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DOE OSTI2020

Materials Data on ZnP3C6(NO6)2 by Materials Project

Zn(PO4)3(C3N)2 crystallizes in the orthorhombic P2_12_12_1 space group. The structure is one-dimensional and consists of eight trimethylamine molecules and two Zn(PO4)3 ribbons oriented in the (1, 0, 0) direction. In each Zn(PO4)3 ribbon, Zn2+ is bonded to four O2- atoms to form ZnO4 tetrahedra that share corners with four PO4 tetrahedra. There are a spread of Zn–O bond distances ranging from 1.94–1.98 Å. There are three inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one ZnO4 tetrahedra. There is two shorter (1.54 Å) and two longer (1.55 Å) P–O bond length. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent ZnO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.52–1.56 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one ZnO4 tetrahedra. There are a spread of P–O bond distances ranging from 1.53–1.55 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the fifth O2- site, O2- is bonded in a bent 120 degrees geometry to one Zn2+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Zn2+ and one P5+ atom. In the seventh O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the eighth O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the ninth O2- site, O2- is bonded in a bent 150 degrees geometry to one Zn2+ and one P5+ atom. In the tenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Zn2+ and one P5+ atom. In the eleventh O2- site, O2- is bonded in a single-bond geometry to one P5+ atom. In the twelfth O2- site, O2- is bonded in a single-bond geometry to one P5+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Hydroxylpyromorphite, a mineral important to lead remediation: Modern description and characterization

Abstract Hydroxylpyromorphite, Pb5(PO4)3(OH), has been documented in the literature as a synthetic and naturally occurring phase for some time but has not previously been formally described as a mineral. It is fully described here for the first time using crystals collected underground in the Copps mine, Gogebic County, Michigan. Hydroxylpyromorphite occurs as aggregates of randomly oriented hexagonal prisms, primarily between about 20–35 μm in length and 6–10 μm in diameter. The mineral is colorless and translucent with vitreous luster and white streak. The Mohs hardness is ~3½–4; the tenacity is brittle, the fracture is irregular, and indistinct cleavage was observed on {001}. Electron microprobe analyses provided the empirical formula Pb4.97(PO4)3(OH0.69F0.33Cl0.06)Σ1.08. The calculated density using the measured composition is 7.32 g/cm3. Powder X-ray diffraction data for the type material is compared to data previously reported for hydroxylpyromorphite from the talc mine at Rabenwald, Austria, and from Whytes Cleuch, Wanlockhead, Scotland. Hydroxylpyromorphite is hexagonal, P63/m, at 100 K, a = 9.7872(14), c = 7.3070(10) Å, V = 606.16(19) Å3, and Z = 2. The structure [R1 = 0.0181 for 494 F>4σ(F) reflections] reveals that hydroxylpyromorphite adopts a column anion arrangement distinct from other members of the apatite supergroup due to the presence of fluorine and steric constraints imposed by stereoactive lone-pair electrons of Pb2+ cations. The F– anion sites are displaced slightly from hydroxyl oxygen anions, which allows for stronger hydrogen-bonding interactions that may in turn stabilize the observed column-anion arrangement and overall structure. Our modern characterization of hydroxylpyromorphite provides deeper understanding to a mineral useful for remediation of lead-contaminated water.

Geochemistry & Geophysics↗

DOE OSTI2020

Materials Data on BiP3(PbO4)3 by Materials Project

Pb3Bi(PO4)3 crystallizes in the monoclinic Cc space group. The structure is three-dimensional. there are three inequivalent Pb2+ sites. In the first Pb2+ site, Pb2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Pb–O bond distances ranging from 2.36–2.75 Å. In the second Pb2+ site, Pb2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Pb–O bond distances ranging from 2.36–2.79 Å. In the third Pb2+ site, Pb2+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Pb–O bond distances ranging from 2.40–2.78 Å. Bi3+ is bonded to six O2- atoms to form distorted BiO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of Bi–O bond distances ranging from 2.24–2.59 Å. There are three inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent BiO6 octahedra. The corner-sharing octahedra tilt angles range from 36–38°. There is two shorter (1.54 Å) and two longer (1.57 Å) P–O bond length. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent BiO6 octahedra. The corner-sharing octahedra tilt angles range from 61–62°. There is two shorter (1.55 Å) and two longer (1.57 Å) P–O bond length. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent BiO6 octahedra. The corner-sharing octahedra tilt angles range from 36–61°. There are a spread of P–O bond distances ranging from 1.54–1.58 Å. There are twelve inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to two Pb2+ and one P5+ atom. In the second O2- site, O2- is bonded in a distorted single-bond geometry to one Pb2+, one Bi3+, and one P5+ atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to one Pb2+, one Bi3+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to two Pb2+ and one P5+ atom. In the fifth O2- site, O2- is bonded in a distorted single-bond geometry to two Pb2+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a 1-coordinate geometry to one Pb2+, one Bi3+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a distorted single-bond geometry to one Pb2+, one Bi3+, and one P5+ atom. In the eighth O2- site, O2- is bonded in a distorted single-bond geometry to two Pb2+ and one P5+ atom. In the ninth O2- site, O2- is bonded in a 1-coordinate geometry to one Pb2+, one Bi3+, and one P5+ atom. In the tenth O2- site, O2- is bonded in a distorted single-bond geometry to two Pb2+ and one P5+ atom. In the eleventh O2- site, O2- is bonded in a distorted single-bond geometry to two Pb2+ and one P5+ atom. In the twelfth O2- site, O2- is bonded in a distorted single-bond geometry to one Pb2+, one Bi3+, and one P5+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Biochemical inhibition of acid phosphatase activity in two mountain spruce forest soils

The product inhibition of the 4-Methylumbelliferyl phosphate (MUB-P) decay rate, a measure of potential acid phosphatase activity, has not been considered in most of the published kinetic studies. The aim of this study was to determine the type and strength of the product inhibition in order to better define reaction conditions at which the acid phosphatase activity assay produces unbiased results. The MUB-P decay rate was measured in the forest floor and topsoil organic horizons of two spruce forest catchments at different initial MUB-P and P-PO4 3- concentrations. Furthermore, the type and strength of the inhibition was analyzed by non-linear regression. We found that MUB-P decay was competitively inhibited by the P-PO4 3- but also by dissolved organic P. By using estimated kinetic parameters, we calculated an underestimation of potential acid phosphatase activity by up to ~20% at concentrations of added MUB-P as high as 300 µmol g-1 dry weight and an incubation time one hour due to background inorganic and organic P concentrations in range of units of µmol per gram of dry soil. We discuss approaches that can be used to minimize the underestimation and show that the previously defined recommendations might not be always sufficient to avoid the bias. Therefore, we recommend to analyze progress curves at a wide range of initial MUB-P concentrations using non-linear methods when the enzyme assay is optimized for a given soil. When changes in inorganic and/or organic P concentrations are expected, we further recommend measuring background inorganic and organic P concentrations.

59 BASIC BIOLOGICAL SCIENCES↗

NASA NTRS2017

Experimental Study into the Stability of Whitlockite in Basaltic Magmas

Apatite Ca5(PO4)3(F,Cl,OH), merrillite Ca18Na2Mg2(PO4)14, and whitlockite Ca9(Mg,Fe2+)(PO4)6[PO3(OH)] are the primary phosphate minerals found in most planetary materials including rocks from Earth, Moon, Mars, and asteroids [1-2]. For many years, the terms merrillite and whitlockite have been used interchangeably in the meteorite literature. Much of the confusion regarding the relationship between terrestrial and extraterrestrial "whitlockite" is based on the presence or absence of hydrogen in the mineral structure. Whitlockite has approximately 8500 ppm H2O, and the term "merrillite" has been adopted to identify the hydrogen-free form of whitlockite [2]. The atomic structures of merrillite and whitlockite were examined in detail by Hughes et al. [3-4]. On Earth, whitlockite has been found in rocks from evolved pegmatitic systems [2-4] and in some mantle rocks [e.g., 5]. Furthermore, terrestrial whitlockite has been shown to have some merrillite component [4]. For the meteoritic and lunar materials that have been investigated, merrillite appears to be far more common than whitlockite, and it has been proposed that the whitlockite component is unique to terrestrial samples [4]. There are some reports of "whitlockite" in the meteorite literature; however, these likely represent misidentifications of merrillite because there have been no reports of extraterrestrial whitlockite that have been verified through crystal structural studies or analyzed for their H contents. Hughes et al. [3] reported the atomic arrangement of lunar merrillite and demonstrated that the phase is similar to meteoritic merrillite and, predictably, devoid of hydrogen. In a follow-up study, Hughes et al. [4] reported the atomic arrangements of two natural samples of whitlockite, one synthetic whitlockite, and samples of synthetic whitlockite that were heated at 500degC and 1050degC for 24 h. The crystal chemistry and crystal structures of the phases were compared, and it was discovered that the latter treatment resulted in the dehydrogenation of whitlockite to form merrillite. The presence of merrillite vs. whitlockite was widely thought to serve as an indication that magmas were anhydrous [e.g., 6-7]. However, McCubbin et al., [8] determined that merrillite in the martian meteorite Shergotty had no discernible whitlockite component despite its coexistence with OH-rich apatite. Consequently, McCubbin et al., (2014) speculated that the absence of a whitlockite component in Shergotty merrillite and other planetary merrillites may be a consequence of the limited thermal stability of H in whitlockite (stable only at T less than1050degC), which would prohibit merrillite-whitlockite solid-solution at high temperatures. In the present study, we have aimed to test this hypothesis experimentally by examining the stability of whitlockite in basaltic magmas at 1.2 GPa and a temperature range of -1000- 1300degC.

McCubbin, F. M.↗

NASA NTRS2018

Experimental Study into the Stability of Whitlockite and Hydroxylapatite in Basaltic Magmas

Apatite (Ca5(PO4)3(F,Cl,OH)), merrillite (Ca18Na2Mg2(PO4)14), and whitlockite (Ca9(Mg,Fe(2+))(PO4)6[PO3(OH)]) are the primary phosphate minerals found in most planetary materials including rocks from Earth, Moon, Mars, and asteroids. For many years, the terms merrillite and whitlockite have been used interchangeably in the meteorite literature. Much of the confusion regarding the relationship between terrestrial and extraterrestrial 'whitlockite' is based on the presence or absence of hydrogen in the mineral structure. Whitlockite has approximately 8500 ppm H2O, and the term 'merrillite' has been adopted to identify the hydrogen-free form of whitlockite. The atomic structures of merrillite and whitlockite were examined in detail by Hughes et al.. On Earth, whitlockite has been found in rocks from evolved pegmatitic systems and in some mantle rocks. Furthermore, terrestrial whitlockite has been shown to have some merrillite component. For the meteoritic and lunar materials that have been investigated, merrillite appears to be far more common than whitlockite, and it has been proposed that the whitlockite component is unique to terrestrial samples. There are some reports of 'whitlockite' in the meteorite literature; however, these may represent misidentifications of merrillite because there have been no reports of extraterrestrial whitlockite that have been verified through crystal structural studies or analyzed for their H contents. Hughes et al. reported the atomic arrangement of lunar merrillite and demonstrated that the phase is similar to meteoritic merrillite and, predictably, devoid of hydrogen. In a follow-up study, Hughes et al. reported the atomic arrangements of two natural samples of whitlockite, one synthetic whitlockite, and samples of synthetic whitlockite that were heated at 500 C or 1050 C for 24 h. The crystal chemistry and crystal structures of the phases were compared, and it was discovered that the latter treatment resulted in the dehydrogenation of whitlockite to form merrillite.

McCubbin, F. M.↗

DOE OSTI2022

Recent Advances in Conduction Mechanisms, Synthesis Methods, and Improvement Strategies for Li 1+ x Al x Ti 2-x (PO 4 ) 3 Solid Electrolyte for All-Solid-State Lithium Batteries

With the increasing use of Li batteries for storage, their safety issues and energy densities are attracting considerable attention. Recently, replacing liquid organic electrolytes with solid-state electrolytes (SSE) has been hailed as the key to developing safe and high-energy-density Li batteries. In particular, Li 1+ x Al x Ti 2- x (PO4) 3 (LATP) has been identified as a very attractive SSE for Li batteries due to its excellent electrochemical stability, low production costs, and good chemical compatibility. However, interfacial reactions with electrodes and poor thermal stability at high temperatures severely restrict the practical use of LATP in solid-state batteries (SSB). Herein, a systematic review of recent advances in LATP for SSBs is provided. Here, this review starts with a brief introduction to the development history of LATP and then summarizes its structure, ion transport mechanism, and synthesis methods. Challenges (e.g., intrinsic brittleness, interfacial resistance, and compatibility) and corresponding solutions (ionic substitution, additives, protective layers, composite electrolytes, etc.) that are critical for practical applications are then discussed. Last, an outlook on the future research direction of LATP-based SSB is provided.

25 ENERGY STORAGE↗

DOE OSTI2023

A new high voltage alluaudite sodium battery insertion material

Large-scale stationary storage forms a key sector that can be economically served by sodium-ion batteries. In realizing practical sodium-ion batteries, discovery and development of novel cathodes is essential. In this spirit, alluaudite-type Na 2 Fe 2 (SO 4 ) 3 was reported in 2014 to have the highest Fe 3+ /Fe 2+ redox potential (~3.8 V vs. Na). This finding led to reports on various PO4 3– and SO4 2– based alluaudite compounds exhibiting high energy densities. In 2017, MoO 4 2– based alluaudite, Na 2.67 Mn 1.67 (MoO 4 ) 3 , was found as a 3.45 V cathode material. Exploring molybdenum chemistry further, this work reports alluaudite type Na 3.36 Co 1.32 (MoO 4 ) 3 (NCMo) as a novel versatile electroactive cathode for Li-ion and Na-ion batteries. It was synthesized by a wet solution-combustion route with a restricted annealing duration of 1 min at 600 °C. Calorimetric study revealed the formation enthalpy from component oxides (ΔH° f,ox = –575.49 ± 7.75 kJ/mol) to be highly exothermic. Unlike the sulfate class of alluaudites, this material is highly stable in air and moisture (ΔH ds = 537.42 ± 0.78 kJ/mol). Having an ionic conductivity of 6.065 × 10 –8 S/cm (at 50 °C), it offers a pseudo two-dimensional Na + migration pathway. Without any material optimization, NCMo was found to work as a high-voltage insertion cathode (ca. 4.0 V vs. Na/Na + and 4.1 V vs. Li/Li + ) in sync with theoretically predicted potential of 3.98 V (vs. Na/Na + ). Ex-situ X-ray diffraction and photoelectron spectroscopy studies revealed the occurrence of solid-solution redox mechanism solely involving Co 3+ /Co 2+ redox centre. Finally, it benchmarks Na 3.36 Co 1.32 (MoO 4 ) 3 as a novel electrochemically active Mo-based alluaudite-type polyanionic cathode insertion material.

25 ENERGY STORAGE↗

DOE OSTI2020

Materials Data on P3(PbO3)4 by Materials Project

Pb4(PO4)3 crystallizes in the cubic I-43d space group. The structure is three-dimensional. Pb+2.50+ is bonded to six equivalent O2- atoms to form distorted PbO6 pentagonal pyramids that share corners with six equivalent PO4 tetrahedra and edges with three equivalent PbO6 pentagonal pyramids. There are three shorter (2.42 Å) and three longer (2.69 Å) Pb–O bond lengths. P+4.67+ is bonded to four equivalent O2- atoms to form PO4 tetrahedra that share corners with eight equivalent PbO6 pentagonal pyramids. All P–O bond lengths are 1.56 Å. O2- is bonded in a distorted single-bond geometry to two equivalent Pb+2.50+ and one P+4.67+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on Fe3P3PbO13 by Materials Project

PbFe3O(PO4)3 crystallizes in the monoclinic P2_1/m space group. The structure is three-dimensional. there are three inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to six O2- atoms to form distorted FeO6 octahedra that share corners with two equivalent FeO6 octahedra, corners with three PO4 tetrahedra, a cornercorner with one FeO5 trigonal bipyramid, and an edgeedge with one PO4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Fe–O bond distances ranging from 1.92–2.37 Å. In the second Fe3+ site, Fe3+ is bonded to six O2- atoms to form FeO6 octahedra that share corners with two equivalent FeO6 octahedra, corners with four PO4 tetrahedra, and edges with two equivalent FeO6 octahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Fe–O bond distances ranging from 2.01–2.17 Å. In the third Fe3+ site, Fe3+ is bonded to five O2- atoms to form FeO5 trigonal bipyramids that share a cornercorner with one FeO6 octahedra and corners with five PO4 tetrahedra. The corner-sharing octahedral tilt angles are 54°. There are a spread of Fe–O bond distances ranging from 1.90–2.02 Å. Pb2+ is bonded in a 7-coordinate geometry to seven O2- atoms. There are a spread of Pb–O bond distances ranging from 2.57–2.70 Å. There are three inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with two equivalent FeO6 octahedra, a cornercorner with one FeO5 trigonal bipyramid, and an edgeedge with one FeO6 octahedra. The corner-sharing octahedral tilt angles are 45°. There is three shorter (1.55 Å) and one longer (1.57 Å) P–O bond length. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four FeO6 octahedra and a cornercorner with one FeO5 trigonal bipyramid. The corner-sharing octahedra tilt angles range from 41–56°. There are a spread of P–O bond distances ranging from 1.53–1.58 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share a cornercorner with one FeO6 octahedra and corners with three equivalent FeO5 trigonal bipyramids. The corner-sharing octahedral tilt angles are 37°. There are a spread of P–O bond distances ranging from 1.52–1.56 Å. There are ten inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted trigonal planar geometry to two equivalent Fe3+ and one P5+ atom. In the second O2- site, O2- is bonded in a 2-coordinate geometry to two Fe3+ and one P5+ atom. In the third O2- site, O2- is bonded in a 2-coordinate geometry to one Fe3+, one Pb2+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a bent 150 degrees geometry to one Fe3+ and one P5+ atom. In the fifth O2- site, O2- is bonded in a 2-coordinate geometry to one Fe3+, one Pb2+, and one P5+ atom. In the sixth O2- site, O2- is bonded in a 3-coordinate geometry to one Fe3+, one Pb2+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a linear geometry to one Fe3+ and one P5+ atom. In the eighth O2- site, O2- is bonded in a 2-coordinate geometry to one Fe3+, one Pb2+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a bent 150 degrees geometry to one Fe3+ and one P5+ atom. In the tenth O2- site, O2- is bonded in a trigonal planar geometry to three Fe3+ atoms.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on CsTi3P5O19 by Materials Project

CsTi3(PO4)3(P2O7) crystallizes in the monoclinic Cc space group. The structure is three-dimensional. Cs1+ is bonded in a 6-coordinate geometry to six O2- atoms. There are a spread of Cs–O bond distances ranging from 3.10–3.64 Å. There are three inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of Ti–O bond distances ranging from 1.88–2.01 Å. In the second Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of Ti–O bond distances ranging from 1.89–2.01 Å. In the third Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There are a spread of Ti–O bond distances ranging from 1.91–2.05 Å. There are five inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 25–43°. There is two shorter (1.55 Å) and two longer (1.56 Å) P–O bond length. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with three TiO6 octahedra and a cornercorner with one PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 9–40°. There are a spread of P–O bond distances ranging from 1.51–1.62 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with three TiO6 octahedra and a cornercorner with one PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 9–38°. There are a spread of P–O bond distances ranging from 1.51–1.62 Å. In the fourth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 19–40°. There is two shorter (1.54 Å) and two longer (1.55 Å) P–O bond length. In the fifth P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 19–38°. There is two shorter (1.54 Å) and two longer (1.55 Å) P–O bond length. There are nineteen inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the second O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Cs1+, one Ti4+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a 2-coordinate geometry to one Cs1+, one Ti4+, and one P5+ atom. In the fifth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the sixth O2- site, O2- is bonded in a bent 150 degrees geometry to one Cs1+, one Ti4+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the eighth O2- site, O2- is bonded in a bent 150 degrees geometry to one Cs1+, one Ti4+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a bent 120 degrees geometry to two P5+ atoms. In the tenth O2- site, O2- is bonded in a linear geometry to one Ti4+ and one P5+ atom. In the eleventh O2- site, O2- is bonded in a linear geometry to one Ti4+ and one P5+ atom. In the twelfth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the thirteenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the fourteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Cs1+, one Ti4+, and one P5+ atom. In the fifteenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the sixteenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the seventeenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the eighteenth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Cs1+, one Ti4+, and one P5+ atom. In the nineteenth O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Materials Data on CsTi3P5O19 by Materials Project

CsTi3(PO4)3(P2O7) crystallizes in the monoclinic Cm space group. The structure is three-dimensional. Cs1+ is bonded in a 11-coordinate geometry to eleven O2- atoms. There are a spread of Cs–O bond distances ranging from 3.12–3.68 Å. There are two inequivalent Ti4+ sites. In the first Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share a cornercorner with one TiO6 octahedra and corners with five PO4 tetrahedra. The corner-sharing octahedral tilt angles are 31°. There are a spread of Ti–O bond distances ranging from 1.83–2.06 Å. In the second Ti4+ site, Ti4+ is bonded to six O2- atoms to form TiO6 octahedra that share corners with six PO4 tetrahedra. There is two shorter (1.95 Å) and four longer (1.96 Å) Ti–O bond length. There are three inequivalent P5+ sites. In the first P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with three TiO6 octahedra and a cornercorner with one PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 15–41°. There are a spread of P–O bond distances ranging from 1.52–1.62 Å. In the second P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with four TiO6 octahedra. The corner-sharing octahedra tilt angles range from 37–41°. All P–O bond lengths are 1.55 Å. In the third P5+ site, P5+ is bonded to four O2- atoms to form PO4 tetrahedra that share corners with three TiO6 octahedra and a cornercorner with one PO4 tetrahedra. The corner-sharing octahedra tilt angles range from 16–46°. There are a spread of P–O bond distances ranging from 1.52–1.61 Å. There are eleven inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the second O2- site, O2- is bonded in a bent 150 degrees geometry to one Cs1+, one Ti4+, and one P5+ atom. In the third O2- site, O2- is bonded in a 2-coordinate geometry to one Cs1+, one Ti4+, and one P5+ atom. In the fourth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Ti4+ and one P5+ atom. In the fifth O2- site, O2- is bonded in a distorted linear geometry to one Cs1+, one Ti4+, and one P5+ atom. In the sixth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Cs1+, one Ti4+, and one P5+ atom. In the seventh O2- site, O2- is bonded in a linear geometry to one Ti4+ and one P5+ atom. In the eighth O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Cs1+, one Ti4+, and one P5+ atom. In the ninth O2- site, O2- is bonded in a bent 150 degrees geometry to one Cs1+ and two equivalent Ti4+ atoms. In the tenth O2- site, O2- is bonded in a bent 120 degrees geometry to two P5+ atoms. In the eleventh O2- site, O2- is bonded in a bent 150 degrees geometry to one Cs1+, one Ti4+, and one P5+ atom.

36 MATERIALS SCIENCE↗

NASA NTRSDate not supplied

The Oxidation State of Sulfur in Martian Apatite- Implications for Redox of Surficial Processes

Meteorites from Mars record fO2 values of ∆IW = -1 to +6.5 [1, 2]. This relatively large range in fO2 has been attributed to igneous processes like differentiation and assimilation, or sometimes to alteration [2, 3], modifying the range inherited from the Martian mantle, which is thought to be closer to the values recorded by lunar basalts (~∆IW -1 [e.g., 1]). Trace element compositions reveal that those Martian meteorites that are light Rare Earth Elements (LREE) enriched record higher fO2 values than those that are LREE-depleted [2]. Sulfur (S) has been used to track redox and alteration processes on Mars because it can be present in multiple redox states varying from S2- in magmatic sulfides to S6+ in sedimentary sulfate deposits and alteration products like jarosite [4, 5]. Apatite (Ca5(PO4)3(F,Cl,OH)) is found in many of the Martian meteorites as a late stage crystallizing mineral. It can incorporate both S^(2-) [6] or S^(6+) [7] or mixtures of both [7, 8] in its crystal structure, and it has been hypothesized that the relative proportions of S^(2-) and S^(6+) in apatite will depend on the prevailing fO2 in which it formed (along with P, T, and major element composition). Note: Extended abstract on document.

P. Chowdhury↗

DOE OSTI2020

Biomimetic composite architecture achieves ultrahigh rate capability and cycling life of sodium ion battery cathodes

Sodium ion batteries are an emerging candidate to replace lithium ion batteries in large-scale electrical energy storage systems due to the abundance and widespread distribution of sodium. Despite the growing interest, the development of high-performance sodium cathode materials remains a challenge. In particular, polyanionic compounds are considered as a strong cathode candidate owing to their better cycling stability, a flatter voltage profile, and stronger thermal stability compared to other cathode materials. Here, we report the rational design of a biomimetic bone-inspired polyanionic Na3V2(PO4)3-reduced graphene oxide composite (BI-NVP) cathode that achieves ultrahigh rate charging and ultralong cycling life in a sodium ion battery. At a charging rate of 1 C, BI-NVP delivers 97% of its theoretical capacity and is able to retain a voltage plateau even at the ultra-high rate of 200 C. It also shows long cycling life with capacity retention of 91% after 10 000 cycles at 50 C. The sodium ion battery cells with a BI-NVP cathode and Na metal anode were able to deliver a maximum specific energy of 350 W h kg−1 and maximum specific power of 154 kW kg−1. In situ and postmortem analyses of cycled BI-NVP (including by Raman and XRD spectra) HRTEM, and STEM-EELS, indicate highly reversible dilation–contraction, negligible electrode pulverization, and a stable NVP-reduced graphene oxide layer interface. The results presented here provide a rational and biomimetic material design for the electrode architecture for ultrahigh power and ultralong cyclability of the sodium ion battery full cells when paired with a sodium metal anode.

25 ENERGY STORAGE↗

DOE OSTI2020

Ion beam irradiation of ABO4 compounds with the fergusonite, monazite, scheelite, and zircon structures

The effects of irradiation on CaWO4, SrWO4, BaWO4, YVO4, LaVO4, YNbO4, and LaNbO4 were investigated on thin crystals using 1.0 MeV Kr ions at 50-1000 K. All of the ABO4 compounds can be amorphized with calculated damage cross sections (σa = 1/Fc0) in the range of ~0.30-1.09 × 10-14 cm2 ion-1 at zero Kelvin. The analysis of fluence-temperature data returned critical temperatures for amorphization (Tc) of 311 ± 1, 358 ± 90, 325 ± 19, 415 ± 17, 541 ± 6, 636 ± 26, and 1012 ± 1 K, respectively, for the compounds listed above. Compared with previous in situ irradiation of ABO4 orthophosphate samples using 0.8 MeV Kr ions, the Tc values of LaVO4 and YVO4 are higher than those of LaPO4 and YPO4 by 82 K and 124 K, respectively. The Tc values of the three scheelite structures, CaWO4, SrWO4, and BaWO4, indicate that they are the most radiation tolerant compounds under these conditions. The A-B cation anti-site energies, EfAB, determined by DFT range from 2.48 to 10.58 eV and are highly correlated with the A-B cation ionic radius ratio, rA/rB, but are not correlated with Tc across the different structure types, suggesting that the formation and migration energies of Frenkel defects play a more important role in damage recovery in these compounds. We also discuss the role of cation and anion charge/iconicity as determined by DFT. ABO4 compounds with the zircon structure and B = P or V have a distinct advantage over those with B = Si as the damaged regions do not appear to be significantly affected by polymerization of (PO4) 3- or (VO4) 3- groups which might stabilize the amorphous fraction and ultimately lead to phase separation as observed in zircon (ZrSiO4).

amorphization↗

NASA NTRS1988

Particulate emissions from a mid-latitude prescribed chaparral fire

Particulate emission from a 400-acre prescribed chaparral fire in the San Dimas Experimental Forest was investigated by collecting smoke aerosol on Teflon and glass-fiber filters from a helicopter, and using SEM and EDAX to study the features of the particles. Aerosol particles ranged in size from about 0.1 to 100 microns, with carbon, oxygen, magnesium, aluminum, silicon, calcium, and iron as the primary elements. The results of ion chromatographic analysis of aerosol-particle extracts (in water-methanol) revealed the presence of significant levels of NO2(-), NO3(-), SO4(2-), Cl(-), PO4(3-), C2O4(2-), Na(+), NH4(+), and K(+). The soluble ionic portion of the aerosol was estimated to be about 2 percent by weight.

Cofer, Wesley R., III↗

NASA NTRS2000

Measures of Water Quality in Merrit Island National Wildlife Refuge Impoundments and Adjacent Indian River Lagoon

The goal of this project was to conduct preliminary investigations to determine appropriate sampling strategies to measure the flux of dissolved nutrients (specifically, NH4+, NO3-, NO2-, and PO4(3-)) and suspended particulate matter (TSS) between impoundments and the IRL in preparation for an intensive three-year monitoring program. In addition to nutrients and TSS, a variety of common water quality indicators were also measured during these preliminary studies. Six impoundments and a single restored marsh were selected for study. Over a month long period, water samples were collected weekly at selected impoundment culverts. Water was collected in duplicate as independent grab samples from both the lagoon side and within the perimeter ditch directly adjacent to the culverts. Water quality indicators inside and outside the marsh impoundments were different. Ammonium, salinity, bacteria, and chlorophyll-a were higher inside the impoundments as expected possibly as a result of the great affect of evaporation on impoundment water. Water quality indicators responded rapidly both inside and outside the impoundments as exemplified by the increase in NH4(+)-N concentrations during a horseshoe crab die-off. Water quality indicators were high variable during the month in which water samples were collected. Because the impoundments are widely spaced it is logistically unrealistic to sample each of the impoundments and associated seagrass beds on a single day, sampling must be stratified to allow patterns of material movement and the annual flux of materials to and from the impoundments to be determined.

Blum, Linda K.↗

NASA NTRS2016

Apatite-Melt Partitioning at 1 Bar: An Assessment of Apatite-Melt Exchange Equilibria Resulting from Non-Ideal Mixing of F and Cl in Apatite

The mineral apatite [Ca5(PO4)3(F,Cl,OH)] is present in a wide range of planetary materials. Due to the presence of volatiles within its crystal structure (X-site), many recent studies have attempted to use apatite to constrain the volatile contents of planetary magmas and mantle sources. In order to use the volatile contents of apatite to precisely determine the abundances of volatiles in coexisting silicate melt or fluids, thermodynamic models for the apatite solid solution and for the apatite components in multi-component silicate melts and fluids are required. Although some thermodynamic models for apatite have been developed, they are incomplete. Furthermore, no mixing model is available for all of the apatite components in silicate melts or fluids, especially for F and Cl components. Several experimental studies have investigated the apatite-melt and apatite-fluid partitioning behavior of F, Cl, and OH in terrestrial and planetary systems, which have determined that apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, McCubbin et al. recently reported that the exchange coefficients may vary in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. In particular, solution calorimetry data of apatite compositions along the F-Cl join exhibit substantial excess enthalpies of mixing. In the present study, we conducted apatite-melt partitioning experiments in evacuated, sealed silica-glass tubes at approximately 1 bar and 950-1050 degrees Centigrade on a synthetic Martian basalt composition equivalent to the basaltic shergottite Queen Alexandria Range (QUE) 94201. These experiments were conducted dry, at low pressure, to assess the effects of temperature and apatite composition on the partitioning behavior of F and Cl between apatite and basaltic melt along the F-Cl apatite binary join, where there is non-ideal mixing of F and Cl in apatite.

McCubbin, F. M.↗