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13 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Synthesis and Morphological Characterization of Electroless-Deposited Ni-P Coatings on Diamond Abrasives

Deposition of a coating on rough surfaces faces unique challenges due to the complexity of substrate morphology. In the present research, electroless deposition of a Ni-P coating was successfully deposited on diamond particles. Microtomography was conducted to study the deposition mechanisms. It revealed that the coating coverage rate on diamond particles was affected by the synergistic action of the deposition time, substrate morphology, and hypophosphite concentration. The best coverage was achieved in a solution with 0.2 mol/L hypophosphite. Two major morphological features of the coating: nodular and smooth, were influenced by the deposition parameters, coating integrity, and substrate morphology. The failure was seen in fractured and peeled off coatings. It was due to residual stress produced by the coalescing of crystallites during the deposition. This failure mechanism explains the tendency of coating fracture at three morphological features of the substrate. This work is beneficial to semiconductor manufacturing where effective cutting in chip fabrication is essential.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Use of Refractory-Volatile Element Deep Eutectic Regions to Grow Single Crystalline Intermetallic Compounds

Compounds containing both refractory and volatile elements present a unique challenge for crystal growth, given the conflicting realities of high melting temperatures and high vapor pressures. Nevertheless, the discovery of superconductivity in FeAs and FeSe based materials and a Weyl semimetal state in TaP are motivations to explore compounds containing such pairs. Here, we discuss use of the low-melting single phase liquid regions above deep M-X eutectics (M=transition metal, X=P, S) as the basis for high temperature solutions for growing intermetallic compounds containing volatile-refractory pairs. We show that Ni-P, Pd-P, Pt-P, and Pd-S compositions form single phase melts at moderate temperatures below 1000 °C and with minimal vapor pressure. We first present the simple case of growing Ni 2 P from Ni-P and next discuss the more complicated growth of RPd 3 S 4 (R=La, Ce, Nd, Eu) from a Pd-S melt. We show how frit-disc alumina crucible sets allow for contamination-free capture of decanted liquid and its reuse in subsequent experiments, demonstrating a fractionation of the CePd 3 S 4 growth to determine the optimal conditions for crystal growth. We conclude by using the single phase liquid regions above the Pt-P and Pd-P eutectics to grow single crystals of MPt 5 P (M=Mn, Fe) and MnPd 5 P. As these materials have primarily been studied in polycrystalline form, we give an overview of the magnetic and transport properties of our single crystals. The examples outlined here illustrate the utility of using the single phase liquid above deep metal-X eutectics for solution growth and materials discovery.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Single Crystal Growth of Synthetic Sulfide- and Phosphide-Based Minerals for Physical Measurements

In this work, we review recent advances in the use of high-temperature solution growth that allow for the growth of single crystalline samples of synthetic minerals. We outline how low-melting binary or ternary solutions are attractive solvents for solution growth and provide examples of the growth of bismuthinite (Bi 2 S 3 ), galena (PbS) and parkerite (Ni 3 Bi 2 S 2 ). We then focus on the Rh-S, Pd-S and Ni-P phase spaces to discuss how the low-melting regions near transition metal-main group eutectic compositions make excellent solvents for crystal growth of several binary and ternary minerals containing both high melting and volatile elements as well as for the discovery of new materials. We end by discussing the growth of synthetic canfieldite (Ag 8 SnS 6 ) and argyrodite (Ag 8 GeS 6 ) from Ag 2 S–Sn-S-based solutions.

58 GEOSCIENCES↗
DOE OSTI2020

Materials Data on Ni12P5 by Materials Project

Ni12P5 crystallizes in the tetragonal I4/m space group. The structure is three-dimensional. there are two inequivalent Ni+1.25+ sites. In the first Ni+1.25+ site, Ni+1.25+ is bonded to four P3- atoms to form a mixture of edge and corner-sharing NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.21–2.45 Å. In the second Ni+1.25+ site, Ni+1.25+ is bonded in a distorted see-saw-like geometry to four equivalent P3- atoms. There are two shorter (2.23 Å) and two longer (2.58 Å) Ni–P bond lengths. There are two inequivalent P3- sites. In the first P3- site, P3- is bonded in a body-centered cubic geometry to eight equivalent Ni+1.25+ atoms. In the second P3- site, P3- is bonded in a 10-coordinate geometry to ten Ni+1.25+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ni2P by Materials Project

Ni2P crystallizes in the hexagonal P-62m space group. The structure is three-dimensional. there are two inequivalent Ni+1.50+ sites. In the first Ni+1.50+ site, Ni+1.50+ is bonded to five P3- atoms to form distorted NiP5 trigonal bipyramids that share corners with six equivalent NiP4 tetrahedra, corners with ten equivalent NiP5 trigonal bipyramids, edges with six equivalent NiP4 tetrahedra, and edges with six equivalent NiP5 trigonal bipyramids. There are one shorter (2.34 Å) and four longer (2.46 Å) Ni–P bond lengths. In the second Ni+1.50+ site, Ni+1.50+ is bonded to four P3- atoms to form NiP4 tetrahedra that share corners with ten equivalent NiP4 tetrahedra, corners with six equivalent NiP5 trigonal bipyramids, edges with two equivalent NiP4 tetrahedra, and edges with six equivalent NiP5 trigonal bipyramids. There are two shorter (2.21 Å) and two longer (2.27 Å) Ni–P bond lengths. There are two inequivalent P3- sites. In the first P3- site, P3- is bonded in a 9-coordinate geometry to nine Ni+1.50+ atoms. In the second P3- site, P3- is bonded in a 9-coordinate geometry to nine Ni+1.50+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ni5P4 by Materials Project

Ni5P4 crystallizes in the hexagonal P6_3mc space group. The structure is three-dimensional. there are four inequivalent Ni2+ sites. In the first Ni2+ site, Ni2+ is bonded to five P+2.50- atoms to form distorted NiP5 trigonal bipyramids that share corners with two equivalent PNiP3 tetrahedra, corners with five equivalent NiP4 tetrahedra, corners with eight NiP5 trigonal bipyramids, corners with two equivalent NiP4 trigonal pyramids, edges with two equivalent NiP4 tetrahedra, edges with three NiP5 trigonal bipyramids, and a faceface with one NiP5 trigonal bipyramid. There are a spread of Ni–P bond distances ranging from 2.29–2.46 Å. In the second Ni2+ site, Ni2+ is bonded to four P+2.50- atoms to form NiP4 trigonal pyramids that share corners with twelve NiP5 trigonal bipyramids and edges with three equivalent NiP4 tetrahedra. There are three shorter (2.16 Å) and one longer (2.19 Å) Ni–P bond lengths. In the third Ni2+ site, Ni2+ is bonded to four P+2.50- atoms to form distorted NiP4 tetrahedra that share a cornercorner with one PNiP3 tetrahedra, corners with four equivalent NiP4 tetrahedra, corners with ten NiP5 trigonal bipyramids, edges with four NiP5 trigonal bipyramids, and an edgeedge with one NiP4 trigonal pyramid. There are a spread of Ni–P bond distances ranging from 2.27–2.46 Å. In the fourth Ni2+ site, Ni2+ is bonded to five P+2.50- atoms to form distorted NiP5 trigonal bipyramids that share corners with two equivalent PNiP3 tetrahedra, corners with five equivalent NiP4 tetrahedra, corners with eight NiP5 trigonal bipyramids, corners with two equivalent NiP4 trigonal pyramids, edges with two equivalent NiP4 tetrahedra, edges with three NiP5 trigonal bipyramids, and a faceface with one NiP5 trigonal bipyramid. There are a spread of Ni–P bond distances ranging from 2.28–2.41 Å. There are four inequivalent P+2.50- sites. In the first P+2.50- site, P+2.50- is bonded in a q6 geometry to nine Ni2+ atoms. In the second P+2.50- site, P+2.50- is bonded to one Ni2+ and three equivalent P+2.50- atoms to form PNiP3 tetrahedra that share corners with three equivalent NiP4 tetrahedra and corners with twelve NiP5 trigonal bipyramids. All P–P bond lengths are 2.20 Å. In the third P+2.50- site, P+2.50- is bonded in a 6-coordinate geometry to five Ni2+ and one P+2.50- atom. In the fourth P+2.50- site, P+2.50- is bonded in a 7-coordinate geometry to seven Ni2+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on NiP2 by Materials Project

NiP2 is Pyrite structured and crystallizes in the cubic Pa-3 space group. The structure is three-dimensional. Ni2+ is bonded to six equivalent P1- atoms to form NiP6 octahedra that share corners with twelve equivalent NiP6 octahedra and corners with six equivalent PNi3P tetrahedra. The corner-sharing octahedral tilt angles are 64°. All Ni–P bond lengths are 2.28 Å. P1- is bonded to three equivalent Ni2+ and one P1- atom to form distorted PNi3P tetrahedra that share corners with three equivalent NiP6 octahedra and corners with fifteen equivalent PNi3P tetrahedra. The corner-sharing octahedral tilt angles are 78°. The P–P bond length is 2.19 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Ni3P by Materials Project

Ni3P crystallizes in the tetragonal I-4 space group. The structure is three-dimensional. there are three inequivalent Ni1+ sites. In the first Ni1+ site, Ni1+ is bonded in a water-like geometry to two equivalent P3- atoms. There are one shorter (2.21 Å) and one longer (2.26 Å) Ni–P bond lengths. In the second Ni1+ site, Ni1+ is bonded in a distorted trigonal non-coplanar geometry to three equivalent P3- atoms. There are a spread of Ni–P bond distances ranging from 2.21–2.35 Å. In the third Ni1+ site, Ni1+ is bonded to four equivalent P3- atoms to form a mixture of edge and corner-sharing NiP4 tetrahedra. There are a spread of Ni–P bond distances ranging from 2.29–2.33 Å. P3- is bonded in a 9-coordinate geometry to nine Ni1+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on NiP3 by Materials Project

NiP3 is Skutterudite structured and crystallizes in the cubic Im-3 space group. The structure is three-dimensional. Ni1+ is bonded to six equivalent P+0.33- atoms to form NiP6 octahedra that share corners with six equivalent NiP6 octahedra and corners with twelve equivalent PNi2P2 tetrahedra. The corner-sharing octahedral tilt angles are 62°. All Ni–P bond lengths are 2.28 Å. P+0.33- is bonded to two equivalent Ni1+ and two equivalent P+0.33- atoms to form distorted PNi2P2 tetrahedra that share corners with four equivalent NiP6 octahedra, corners with ten equivalent PNi2P2 tetrahedra, and an edgeedge with one PNi2P2 tetrahedra. The corner-sharing octahedra tilt angles range from 68–69°. There are one shorter (2.24 Å) and one longer (2.25 Å) P–P bond lengths.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on NiP by Materials Project

NiP is Millerite-like structured and crystallizes in the orthorhombic Pbca space group. The structure is three-dimensional. Ni2+ is bonded in a 5-coordinate geometry to five equivalent P2- atoms. There are a spread of Ni–P bond distances ranging from 2.25–2.33 Å. P2- is bonded in a 5-coordinate geometry to five equivalent Ni2+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on NiP2 by Materials Project

NiP2 crystallizes in the monoclinic C2/c space group. The structure is three-dimensional. Ni2+ is bonded in a square co-planar geometry to four equivalent P1- atoms. All Ni–P bond lengths are 2.21 Å. P1- is bonded to two equivalent Ni2+ and two equivalent P1- atoms to form distorted corner-sharing PNi2P2 tetrahedra. Both P–P bond lengths are 2.24 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on NiP by Materials Project

NiP crystallizes in the orthorhombic Pnma space group. The structure is three-dimensional. there are three inequivalent Ni2+ sites. In the first Ni2+ site, Ni2+ is bonded to five P2- atoms to form distorted NiP5 square pyramids that share corners with four equivalent NiP6 octahedra, corners with two equivalent NiP5 square pyramids, edges with two equivalent NiP6 octahedra, and edges with three equivalent NiP5 square pyramids. The corner-sharing octahedra tilt angles range from 43–61°. There are a spread of Ni–P bond distances ranging from 2.24–2.34 Å. In the second Ni2+ site, Ni2+ is bonded to six P2- atoms to form distorted NiP6 octahedra that share corners with eight equivalent NiP5 square pyramids, edges with four equivalent NiP5 square pyramids, and faces with two equivalent NiP6 octahedra. There are a spread of Ni–P bond distances ranging from 2.27–2.38 Å. In the third Ni2+ site, Ni2+ is bonded in a 5-coordinate geometry to five P2- atoms. There are a spread of Ni–P bond distances ranging from 2.25–2.29 Å. There are three inequivalent P2- sites. In the first P2- site, P2- is bonded in a 6-coordinate geometry to six Ni2+ atoms. In the second P2- site, P2- is bonded in a 5-coordinate geometry to five Ni2+ atoms. In the third P2- site, P2- is bonded in a 7-coordinate geometry to five Ni2+ atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on NiP by Materials Project

NiP crystallizes in the orthorhombic Cmc2_1 space group. The structure is three-dimensional. there are two inequivalent Ni2+ sites. In the first Ni2+ site, Ni2+ is bonded in a 5-coordinate geometry to five P2- atoms. There are a spread of Ni–P bond distances ranging from 2.26–2.34 Å. In the second Ni2+ site, Ni2+ is bonded to six P2- atoms to form distorted face-sharing NiP6 octahedra. There are a spread of Ni–P bond distances ranging from 2.28–2.37 Å. There are two inequivalent P2- sites. In the first P2- site, P2- is bonded in a 6-coordinate geometry to six Ni2+ atoms. In the second P2- site, P2- is bonded in a 5-coordinate geometry to five Ni2+ atoms.

36 MATERIALS SCIENCE↗