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All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Thermodynamic, kinetic and electrical switching studies on Si{sub 15}Te{sub 85-x}In{sub x} glasses: Observation of Boolchand intermediate phase

An interesting topic for quite some time is an intermediate phase observed in chalcogenide glasses, which is related to network connectivity and rigidity. This phenomenon is exhibited by Si-Te-In glasses also. It has been addressed here by carrying out detailed thermal investigations by using Alternating Differential Scanning Calorimetry technique. An effort has also been made to determine the stability of these glasses using the data obtained from different thermodynamic quantities and crystallization kinetics of these glasses. Electrical switching behavior by recording I-V characteristics and variation of switching voltages with indium composition have been studied in these glasses for phase change memory applications. - Graphical abstract: The variation of non-reversing heat flow ({Delta}H{sub NR}) of Si{sub 15}Te{sub 85-x}In{sub x} glasses with composition (x) and average coordination number (Left-Pointing-Angle-Bracket r Right-Pointing-Angle-Bracket). The Boolchand intermediate phase can be seen in the composition range 2{<=}x{<=}6. Highlights: Black-Right-Pointing-Pointer Observation of Boolchand intermediate phase. Black-Right-Pointing-Pointer Crystallization kinetic studies. Black-Right-Pointing-Pointer Electrical switching studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Structure of AgI-doped Ge-In-S glasses: Experiment, reverse Monte Carlo modelling, and density functional calculations

We report an investigation of the structure and vibrational modes of Ge-In-S-AgI bulk glasses using X-ray diffraction, EXAFS spectroscopy, Reverse Monte-Carlo (RMC) modelling, Raman spectroscopy, and density functional theoretical (DFT) calculations. The combination of these techniques made it possible to elucidate the short- and medium-range structural order of these glasses. Data interpretation revealed that the AgI-free glass structure is composed of a network where GeS{sub 4/2} tetrahedra are linked with trigonal InS{sub 3/2} units; S{sub 3/2}Ge-GeS{sub 3/2} ethane-like species linked with InS{sub 4/2}{sup -} tetrahedra form sub-structures which are dispersed in the network structure. The addition of AgI into the Ge-In-S glassy matrix causes appreciable structural changes, enriching the Indium species with Iodine terminal atoms. The existence of trigonal species InS{sub 2/2}I and tetrahedral units InS{sub 3/2}I{sup -} and InS{sub 2/2}I{sub 2}{sup -} is compatible with the EXAFS and RMC analysis. Their vibrational properties (harmonic frequencies and Raman activities) calculated by DFT are in very good agreement with the experimental values determined by Raman spectroscopy. - Graphical abstract: Experiment (XRD, EXAFS, RMC, Raman scattering) and density functional calculations are employed to study the structure of AgI-doped Ge-In-S glasses. The role of mixed structural units as illustrated in the figure is elucidated. Highlights: Black-Right-Pointing-Pointer Doping Ge-In-S glasses with AgI causes significant changes in glass structure. Black-Right-Pointing-Pointer Experiment and DFT are combined to elucidate short- and medium-range structural order. Black-Right-Pointing-Pointer Indium atoms form both (InS{sub 4/2}){sup -} tetrahedra and InS{sub 3/2} planar triangles. Black-Right-Pointing-Pointer (InS{sub 4/2}){sup -} tetrahedra bond to (S{sub 3/2}Ge-GeS{sub 3/2}){sup 2+} ethane-like units forming neutral sub-structures. Black-Right-Pointing-Pointer Mixed chalcohalide species (InS{sub 3/2}I){sup -} offer vulnerable sites for the uptake of Ag{sup +}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Thermal stability and thermoelectric properties of Cu{sub x}As{sub 40−x}Te{sub 60−y}Se{sub y} semiconducting glasses

We report on the thermal behavior and thermoelectric properties of bulk chalcogenide glasses in the systems Cu{sub x}As{sub 40−x}Te{sub 60} (20≤x≤32.5) and Cu{sub x}As{sub 40−x}Te{sub 60−y}Se{sub y}, (0≤y≤9) synthesized by conventional melt-quenching techniques. The thermal stability of these glasses was probed by differential scanning calorimetry to determine the characteristic T{sub g} and ΔT temperatures, both of which increasing noticeably with y. Thermoelectric properties were found to be mainly influenced by the Cu concentration with respect to the Se content. The thermal conductivity is practically composition-independent throughout the compositional range covered. A maximum ZT value of 0.02 at 300 K increasing to 0.06 at 375 K was achieved for the composition Cu{sub 30}As{sub 10}Te{sub 54}Se{sub 6}. - Graphical abstract: Effect of substitution of Te by Se and As by Cu on thermal stability and thermoelectric properties of Cu{sub x}As{sub 40−x}Te{sub 60−y}Se{sub y} semiconducting glasses. - Highlights: • We studied substitution of Te by Se in Cu–As–Te thermoelectric chalcogenide glasses. • Cu–As–Te–Se glasses were prepared by conventional melt-quenching method. • Se inclusion increases thermal stability in Cu–As–Te glasses. • Increasing copper concentration enhances thermoelectric properties. • ZT of 0.02 was achieved at 300 K and 0.06 at 375 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Study on glass-forming ability and hydrogen storage properties of amorphous Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0, 4) alloys

Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0, 4) amorphous alloys were prepared by rapid solidification, using a melt-spinning technique. X-ray diffraction and differential scanning calorimetry analysis were employed to measure their microstructure, thermal stability and glass-forming ability, and hydrogen storage properties were studied by means of PCTPro2000. Based on differential scanning calorimetry results, their glass-forming ability and thermal stability were investigated by Kissinger method, Lasocka curves and atomic cluster model, respectively. The results indicate that glass-forming ability, thermal properties and hydrogen storage properties in the Mg-rich corner of Mg–Ni–La–Co system alloys were enhanced by Co substitution for La. It can be found that the smaller activation energy (ΔΕ) and frequency factor (υ{sub 0}), the bigger value of B (glass transition point in Lasocka curves), and higher glass-forming ability of Mg–Ni–La–Co alloys would be followed. In addition, atomic structure parameter (λ), deduced from atomic cluster model is valuable in the design of Mg–Ni–La–Co system alloys with good glass-forming ability. With an increase of Co content from 0 to 4, the hydrogen desorption capacity within 4000 s rises from 2.25 to 2.85 wt.% at 573 K. - Highlights: • Amorphous Mg{sub 60}Ni{sub 30}La{sub 10−x}Co{sub x} (x = 0 and 4) alloys were produced by melt spinning. • The GFA and hydrogen storage properties were enhanced by Co substitution for La. • With an increase of Co content, the hydrogen desorption capacity rises at 573 K.

36 MATERIALS SCIENCE↗
DOE OSTI2011

The third-order optical nonlinearities of Ge-Ga-Sb(In)-S chalcogenide glasses

Research highlights: {yields} It is firstly demonstrated that the nonlinear refractive index n{sub 2} is dependent on the covalency of bonds in chalcogenide glass. {yields} Homopolar metallic bonds in chalcogenide glass have positive contribution to large nonlinear refractive index n{sub 2} also. {yields} The 80GeS{sub 2}.20Sb{sub 2}S{sub 3} glass would be expected to be used in the all-optical switches working at 1330 nm and 1550 nm telecommunication wavelengths. -- Abstract: The third-order optical nonlinearities of 80GeS{sub 2}.(20 - x)Ga{sub 2}S{sub 3}.xY{sub 2}S{sub 3} (x = 0, 5, 10, 15, 20 and Y = Sb or In) chalcogenide glasses were investigated utilizing the Z-scan method at the wavelength of 800 nm and their linear optical properties and structure were also studied. By analyzing the compositional dependences and possible influencing factors including the linear refractive index, the concentration of lone electron pairs, the optical bandgap and the amount of weak covalent/homopolar bonds, it indicates that the electronic contribution in weak heteropolar covalent and homopolar metallic bonds is responsible for large nonlinear refractive index n{sub 2} in the chalcogenide glasses. These chalcogenide glasses have characteristics of environmentally friendship, wide transparency in the visible region, high nonlinear refractive index n{sub 2} and low nonlinear absorption coefficient {beta}, and would be expected to be used in the all-optical switches working at 1330 nm and 1550 nm telecommunication wavelengths.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Photoactive transparent nano-crystalline glass-ceramic for remazole red dye degradation

Graphical abstract: Display Omitted Highlights: ► Preparation and characterization of novel transparent nanocrystalline glass-ceramic. ► Precipitation of photoactive phases by using controlled heat-treatment. ► Conservation of transparency along with photoactivity. ► Using the prepared nanocrystalline glass-ceramic in water purification. -- Abstract: Transparent glass ceramic material was prepared from alkali-borosilicate glass containing titania by proper heat treatment scheme. The prepared samples were characterized using differential thermal analysis, X-ray diffraction, transmission electron microscope, selected area electron diffraction and UV–visible spectroscopy. The applied heat treatment program allowed the crystallization of nano-crystalline anatase, rutile, barium titanate, titanium borate and silicate phases while maintaining the transparency. The precipitated nano-crystalline anatase and rutile phases were responsible for the observed high photocatalytic activity of the prepared samples. Samples of 24.29 and 32.39 TiO{sub 2} wt% showed better efficiency for the decolorization of remazole red dye compared with commercial-TiO{sub 2} used in preparation of glass-ceramic. The reuse of prepared glass-ceramic photocatalyst with nearly same efficiency for different times was also proved.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2013

Broadband anti-reflective and water-repellent coatings on glass substrates for self-cleaning photovoltaic cells

Graphical abstract: High performance broadband antireflective and water-repellent coatings were fabricated on glass substrates, which can improve the short-circuit current of solar cells as much as 6.6% in comparison with glass substrates without the coatings. - Highlights: • Broadband anti-reflective and water-repellent coatings were fabricated. • Transmittance increased to 99.0%, significantly higher than that of commercial solar glasses. • The performance of standard solar cells with the AR coating was enhanced as much as 6.6%. - Abstract: High performance broadband antireflective (AR) and water-repellent coatings were fabricated on glass substrates by assembly of silica nanoparticles and polyelectrolytes via the layer-by-layer (LbL) assembly technique, followed by calcination and hydrophobic modification. A porous poly(diallyladimethylammonium chloride) (PDDA)/20 nm SiO{sub 2} nanoparticles (S-20) multilayer coating with AR property was prepared first. The maximum transmittance is as high as 99.0%, while that of the glass substrate is only 91.3%. After calcination and hydrophobic modification, the coating became water-repellent while maintaining the good AR property. Such water-repellent AR coatings can improve the short-circuit current of solar cells as much as 6.6% in comparison with glass substrates without the coatings. Scanning electron microscopy (SEM) was used to observe the morphology and thickness of coatings. Transmission spectra and reflection spectra were characterized by UV–vis spectrophotometer. The surface wettability was studied by a contact angle/interface system.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Mid-infrared emissions of Pr{sup 3+}-doped GeS{sub 2}–Ga{sub 2}S{sub 3}–CdI{sub 2} chalcohalide glasses

Graphical abstract: ∼4.6 μm mid-infrared fluorescence emission from Pr{sup 3+} in the sulfide glass is successfully observed at room temperature excited by a 2.01 μm Tm{sup 3+}:YAG ceramic laser system. - Highlights: • Serial Pr{sup 3+}-doped GeS{sub 2}–Ga{sub 2}S{sub 3}–CdI{sub 2} chalcohalide glasses were synthesized. • ∼4.6 μm mid-infrared fluorescence from Pr{sup 3+} was observed at room temperature. • The compositional dependence of luminescence properties was studied. • Radiative properties have been determined using the Judd–Ofelt theory. - Abstract: For elucidation of the glass composition’s influence on the spectroscopic properties in the chalcohalide system and the discovery of a new material for applications in mid-infrared fiber-lasers, a serial Pr{sup 3+}-doped (100 − x)(0.8GeS{sub 2}·0.2Ga{sub 2}S{sub 3})xCdI{sub 2} (x = 5, 10, 15 and 20) chalcohalide glasses were prepared. ∼4.6 μm mid-infrared fluorescence emission from Pr{sup 3+} in the sulfide glass is successfully observed at room temperature excited by a 2.01 μm Tm{sup 3+}:YAG ceramic laser system, and the effective line-width of fluorescence band is 106–227 nm. Intense compositional dependence of mid-infrared emissions is found. The radiative rates of Pr{sup 3+} ions in these glasses were calculated by using the Judd–Ofelt theory.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Dy{sup 3+}-doped Ga–Sb–S chalcogenide glasses for mid-infrared lasers

Highlights: • Novel Ga–Sb–S chalcogenide glasses doped with Dy{sup 3+} ions were synthesized. • The glasses show good thermal stability and excellent infrared transparency. • The glasses show low phonon energy and intense mid-infrared emissions. • The mid-infrared emissions have high quantum efficiency. • The mid-infrared emissions have large stimulated emission cross sections. - Abstract: Novel Ga–Sb–S chalcogenide glasses doped with different amount of Dy{sup 3+} ions were prepared. Their thermal stability, optical properties, and mid-infrared (MIR) emission properties were investigated. The glasses show good thermal stability, excellent infrared transparency, very low phonon energy (∼306 cm{sup −1}), and intense emissions centered at 2.95, 3.59, 4.17 and 4.40 μm. Three Judd–Ofelt intensity parameters (Ω{sub 2} = 8.51 × 10{sup −20} cm{sup 2}, Ω{sub 4} = 2.09 × 10{sup −20} cm{sup 2}, and Ω{sub 6} = 1.60 × 10{sup −20} cm{sup 2}) are obtained, and the related radiative transition properties are evaluated. The high quantum efficiencies and large stimulated emission cross sections of the MIR emissions (88.10% and 1.11 × 10{sup −20} cm{sup 2} for 2.95 μm emission, 75.90% and 0.38 × 10{sup −20} cm{sup 2} for 4.40 μm emission, respectively) in the Dy{sup 3+}-doped Ga–Sb–S glasses make them promising gain materials for the MIR lasers.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Controllable synthesis and tunable luminescence of glass ceramic containing Mn{sup 2+}:ZnAl{sub 2}O{sub 4} and Pr{sup 3+}:YF{sub 3} nano-crystals

Highlights: • Glass ceramic containing ZnAl{sub 2}O{sub 4} and YF{sub 3} nano-crystals is fabricated. • Mn{sup 2+} and Pr{sup 3+} are selectively incorporated into ZnAl{sub 2}O{sub 4} and YF{sub 3}, respectively. • The luminescence color can be tuned by adjusting the excitation wavelength. - Abstract: Glass ceramic containing spinel ZnAl{sub 2}O{sub 4}:Mn{sup 2+} and orthorhombic YF{sub 3}:Pr{sup 3+} nano-crystals has been successfully prepared by a melt-quenching technique. X-ray diffraction and transmission electron microscopy demonstrated that two nano-phases, i.e. ZnAl{sub 2}O{sub 4} and YF{sub 3}, were homogeneously distributed among the glass matrix. Importantly, the selective incorporation of Pr{sup 3+} ions into the Y{sup 3+} nine-fold coordinated sites of YF{sub 3} and the segregation of Mn{sup 2+} dopants in the Zn{sup 2+} tetrahedral sites of ZnAl{sub 2}O{sub 4} were confirmed based on the excitation/emission spectra and the crystal field calculation. Under blue light excitation, both Pr{sup 3+} and Mn{sup 2+} in the glass ceramic can be simultaneously excited, and emit red and green luminescence, respectively, owing to the suppression of energy transfer between them. The luminescence color of the obtained glass ceramic can be easily tuned by adjusting the excitation wavelength. These results indicate the potential application of the glass ceramic as converting phosphor to generate white-light after coupling with the blue LED chip.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Effects of titanium nanoparticles on self-cleaning and structural features of zinc-magnesium-phosphate glass

Graphical abstract: Water contact angle for sample S2, S3, S4 and S5. The water contact angle increased with increased the titanium NPs content (mol%). - Highlights: • ZnO–MgO–P{sub 2}O{sub 5} embedded TiO{sub 2} NPs prepared by conventional melt-quenching method. • The amorphous nature is confirmed by X-ray diffraction spectroscopy. • The structural characteristics of glasses is investigated using FTIR and Raman. • Wettability of the glasses surface by water contact angle. - Abstract: The loss of glass transparency on surface pollutants contamination unless inhibited not only causes vision obscurity but also responsible for major aesthetic damages of cultural heritage. It is due to the sticking of fine dirt particles on wetting layers, a complex process with several possible ramifications still to be clarified. We report the influence of titanium dioxide or titania (TiO{sub 2}) nanoparticles (NPs) on the structural and self-cleaning properties of zinc–magnesium–phosphate glasses. Following melt-quenching method glass samples of optimized composition (42 − x)P{sub 2}O{sub 5}–8MgO–50ZnO–xTiO{sub 2} with x = 0, 1, 2, 3 and 4 mol% are prepared. XRD patterns verified their amorphous nature and TEM images revealed the nucleation of TiO{sub 2} NPs of average diameter ≈4.05 ± 0.01 nm. Fourier transform infrared (FTIR) spectra displayed four absorption band centred at 1618–3438 cm{sup −1}, 902– 931 cm{sup −1}, 757–762 cm{sup −1} and 531–560 cm{sup −1}. Raman spectra exhibited four peaks each accompanied by a blue-shift. Water contact angle is found to increase with the increase of titanium NPs concentration into the amorphous matrix. This knowledge can be used to set up strategies and selective treatments to preventing glass transparency loss via the modification of self-cleaning attributes.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Braunite phase embedded Y2O3/MnO2-Al2O3-CaO-SiO2 glass ceramics and their properties

Highlights: • Nucleation of synthetic braunite structure (Mn{sub 7}SiO{sub 12}) on sintering of Y{sub 2}O{sub 3}/MnO{sub 2}-CaO-Al{sub 2}O{sub 3}-SiO{sub 2} glasses at 850 °C. • Lossy capacitor behaviour. • Exhibits a critical temperature in 500–600 °C range. • Conduction mechanism shift from Superlinear power law to universal dielectric response law with increase in temperature. - Abstract: Glass series (20-x)Y{sub 2}O{sub 3}-xMnO{sub 2}-20Al{sub 2}O{sub 3}-40SiO{sub 2}-20CaO (x = 5, 10, 15 and 20, mol%) have been synthesized by melt quench technique followed by sintering at 850 °C. The optical band gap of the samples is in wide semiconductor range and increased with MnO{sub 2} content. Photoluminescence study exhibits emission in Mn{sup 2+} d-states. On the other hand, hardness decreases with MnO{sub 2} content except for 10 mol% MnO{sub 2} containing glasses (YM10). The formation of braunite phase in glass ceramics induces capacitive losses. In lower temperature region, the conductivity behaviour of samples follows superlinear power law. In higher temperature region, it follows the universal law of conduction. The dielectric constant for the sintered glasses is constant with respect to temperature, approximately upto 350 °C and 1 MHz frequency. Above 350 °C, the ionic conduction dominates in all the sintered glasses. The anomaly in properties is observed when the ratio of Y{sub 2}O{sub 3}/MnO{sub 2} is 1:1.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Photoluminescence properties and device application of CsPb2Br5 quantum dots in glasses

Highlights: • Photoluminescence spectra of CsPb{sub 2}Br{sub 5} QDs were tuned from 499 to 506 nm. • The CsPb{sub 2}Br{sub 5} glass showed an thermal stability from 298 K to 433 K. • WLED were realized through incorporating QDs glasses with red phosphor. - Abstract: Herein, CsPb{sub 2}Br{sub 5} quantum dots (QDs) in glasses under various durations of heat-treatment at 420 °C was investigated. Photoluminescence (PL) spectra of CsPb{sub 2}Br{sub 5} QDs were tuned from 499 to 506 nm and the decay time show a increasing for the structure defect and electron-hole consist in CsPb{sub 2}Br{sub 5} QDs glasses. The CsPb{sub 2}Br{sub 5} glass showed an thermal stability with about 85% emission loss when elevating temperature from 298 K to 433 K. Moreover, The warm white light emitting diode (WLED) was realized through incorporating CaAlSiN{sub 3}:Eu{sup 2+} red phosphor with CsPb{sub 2}Br{sub 5} QDs doped borosilicate glasses on an InGaN blue chip. Finally, we achieved a luminous efficacy of 42.7 lm/W, CCT of 3915 K and CRI of 68.5 under 20 mA current driving.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2021

A constitutive model for glass–ceramic materials

Glass–ceramics have received recent attention for use in glass–ceramic to metal hermetic seals. Due to their heterogeneous microstructure, these materials exhibit a number of advantageous responses over conventional glass based seals. Key amongst them is the possibility of a controllable thermal strain response and apparent coefficient of thermal expansion which may be used to minimize thermally induced residual stresses for aforementioned seals. Furthermore, these behaviors result from an inorganic glass matrix and variety of crystalline ceramic phases including silica polymorph(s) that may undergo reversible solid-to-solid transformations with associated inelastic strain. Correspondingly, these materials exhibit complex thermomechanical responses associated with multiple inelastic mechanisms (viscoelasticity and phase transformation). While modeling these behaviors is essential for developing and analyzing the corresponding applications, no such model exists. Therefore, in this work a three-dimensional continuum constitutive model for glass–ceramic materials combining these various inelastic mechanisms is developed via an internal state variable approach. A corresponding fully implicit three dimensional numerical formulation is also proposed and implemented. The model is used to simulate existing experiments and validate the proposed formalism. As an example, the simple seal problem of a glass–ceramic seal inside a concentric metal shell is explored. Finally, the impact of the cooling rates, viscoelastic shift factors, and inelastic strain on final residual stress state are all investigated and the differing contributions highlighted.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Radiation hardness characterization of LKH-5 scintillating glass

Radiation hardness is an important property to examine in scintillators to help determine their expected lifetime in application cases where significant radiation dose is expected. Industrial imaging systems using 9 MV linear accelerators for x-ray radiography are one such application where significant radiation doses are expected to the scintillators used. Cadmium tungstate scintillators (CWO) and Thallium doped Cesium Iodide scintillators (CsI(Tl)) are used in some high energy cargo x-ray radiography systems. However, CWO has a high manufacturing cost for adequately uniform crystals and CsI(Tl) does not have sufficient radiation hardness. LKH-5 glass is being investigated as a potential low cost replacement for CWO and CsI(Tl). In this experiment 36 samples of a terbium doped silicate glass called LKH-5 were irradiated at doses up to 5 MRad using a 9 MV linear accelerator, and the change in their transmission properties was observed. Additionally, the glass was discovered to be a radiation hard glass due to the relatively small change in the transmission of the glass: less than 3% per cm at its emission peak of 550 nm and 5 MRad. This is similar to CWO which has a reported reduction in transmitted light of 2% per cm at 5 MRad and the emission peak of 475 nm and better than CsI(Tl) which is reported to have a reduction in transmitted light of 5% per cm at the emission peak of 550 nm and 4.2 MRad dose. Furthermore, an annealing procedure is described that returned the transmission of the glass to pre-irradiation values.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2015

Development of a sintering process for recycling oil shale fly ash and municipal solid waste incineration bottom ash into glass ceramic composite

Highlights: • Glass ceramic composite is prepared from oil shale fly ash and MSWI bottom ash. • A novel method for the production of glass ceramic composite is presented. • It provides simple route and lower energy consumption in terms of recycling waste. • The vitrified slag can promote the sintering densification process of glass ceramic. • The performances of products decrease with the increase of oil shale fly ash content. - Abstract: Oil shale fly ash and municipal solid waste incineration bottom ash are industrial and municipal by-products that require further treatment before disposal to avoid polluting the environment. In the study, they were mixed and vitrified into the slag by the melt-quench process. The obtained vitrified slag was then mixed with various percentages of oil shale fly ash and converted into glass ceramic composites by the subsequent sintering process. Differential thermal analysis was used to study the thermal characteristics and determine the sintering temperatures. X-ray diffraction analysis was used to analyze the crystalline phase compositions. Sintering shrinkage, weight loss on ignition, density and compressive strength were tested to determine the optimum preparation condition and study the co-sintering mechanism of vitrified amorphous slag and oil shale fly ash. The results showed the product performances increased with the increase of sintering temperatures and the proportion of vitrified slag to oil shale fly ash. Glass ceramic composite (vitrified slag content of 80%, oil shale fly ash content of 20%, sintering temperature of 1000 °C and sintering time of 2 h) showed the properties of density of 1.92 ± 0.05 g/cm{sup 3}, weight loss on ignition of 6.14 ± 0.18%, sintering shrinkage of 22.06 ± 0.6% and compressive strength of 67 ± 14 MPa. The results indicated that it was a comparable waste-based material compared to previous researches. In particular, the energy consumption in the production process was reduced compared to conventional vitrification and sintering method. Chemical resistance and heavy metals leaching results of glass ceramic composites further confirmed the possibility of its engineering applications.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

Structure of shock compressed model basaltic glass: Insights from O K-edge X-ray Raman scattering and high-resolution 27Al NMR spectroscopy

The detailed atomic structures of shock compressed basaltic glasses are not well understood. Here, we explore the structures of shock compressed silicate glass with a diopside-anorthite eutectic composition (Di{sub 64}An{sub 36}), a common Fe-free model basaltic composition, using oxygen K-edge X-ray Raman scattering and high-resolution {sup 27}Al solid-state NMR spectroscopy and report previously unknown details of shock-induced changes in the atomic configurations. A topologically driven densification of the Di{sub 64}An{sub 36} glass is indicated by the increase in oxygen K-edge energy for the glass upon shock compression. The first experimental evidence of the increase in the fraction of highly coordinated Al in shock compressed glass is found in the {sup 27}Al NMR spectra. This unambiguous evidence of shock-induced changes in Al coordination environments provides atomistic insights into shock compression in basaltic glasses and allows us to microscopically constrain the magnitude of impact events or relevant processes involving natural basalts on Earth and planetary surfaces.

58 GEOSCIENCES↗
DOE OSTI2017

Hidden amorphous phase and reentrant supercooled liquid in Pd-Ni-P metallic glasses

An anomaly in differential scanning calorimetry has been reported in a number of metallic glass materials in which a broad exothermal peak was observed between the glass and crystallization temperatures. The mystery surrounding this calorimetric anomaly is epitomized by four decades long studies of Pd-Ni-P metallic glasses, arguably the best glass-forming alloys. Here we show, using a suite of in-situ experimental techniques, that Pd-Ni-P alloys have a hidden amorphous phase in the supercooled liquid region. The anomalous exothermal peak is the consequence of a polyamorphous phase transition between two supercooled liquids, involving a change in the packing of atomic clusters over medium-range length scales as large as 18 Å. With further temperature increase, the alloy reenters the supercooled liquid phase which forms the room-temperature glass phase upon quenching. Finally, the outcome of this study raises a possibility to manipulate the structure and hence the stability of metallic glasses through heat-treatment.

36 MATERIALS SCIENCE↗