact using trapped silver mesh and electrostatic bonding

A new system to provide a contact with a silver mesh trapped between the cell and an encapsulating glass cover is described. Borosilicate glass is joined to the cell by electrostatic bonding during which the glass is deformed around the silver mesh to form a permanent optically coupled integral bond to the cell. The hermetic seal prevents the silver from oxidizing and destroying the electrical contact formed during the bonding process. It is demonstrated that electrostatic glass/silicon bonds have excellent stability under a variety of accelerated environmental tests. Electrostatic bonds to thin films of AL2O3, Ta2O5, and ZrO2 on glass can be used to make antireflective coatings for solar cells manufactured by this process. Test solar cells were manufactured by electrostatic bonding with good curve fill factors and efficiencies of 10 percent.

Landis, Geoffrey A.↗

Effects of Al:Si and (Al+Na):Si ratios on the static corrosion of sodium‐boroaluminosilicate glasses

Abstract Understanding alteration mechanisms of borosilicate glasses in aqueous media is essential to nuclear waste performance assessments to ensure radioisotopes are contained for extended durations. Aluminum is typically added to glass compositions to reduce the extent of alteration. However, previous work on 7‐day durability tests has suggested that Al has a nonlinear relationship with extent of alteration. The effects of Al:Si and (Al+Na):Si substitutions on glass durability were evaluated using series of glasses based on the International Simple Glass corroded in static conditions up to 13 months in deionized water at 90°C. The alteration behavior was determined by measurement of element release in solution. The ⁓7‐day alteration trends across the series were consistent with predicted trends. The 13‐month results indicated overall alteration decreased as Al:Si ratios increased and was unaffected by changes in (Al+Na):Si except for the glass with the highest (Al+Na):Si ratio (ISG‐A23N), which completely altered within 14 days. Frequent sampling and in situ Raman measurements of solutions revealed ISG‐A23N experienced several distinguishable alteration rate regimes within 7 days, forming a ⁓100 µm alteration layer and a NaSiAlO 4 zeolite.

Reiser, Joelle T.↗

The production of advanced glass ceramic HLW forms using cold crucible induction melter

Cold Crucible Induction Melters (CCIM) will favorably change how High-Level radioactive Waste (from nuclear fuel recovery) is treated in a near future. Unlike the existing Joule-Heated Melters (JHM) currently in operation for the glass-based immobilization of High-Level Waste (HLW), CCIM offers unique material features that will increase melt temperatures, increase throughput, increase mixing, increase loading in the waste form, lower melter foot prints, eliminate melter corrosion and lower costs. These features not only enhance the technology for producing HLW forms, but also provide advantageous attributes to the waste form by allowing more durable alternatives to glass. It is concluded that glass ceramic waste forms that are tailored to immobilize fission products of HLW can be can be made from the HLW processed with the CCIM. The advantageous higher temperatures reached with the CCIM and unachievable with JHM allows the lanthanides, alkali, alkaline earths, and molybdenum to dissolve into a molten glass. Upon controlled cooling they go into targeted crystalline phases to form a glass ceramic waste form with higher waste loadings than achievable with borosilicate glass waste forms. Natural cooling proves to be too fast for the formation of all targeted crystalline phases.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Wettability measurement under high P-T conditions using X-ray imaging with application to the brine-supercritical CO 2 system

We present a new method for measuring wettability or contact angle of minerals at reservoir pressure-temperature conditions using high-resolution X-ray computed tomography (HRXCT) and radiography. In this method, a capillary or a narrow slot is constructed from a mineral or a rock sample of interest wherein two fluids are allowed to form an interface that is imaged using X-rays. After some validation measurements at room pressure-temperature conditions, we illustrate this method by measuring the contact angle of CO 2 -brine on quartz, muscovite, shale, borosilicate glass, polytetrafluoroethylene (PTFE or Teflon), and polyether ether ketone (PEEK) surfaces at 60–71°C and 13.8–22.8 MPa. At reservoir conditions, PTFE and PEEK surfaces were found to be CO 2 -wet with contact angles of 140° and 127°, respectively. Quartz and muscovite were found to be water-wet with contact angles of 26° and 58°, respectively, under similar conditions. Borosilicate glass-air-brine at room conditions showed strong water-wet characteristics with a contact angle of 9°, whereas borosilicate glass-CO 2 -brine at 13.8 MPa and 60°C showed a decrease in its water-wetness with contact angle of 54°. This method provides a new application for X-ray imaging and an alternative to other methods.

58 GEOSCIENCES↗

White light emitting Ho{sup 3+}-doped CdS nanocrystal ingrained glass nanocomposites

We report the generation of white light from Ho{sup 3+} ion doped CdS nanocrystal ingrained borosilicate glass nanocomposites prepared by the conventional melt-quench method. Near visible 405 nm diode laser excited white light emission is produced by tuning the blue emission from the Ho{sup 3+} ions, green band edge, and orange-red surface-state emissions of the nanocrystalline CdS, which are further controlled by the size of the nanocrystals. The absorption and emission spectra evidenced the excitation of Ho{sup 3+} ions by absorption of photons emitted by the CdS nanocrystals. The high color rendering index (CRI = 84–89) and befitting chromaticity coordinates (x = 0.308–0.309, y = 0.326–0.338) of white light emission, near visible harmless excitation wavelength (405 nm), and high absorbance values at excitation wavelength point out that these glass nanocomposites may serve as a prominent candidate for resin free high power white light emitting diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis and properties of ZnTe and Eu{sup 3+} ion co-doped glass nanocomposites

In this study, ZnTe (II-VI) semiconductor and Eu{sup +3}-ion co-doped borosilicate glass has been prepared in the SiO{sub 2}-K{sub 2}O-CaO-BaO-B{sub 2}O{sub 3} glass system followed by controlled heat-treatment to produce glass nanocomposites. Glass transition temperature and crystallization peak temperature have been evaluated using DSC analysis. Dilatometric studies were carried out to evaluate thermal expansion co-efficient, glass transition temperature, and dilatometric softening temperature and found to be 10.7 × 10{sup −6}/K, 580° C and 628° C, respectively. TEM micrographs demonstrate formation of nano sized crystallites of less than 50 nm. The ZnTe crystal formation also established through selected area electron diffraction (SAED) analysis and high resolution images obtained through TEM studies. With increasing heat treatment time, optical transmission cut-off wavelength (λ{sub cut-off}) shifted towards higher wavelength. Excitation spectra were recorded by monitoring emission at 613 nm corresponding to the {sup 5}D{sub 0} → {sup 7}F{sub 2} transition. An intense 394 nm excitation band corresponding to the {sup 7}F{sub 0} → {sup 5}L{sub 6} transition was observed. Emission spectra were then recorded by exciting the glass samples at 394 nm. When the glass is heat-treated for 30 min at 610° C, a 6-fold increase in the intensity of the red emission at 612 nm has been observed, which is attributed to the segregation of Eu{sup 3+} ions into the low phonon energy ZnTe crystallites and as the size of the nanocrystals is smaller than the size of the exciton, quantum confinement effect is visible. Further increase in heat-treatment duration led to decrease in luminescence intensity due to the growth of larger size crystals. {sup 5}D{sub 1} → {sup 7}F{sub 0} transition is visible only in the samples heat-treated for 30 min and 1 h, which is a characteristic of presence of Eu{sup 3+} ions in the low phonon energy ZnTe crystal sites. The micro hardness of the precursor glass and glass nanocomposites was evaluated; base glass shows hardness of 6.7 GPa and hardness of heat-treated glass nanocomposites has been found to decrease with increase in heat-treatment duration (5.5-5.3 GPa). However, mechanical properties are found to be suitable for device applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Defense Waste Processing Facility (DWPF) Durability-Composition Models and the Applicability of the Associated Reduction of Constraints (ROC) Criteria for High TiO 2 Containing Glasses

Radioactive high-level waste (HLW) at the Savannah River Site (SRS) has successfully been vitrified into borosilicate glass in the DWPF since 1996. Vitrification requires stringent product/process (P/P) constraints since the glass cannot be reworked once it has been poured into ten foot tall by two foot diameter canisters. A unique “feed forward” statistical process control (SPC) was developed for this control rather than relying on statistical quality control (SQC). In SPC, the feed composition to the DWPF melter is controlled prior to vitrification. In SQC, the glass product would be sampled after it is vitrified. Individual glass property-composition models form the basis for the “feed forward” SPC. The models transform constraints on the melt and glass properties into constraints on the feed composition going to the melter in order to determine, at the 95% confidence level, that the feed will be processable and that the durability of the resulting waste form will be acceptable to a geologic repository. The DWPF SPC system is known as the Product Composition Control System (PCCS). One of the process models within PCCS is known as the Thermodynamic Hydration Energy Reaction MOdel (THERMO™). The DWPF will soon be receiving increased concentrations of TiO 2 -, Na 2 O-, and Cs 2 O-enriched wastes from the Salt Waste Processing Facility (SWPF). The SWPF has been built to pretreat the high-curie fraction of the salt waste to be removed from the HLW tanks in the F- and H-Area Tank Farms at the SRS. In order to validate the existing TiO 2 term in THERMO™ beyond 2.0 wt% in the DWPF, new durability data were developed over the target range of 2.00 to 6.00 wt% TiO 2 and evaluated against the 1995 durability model. The durability was measured by the 7-day Product Consistency Test. This study documents the adequacy of the existing THERMO™ terms. It is recommended that the modified THERMO™ durability models and the modified property acceptable region limits for the durability constraints be incorporated in the next revision of the technical bases for PCCS and then implemented into PCCS. It is also recommended that an reduction of constraints of 4 wt% Al 2 O 3 be implemented with no restrictions on the amount of alkali in the glass for TiO 2 values ≥2 wt%. The ultimate limit on the amount of TiO 2 that can be accommodated from SWPF will be determined by the three PCCS models, the waste composition of a given sludge batch, the waste loading of the sludge batch, and the frit used for vitrification.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Defense Waste Processing Facility (DWPF) Viscosity Model: Revisions for Processing High TiO 2 Containing Glasses

Radioactive high-level waste (HLW) at the Savannah River Site (SRS) has successfully been vitrified into borosilicate glass in the Defense Waste Processing Facility (DWPF) since 1996. Vitrification requires stringent product/process (P/P) constraints since the glass cannot be reworked once it is poured into ten foot tall by two foot diameter canisters. A unique “feed forward” statistical process control (SPC) was developed for this control rather than statistical quality control (SQC). In SPC, the feed composition to the DWPF melter is controlled prior to vitrification. In SQC, the glass product would be sampled after it is vitrified. Individual glass property-composition models form the basis for the “feed forward” SPC. The models transform constraints on the melt and glass properties into constraints on the feed composition going to the melter in order to guarantee, at the 95% confidence level, that the feed will be processable and that the durability of the resulting waste form will be acceptable to a geologic repository. The DWPF SPC system is known as the Product Composition Control System (PCCS). The DWPF will soon be receiving wastes from the Salt Waste Processing Facility (SWPF) containing increased concentrations of TiO 2 , Na 2 O, and Cs 2 O . The SWPF is being built to pretreat the high-curie fraction of the salt waste to be removed from the HLW tanks in the F- and H-Area Tank Farms at the SRS. In order to process TiO 2 concentrations >2.0 wt% in the DWPF, new viscosity data were developed over the range of 1.90 to 6.09 wt% TiO 2 and evaluated against the 2005 viscosity model. An alternate viscosity model is also derived for potential future use, should the DWPF ever need to process other titanate-containing ion exchange materials. The ultimate limit on the amount of TiO 2 that can be accommodated from SWPF will be determined by the three PCCS models, the waste composition of a given sludge batch, the waste loading of the sludge batch, and the frit used for vitrification.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Specific Heat and Thermal Expansion of Triglycine Sulfate–Porous Glass Nanocomposites

The effect of restricted geometry on specific heat capacity and thermal expansion of the triglycine sulfate (TGS)–borosilicate glass composites have been studied first. A decrease in the entropy and temperature of the P2{sub 1} ↔ P2{sub 1}/m phase transition in the TGS component with decreasing the glass matrix pore diameter at the invariable specific heat and thermal expansion coefficient has been observed. The estimates are indicative of the minor effect of internal pressure on the TGS pressure coefficient dT{sub C}/dp in the composites.

36 MATERIALS SCIENCE↗

Advanced Thin Film Core Technology: CIGS Final Technical Report (FTR)

Cu(In,Ga)Se 2 (CIGS) thin-film photovoltaics are a high-efficiency and reliable technology. This project completed research in two important areas and was designed to work collaboratively with industrial partners. Task 1: Alkali Science focused on alkali post-deposition treatments (PDT). PDTs have been instrumental in the dramatic voltage improvements that have moved CIGS device efficiencies from 20% to 23.35% [1]. Based on a survey of CIGS companies at the beginning of the project, the single biggest breakthrough for the CIGS community would be a mechanistic understanding of the role of alkalis in the material system. Significant accomplishments of Task 1: Alkali Science: 1) KF post-deposition treatments were shown to improve lifetime, open-circuit voltage (VOC), and efficiency of industrial partner samples, even when done as a later step, separate from the original CIGS deposition. 2) KF boosted efficiency when incorporated at the end of the third stage of NREL CIGS growth. 3) XPS characterization of CIGS surfaces with and without PDTs led to a proposed mechanism whereby K drives structural transformation at 350 degrees C that is locked in at room temperature even after K is rinsed away. 4) Published recipes for KF and RbF PDTs. Literature to date did not provide enough detail to quickly reproduce experimental results. 5) Identified most important parameters (RbF cell temperature and lamp setpoint temperature) and set boundaries for successful RbF PDTs. The purpose of Task 2: Cell-level Reliability was to overcome the largest challenges to investor confidence and long product lifetime in CIGS-based photovoltaic products: metastability, shading-induced hot spots, and potential-induced degradation (PID). Key findings were made in each of these areas by studying CIGS reliability at the cell level: 1) Published NREL's cell-level reliability testing procedures along with challenges that were encountered while developing them. These were also distributed to the community through an MRS conference presentation. 2) Decreased metastability by adding a CdS hole-injection layer between the CIGS and Zn(O,S) in the device stack. It also improved device performance. Materials other than CdS can be used for the same purpose. 3) Reduced front-glass PID by replacing soda-lime glass with low-Na borosilicate glass. 4) Found that PID depends on leakage current and light/electrical bias. This will help labs avoid test-specific degradation. 5) Discovered that CIGS can suffer from two different types of PID with different mechanisms. Front is slower and leads to shunting ZnO. Back is faster and degrades the p-n junction. 6) Holding cells at open circuit slows PID compared to short circuit. This affects testing protocols for glass/glass modules.

14 SOLAR ENERGY↗

The Production of Advanced Glass Ceramic HLW Forms using Cold Crucible Induction Melter

Cold Crucible Induction Melters (CCIMs) will favorably change how High-Level radioactive Waste (from nuclear fuel recovery) is treated in the 21st century. Unlike the existing Joule-Heated Melters (JHMs) currently in operation for the glass-based immobilization of High-Level Waste (HLW), CCIMs offer unique material features that will increase melt temperatures, increase throughput, increase mixing, increase loading in the waste form, lower melter foot prints, eliminate melter corrosion and lower costs. These features not only enhance the technology for producing HLW forms, but also provide advantageous attributes to the waste form by allowing more durable alternatives to glass. This paper discusses advantageous features of the CCIM, with emphasis on features that overcome the historical issues with the JHMs presently utilized, as well as the benefits of glass ceramic waste forms over borosilicate glass waste forms. These advantages are then validated based on recent INL testing to demonstrate a first-of-a-kind formulation of a non-radioactive ceramic-based waste form utilizing a CCIM.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗