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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

High-pressure phase transitions and melt structure of Pb O 2 : An analog for silica

In situ x-ray diffraction measurements and inverse Monte Carlo simulations of pair distribution functions were used to study the structural response of PbO 2 under pressure and to characterize the local structure of liquid PbO 2 . Two phase transitions are observed upon room-temperature compression of crystalline PbO 2 up to ~65 GPa. Here, the starting mixture of rutile structured β– PbO 2 and orthorhombic α– PbO 2 undergoes a transition to a ZrO 2 -type orthorhombic phase with space group Pbca at ~21 GPa. Above 42 GPa, the Pbca phase transforms to a cotunnite-type phase with space group Pnam. In this paper, we also report short-range order in liquid PbO 2 , showing ~8–9-fold and 4–5-fold coordination around Pb and O atoms, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Do Piperonyl Butoxide Long-Lasting Insecticide Treated Nets Provide Additional Protection Against Malaria Infections Compared with Conventional Nets in an Operational Setting in Western Kenya?

Malaria control in sub-Saharan Africa has stagnated despite widespread adoption of control measures such as long-lasting insecticidal nets (LLINs). Progress has stalled, in part, because of pyrethroid insecticide resistance, driving the need for retooling to increase the effectiveness of bed nets. Consequently, LLINs have been treated with the chemical synergist piperonyl butoxide (PBO). Piperonyl butoxide LLINs have been shown to be efficacious in controlled settings; however, their effectiveness in real-world settings warrants investigation. In Bungoma County, Western Kenya, a cohort of 768 participants was followed from June 2017 to December 2023 via active and passive surveillance. Household visits were conducted monthly, during which LLIN use for nets distributed in 2017 and 2021 was recorded, and symptomatic malaria cases were identified using rapid diagnostic tests (RDTs). The comparative effectiveness of PBO versus conventional LLINs was assessed in terms of malaria infections. A multilevel logistic regression model was fit with monthly RDT results as the dependent variable. The study results indicate that PBO LLINs provide greater protection against malaria at the individual level than conventional LLINs (odds ratio: 0.70; 95% CI: 0.47–1.03), although the findings were not statistically significant. The added protection against malaria infections provided by PBO LLINs compared with conventional LLINs observed in the current study aligns with findings from most previous studies, although this finding was not statistically significant. In areas with documented pyrethroid resistance, the use of LLINs with an added synergist, such as PBO, can provide additional protection against malaria infections (compared with pyrethroid-only LLINs) and should be considered for scaled-up scenarios despite the additional cost.

60 APPLIED LIFE SCIENCES↗
NASA NTRS1993

Polybenzoxazole via aromatic nucleophilic displacement

Polybenzoxazoles (PBO) are heterocyclic macromolecules which were first synthesized in a two-step process by the initial formation of aromatic diacid chlorides with bis(o-aminophenol)s through solution condensation of aromatic diacid chlorides with bis(o-aminophenol)s followed by thermal cyclodehydration. Since then several methods were utilized in their synthesis. The most common synthetic method for PBO involves a polycondensation of bis(o-aminophenol)s with aromatic diacid diphenyl esters. Another preparative route involves the solution polycondensation of the hydrochloride salts of bis(o-amino phenol)s with aromatic diacids in polyphosphoric acid. Another synthetic method involves the initial formation of poly(o-hydroxy amide)s from silylated bis(o-aminophenol)s with aromatic diacid chlorides followed by thermal cyclodehydration to PBO. A recent preparative route involves the reaction of aromatic bisphenols with bis(fluorophenyl) benzoxazoles by the displacement reaction to form PBO. The novelty of the present invention is that high molecular weight PBO of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Hergenrother, Paul M.↗
NASA NTRS1995

Development and evaluation of polybenzoxazole fibrous structures

Woven and braided polybenzoxazole (PBO) structures have been developed for aerospace applications. The properties of PBO fibers are compared to those of other high performance fibers. PBO is unique for combining excellent flammability properties with the highest tensile strength and modulus of all synthetic organic fibers. The PBO structures are specifically developed to be compared to similar Kevlar structures. The physical, mechanical, thermal, and oxidative properties of the PBO woven and braided structures are determined. The resistance to various chemicals and to UV light is evaluated. Recommendations for specific aerospace applications are given with comments for further development and industrial applications.

Orndoff, Evelyne↗
NASA NTRS1959

Lubricating Properties of Lead-Monoxide-Base Coatings of Various Compositions at Temperatures to 1250 F

A number of ceramic coatings of different compositions containing lead monoxide (PbO) were studied to determine their relative merits as dry-film lubricants. Lead monoxide is known to be an effective solid lubricant at elevated temperatures, and this oxide was the main component in all compositions studied. Friction and wear properties were determined at temperatures from 750 to 1250 F, at a sliding velocity of 430 feet per minute, and at a normal load of 1 kilogram. In all of the coatings, PbO was the component primarily responsible for the lubricating properties. Oxides other than PbO had an indirect effect on lubrication by influencing such properties as adhesion, hardness, vitrifying or glaze-forming tendency, melting or softening point, and chemical stability of the coatings. Notable among these oxides were magnetite (Fe3O4.), which had generally a beneficial influence on ceramic- to-metal adhesion, and silica (SiO2), which inhibited the oxidation of PbO and enhanced the tendency for glaze formation on the sliding surfaces. Several of the compositions studied provided protection against metal-to-metal adhesive wear, galling, or seizure at test temperatures from 750 to 1250 F. Coating friction coefficients ranged from 0.20 to 0.37 at 75 F but were around 0.08 to 0.20 at temperatures of 1250 F.

Sliney, Harold E.↗
NASA NTRS2008

Hybrid Wound Filaments for Greater Resistance to Impacts

A hybrid material containing wound filaments made of a hybrid of high-strength carbon fibers and poly(phenylene benzobisoxazole) [PBO] fibers is discussed. This hybrid material is chosen in an effort to increase the ability of the pressure vessel to resist damage by low-speed impacts (e.g., dropping of tools on the vessel or bumping of the vessel against hard objects during installation and use) without significantly increasing the weight of the vessel. While the basic concept of hybridizing fibers in filament-wound structures is not new, the use of hybridization to increase resistance to impacts is an innovation, and can be expected to be of interest in the composite-pressure-vessel industry. The precise types and the proportions of the high-strength carbon fibers and the PBO fibers in the hybrid are chosen, along with the filament-winding pattern, to maximize the advantageous effects and minimize the disadvantageous effects of each material. In particular, one seeks to (1) take advantage of the ability of the carbon fibers to resist stress rupture while minimizing their contribution to vulnerability of the vessel to impact damage and (2) take advantage of the toughness of the PBO fibers while minimizing their contribution to vulnerability of the vessel to stress rupture. Experiments on prototype vessels fabricated according to this concept have shown promising results. At the time of reporting the information for this article, research toward understanding and optimizing the performances of PBO fibers so as to minimize their contribution to vulnerability of the pressure vessel to stress rupture had yet to be performed.

DeLay, Thomas K.↗
DOE OSTI2022

Excellent antioxidizing, thermally insulating and flame resistance silica‐polybenzoxazine aerogels for aircraft ablative materials

Abstract High‐performance thermal protective composites with lightweight, micro‐ ablation and high‐efficient thermal insulation are urgently required for thermal protection systems in advanced hypersonic speed vehicles. However, the practical applications of thermal protective composites have long been hampered by the main issues such as low mass residual rate and poor long‐term antioxidation of the matrix in high‐temperature aerobic environments. Here, we report a novel silica‐polybenz oxazine (SiO 2 ‐PBO) aerogels with interpenetrated networks, possessing the ability to antioxidation, thermal insulation, and flame‐retardant properties. The resulting SiO 2 ‐PBO aerogels exhibit low density (0.25 g/cm 3 ), low thermal conductivity (0.035 W/(m·K)), and superior peak heat release rate value (15.3 W/g). Moreover, the mass residual rate is up to 70.46 wt% in the N 2 atmosphere and remains 57.83 wt% despite existing in the air atmosphere and experiencing the highest temperature of 800°C. Briefly, SiO 2 ‐PBO aerogels as‐prepared could be a potential matrix for a new gene ration of high‐performance thermal protective composites in the future.

Xiao, Yunyun↗
DOE OSTI2022

Study of alkaline carbonate cooling to mitigate Ex-Vessel molten corium accidents

To mitigate adverse effects from molten corium following a reactor pressure vessel failure (RPVF), some new reactor designs employ a core catcher and a sacrificial material (SM), such as ceramic or concrete, to stabilize the molten corium and avoid containment breach. Existing reactors cannot easily be modified to include these SMs but could be modified to allow injectable cooling materials. Current reactor designs are limited to using water to stabilize the corium, but this can create other issues such as reaction of water with the concrete forming hydrogen gas. Here the novel SM proposed is a granular carbonate mineral that can be used in existing light water reactor plants. The granular carbonate will decompose when exposed to heat, inducing an endothermic reaction to quickly solidify the corium in place and producing a mineral oxide and carbon dioxide. Corium spreading is a complex process strongly influenced by coupled chemical reactions, including decay heat from the corium, phase change, and reactions between the concrete containment and available water. A recently completed Sandia National Laboratories laboratory directed research and development (LDRD) project focused on two research areas: experiments to demonstrate the feasibility of the novel SM concept, and modeling activities to determine the potential applications of the concept to actual nuclear plants. Small-scale experiments using lead oxide (PbO) as a surrogate for molten corium demonstrate that the reaction of the SM with molten PbO results in a fast solidification of the melt due to the endothermic carbonate decomposition reaction and the formation of open pore structures in the solidified PbO from CO 2 released during the decomposition. A simplified carbonate decomposition model was developed to predict thermal decomposition of carbonate mineral in contact with corium. This model was incorporated into MELCOR, a severe accident nuclear reactor code. A full-plant MELCOR simulation suggests that by the introduction of SM to the reactor cavity prior to RPVF ex-vessel accident progression, e.g., core-concrete interaction and core spreading on the containment floor, could be delayed by at least 15 h; this may be enough for additional accident management to be implemented to alleviate the situation.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2020

Materials Data on Pb2ClO2 by Materials Project

(PbO)4Cl2 crystallizes in the tetragonal I4/mmm space group. The structure is two-dimensional and consists of two hydrochloric acid molecules and two PbO sheets oriented in the (0, 0, 1) direction. In each PbO sheet, Pb is bonded in a 4-coordinate geometry to four equivalent O atoms. All Pb–O bond lengths are 2.35 Å. O is bonded to four equivalent Pb atoms to form a mixture of edge and corner-sharing OPb4 tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on H2Pb4SO8 by Materials Project

(H(PbO)2)2SO4 crystallizes in the triclinic P-1 space group. The structure is one-dimensional and consists of two sulfuric acid molecules and one H(PbO)2 ribbon oriented in the (0, 1, 0) direction. In the H(PbO)2 ribbon, there are four inequivalent Pb4+ sites. In the first Pb4+ site, Pb4+ is bonded in a 3-coordinate geometry to three O2- atoms. There are a spread of Pb–O bond distances ranging from 2.33–2.37 Å. In the second Pb4+ site, Pb4+ is bonded in a 4-coordinate geometry to four O2- atoms. There are a spread of Pb–O bond distances ranging from 2.30–2.71 Å. In the third Pb4+ site, Pb4+ is bonded in a 5-coordinate geometry to three O2- atoms. There are a spread of Pb–O bond distances ranging from 2.28–2.43 Å. In the fourth Pb4+ site, Pb4+ is bonded in a 3-coordinate geometry to three O2- atoms. There are one shorter (2.34 Å) and two longer (2.40 Å) Pb–O bond lengths. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.98 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted single-bond geometry to three Pb4+ and one H1+ atom. In the second O2- site, O2- is bonded to four Pb4+ atoms to form a mixture of corner and edge-sharing OPb4 tetrahedra. In the third O2- site, O2- is bonded in a single-bond geometry to two Pb4+ and one H1+ atom. In the fourth O2- site, O2- is bonded to four Pb4+ atoms to form a mixture of corner and edge-sharing OPb4 tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on HPb3ClO3 by Materials Project

(H(PbO)3)2Cl2 crystallizes in the orthorhombic Pmc2_1 space group. The structure is two-dimensional and consists of four hydrochloric acid molecules and one H(PbO)3 sheet oriented in the (0, 1, 0) direction. In the H(PbO)3 sheet, there are six inequivalent Pb2+ sites. In the first Pb2+ site, Pb2+ is bonded in a 3-coordinate geometry to three O2- atoms. There are two shorter (2.22 Å) and one longer (2.45 Å) Pb–O bond lengths. In the second Pb2+ site, Pb2+ is bonded in a 4-coordinate geometry to four O2- atoms. There are two shorter (2.43 Å) and two longer (2.45 Å) Pb–O bond lengths. In the third Pb2+ site, Pb2+ is bonded in a 3-coordinate geometry to three O2- atoms. There are two shorter (2.30 Å) and one longer (2.41 Å) Pb–O bond lengths. In the fourth Pb2+ site, Pb2+ is bonded in a 7-coordinate geometry to four O2- atoms. There are two shorter (2.42 Å) and two longer (2.43 Å) Pb–O bond lengths. In the fifth Pb2+ site, Pb2+ is bonded in a 3-coordinate geometry to three O2- atoms. There are two shorter (2.25 Å) and one longer (2.38 Å) Pb–O bond lengths. In the sixth Pb2+ site, Pb2+ is bonded in a 3-coordinate geometry to three O2- atoms. There are two shorter (2.30 Å) and one longer (2.37 Å) Pb–O bond lengths. There are two inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. In the second H1+ site, H1+ is bonded in a single-bond geometry to one O2- atom. The H–O bond length is 0.99 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded to four Pb2+ atoms to form a mixture of corner and edge-sharing OPb4 tetrahedra. In the second O2- site, O2- is bonded to four Pb2+ atoms to form a mixture of corner and edge-sharing OPb4 tetrahedra. In the third O2- site, O2- is bonded in a distorted single-bond geometry to two Pb2+ and one H1+ atom. In the fourth O2- site, O2- is bonded in a distorted single-bond geometry to two Pb2+ and one H1+ atom.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Pb3NO6 by Materials Project

(PbO)3NO3 crystallizes in the orthorhombic Pca2_1 space group. The structure is two-dimensional and consists of four nitric acid molecules and two PbO sheets oriented in the (0, 0, 1) direction. In each PbO sheet, there are three inequivalent Pb sites. In the first Pb site, Pb is bonded in a 4-coordinate geometry to four O atoms. There are a spread of Pb–O bond distances ranging from 2.33–2.42 Å. In the second Pb site, Pb is bonded in a 4-coordinate geometry to four O atoms. There are a spread of Pb–O bond distances ranging from 2.29–2.76 Å. In the third Pb site, Pb is bonded in a 3-coordinate geometry to three O atoms. There are a spread of Pb–O bond distances ranging from 2.28–2.35 Å. There are three inequivalent O sites. In the first O site, O is bonded to four Pb atoms to form a mixture of corner and edge-sharing OPb4 tetrahedra. In the second O site, O is bonded to four Pb atoms to form a mixture of corner and edge-sharing OPb4 tetrahedra. In the third O site, O is bonded in a distorted L-shaped geometry to three Pb atoms.

36 MATERIALS SCIENCE↗
NASA NTRS1997

Three-Dimensional Polybenzobisoxazoles and Polybenzobisthiazoles

Due to the poor compressive strength properties of high performance liquid crystalline polymers such as polybenzobisoxazoles (PBOs) and polybenzobisthiazoles (PBTs), we have prepared homopolymers and copolymers with PBO and PBT pendant groups on a central star-like unit, 2.7-diamino-9,9'-bis(4-aminophenyl)fluorene, in order to improve upon their compressive strength properties. The fluorene moiety was prepared by the reaction of 2,7-dinitro-9-fluorene with aniline and aniline hydrochloride, followed by reduction with palladium on carbon. The central star-like unit was characterized by FTIR, FTNMR, and elemental analysis. The PBO and PBT pendant groups were synthesized by the polycondensation of 4,6-diaminoresorcinol dihydrochloride with terephthaloyl chloride and 2,5-diamino-1,4-benzendithiol dihydrochloride with terephthaloyl chloride in poly(phosphoric acid), respectively. The resulting linear polymers containing the dicarboxylic end groups were attached to the central star-like unit by refluxing with 2,7-diamino-9,9'-bis(4-aminophenyl) fluorene to give the star-like polymers. The star-like PBO and PBT were soluble in methanesulfonic acid. Further characterization of the polymers is ongoing.

Bray, M.↗
DOE OSTI2023

Lead leaching and electrowinning in acetic acid for solar module recycling

It is imperative to recover lead (Pb) contained in end-of-life solar modules. In this paper, a two-step leaching and electrowinning process using acetic acid is investigated for Pb recovery. Acetic acid with hydrogen peroxide can dissolve Pb quickly and, under some conditions, in a matter of minutes. Pb electrowinning has been successfully demonstrated from aqueous solutions of 0.009 M lead(II) acetate with 0–10% v/v acetic acid. Pb-containing deposits are found on both the copper cathode and graphite anode. X-ray diffraction, energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy confirm the presence of metallic Pb and Pb(II) oxide (PbO) co-deposits on the cathode. Further, there is also the formation of lead subacetate on the cathode under certain conditions. On the anode, the deposit consists of lead(IV) oxide and superoxide (PbO 2 and Pb 1–x O 2 ). A Pb recovery rate of 99% is achieved in 0.009 M lead(II) acetate solutions with 10% v/v acetic acid by applying a reduction potential of either –0.8 V or –1.0 V versus the silver/silver chloride reference electrode for 24h. Pb leaching with acetic acid is also demonstrated from milled silicon solar modules.

14 SOLAR ENERGY↗
DOE OSTI2020

Materials Data on AgPbBrO by Materials Project

AgBrPbO crystallizes in the tetragonal P4/nmm space group. The structure is two-dimensional and consists of one AgBr sheet oriented in the (0, 0, 1) direction and one PbO sheet oriented in the (0, 0, 1) direction. In the AgBr sheet, Ag1+ is bonded to five equivalent Br1- atoms to form a mixture of corner and edge-sharing AgBr5 square pyramids. There are four shorter (2.86 Å) and one longer (2.94 Å) Ag–Br bond lengths. Br1- is bonded to five equivalent Ag1+ atoms to form a mixture of corner and edge-sharing BrAg5 square pyramids. In the PbO sheet, Pb2+ is bonded in a 4-coordinate geometry to four equivalent O2- atoms. All Pb–O bond lengths are 2.35 Å. O2- is bonded to four equivalent Pb2+ atoms to form a mixture of corner and edge-sharing OPb4 tetrahedra.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Recycling of Lead Pastes from Spent Lead–Acid Batteries: Thermodynamic Constraints for Desulphurization

Lead–acid batteries are important to modern society because of their wide usage and low cost. The primary source for production of new lead–acid batteries is from recycling spent lead–acid batteries. In spent lead–acid batteries, lead is primarily present as lead pastes. In lead pastes, the dominant component is lead sulfate (PbSO 4 , mineral name anglesite) and lead oxide sulfate (PbO•PbSO 4 , mineral name lanarkite), which accounts for more than 60% of lead pastes. In the recycling process for lead–acid batteries, the desulphurization of lead sulfate is the key part to the overall process. In this work, the thermodynamic constraints for desulphurization via the hydrometallurgical route for recycling lead pastes are presented. The thermodynamic constraints are established according to the thermodynamic model that is applicable and important to recycling of lead pastes via hydrometallurgical routes in high ionic strength solutions that are expected to be in industrial processes. The thermodynamic database is based on the Pitzer equations for calculations of activity coefficients of aqueous species. The desulphurization of lead sulfates represented by PbSO 4 can be achieved through the following routes. (1) conversion to lead oxalate in oxalate-bearing solutions; (2) conversion to lead monoxide in alkaline solutions; and (3) conversion to lead carbonate in carbonate solutions. Among the above three routes, the conversion to lead oxalate is environmentally friendly and has a strong thermodynamic driving force. Oxalate-bearing solutions such as oxalic acid and potassium oxalate solutions will provide high activities of oxalate that are many orders of magnitude higher than those required for conversion of anglesite or lanarkite to lead oxalate, in accordance with the thermodynamic model established for the oxalate system. An additional advantage of the oxalate conversion route is that no additional reductant is needed to reduce lead dioxide to lead oxide or lead sulfate, as there is a strong thermodynamic force to convert lead dioxide directly to lead oxalate. As lanarkite is an important sulfate-bearing phase in lead pastes, this study evaluates the solubility constant for lanarkite regarding the following reaction, based on the solubility data, PbO•PbSO 4 + 2H + ⇌ 2Pb 2+ + SO 4 2– + H 2 O(l).

25 ENERGY STORAGE↗
NASA NTRS1986

Conductimetric determination of decomposition of silicate melts

A description of a procedure is given to detect decomposition of silicate systems in the liquid state by conductivity measurements. Onset of decomposition can be determined from the temperature curves of resistances measured on two pairs of electrodes, one above the other. Degree of decomposition can be estimated from temperature and concentration dependency of conductivity of phase boundaries. This procedure was tested with systems PbO-B2O3 and PbO-B2O3-SiO2.

Kroeger, C.↗