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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Node Distortions as a Means of Defect Engineering in Zr-Based MOFs

Defect engineering in Zr-based metal–organic frameworks (Zr-MOFs) has focused primarily on missing-linker defects. However, recent studies suggest that node dehydroxylation–which creates distortions and coordinatively unsaturated Zr sites (Zr cus )–may have a more significant impact on properties. The present work uses pair distribution function (PDF) and thermogravimetric analysis coupled with systematic defect manipulation to study the effect of node dehydroxylation and missing-linker defects in UiO-66. By employing rapid heat treatment (RHT) under humid flow, we tracked the transition from high-symmetry [Zr 6 O 4 (OH) 4 ] 12+ to distorted [Zr 6 O 6 ] 12+ nodes. This structural evolution significantly improves As(V) uptake, whereas increasing the number of missing linkers–via chemical treatment or RHT of mixed-ligand frameworks–fails to enhance performance. Crucially, our detection of distorted nodes in as-synthesized UiO-66 also raises the possibility that these defects were silently present in many earlier studies that span various applications, where their role in governing performance may have been inadvertently overlooked. The present study challenges the prevailing “missing-linker” paradigm and establishes cluster dehydroxylation as a defect-engineering strategy to enhance Lewis-acidic performance in Zr-MOFs.

Adsorption↗
DOE OSTI2025

Microstructure, mechanical, and thermal properties of compositionally complex (Hf,Zr,Nb,Ti)B 2 ‒LaB 6 ceramics

Novel compositionally complex borides, (Hf,Zr,Nb,Ti)B 2 and (Hf,Zr,Nb,Ti)B 2 ‒LaB 6 , were fabricated using spark plasma sintering process. (Hf,Zr,Nb,Ti)B 2 ‒LaB 6 exhibits a dual-phase microstructure, in which (Hf,Zr,Nb,Ti)B 2 is a primary phase with the hexagonal structure and LaB 6 is a secondary phase with a cubic structure. The mechanical properties of both (Hf,Zr,Nb,Ti)B 2 and (Hf,Zr,Nb,Ti)B 2 ‒LaB 6 are comparable, with a combination of high hardness and moderate fracture toughness. Thermal diffusivity and conductivity of (Hf,Zr,Nb,Ti)B 2 are much lower than the individual transition metal borides but are significantly increased by the addition of LaB 6 . Herein, it is implied that the thermal properties of boride ceramics can be controlled through the appropriate design of principal metal element compositions.

borides↗
DOE OSTI2020

Materials Data on Zr(FeSn)6 by Materials Project

Fe6Sn6Zr crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Zr is bonded to twelve equivalent Fe and eight Sn atoms to form distorted face-sharing ZrFe12Sn8 hexagonal bipyramids. All Zr–Fe bond lengths are 3.47 Å. There are two shorter (2.98 Å) and six longer (3.10 Å) Zr–Sn bond lengths. Fe is bonded in a 12-coordinate geometry to two equivalent Zr, four equivalent Fe, and six Sn atoms. All Fe–Fe bond lengths are 2.69 Å. There are a spread of Fe–Sn bond distances ranging from 2.69–2.79 Å. There are three inequivalent Sn sites. In the first Sn site, Sn is bonded in a 8-coordinate geometry to one Zr, six equivalent Fe, and one Sn atom. The Sn–Sn bond length is 2.94 Å. In the second Sn site, Sn is bonded in a 12-coordinate geometry to three equivalent Zr and six equivalent Fe atoms. In the third Sn site, Sn is bonded in a 6-coordinate geometry to six equivalent Fe atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Materials Data on Zr(PO4)2 by Materials Project

Zr(PO4)2 crystallizes in the tetragonal I4_1cd space group. The structure is three-dimensional. Zr is bonded to six O atoms to form ZrO6 octahedra that share corners with six equivalent PO4 tetrahedra. There are a spread of Zr–O bond distances ranging from 2.08–2.12 Å. P is bonded to four O atoms to form PO4 tetrahedra that share corners with three equivalent ZrO6 octahedra. The corner-sharing octahedra tilt angles range from 15–28°. There are a spread of P–O bond distances ranging from 1.53–1.55 Å. There are four inequivalent O sites. In the first O site, O is bonded in a bent 150 degrees geometry to one Zr and one P atom. In the second O site, O is bonded in a bent 150 degrees geometry to one Zr and one P atom. In the third O site, O is bonded in a single-bond geometry to one P atom. In the fourth O site, O is bonded in a linear geometry to one Zr and one P atom.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Modulating Ce 3+ Sites in Ce-Zr Oxide Nanocatalysts through Protamine Biomineralization for Organophosphate Dephosphorylation

Catalytic is a crucial reaction for environmental detoxication of pesticides and neutralization of various molecules classified as chemical warfare agents. Herein, we report on a series of tunable Ce-Zr-based metal oxides, (Zr a Ce 1–a O x ) prepared using a facile biomineralization technique, as catalysts for organophosphates dephosphorylation. Synchrotron scattering and spectroscopy methods showcase that Zr a Ce 1–a O x catalysts are highly defective and exhibit an abundance of Ce 3+ sites that promote oxygen vacancies needed for enhanced dephosphorylation reactions. The catalytic performance was assessed using a model para-nitrophenyl phosphate reaction and showcases a strong dependence on Zr dopant concentration and subsequent tuning of the Ce 3+ /Ce 4+ ratio. Analysis of synchrotron datasets allowed structure-performance correlations between the Ce 3+ concentration and associated oxygen vacancies, the dephosphorylation rate constant, and Zr concentration to be established, confirming that Ce 3+ as active sites is positively correlated with the rate constant. We envision that similar biomineralization approaches can be used to fabricate Ce 3+ -rich Ce-Zr oxide for environmental application in dephosphorylation and other hydrolysis reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Materials Data on Zr by Materials Project

Zr crystallizes in the hexagonal P6/mmm space group. The structure is two-dimensional and consists of one Zr sheet oriented in the (0, 0, 1) direction. Zr is bonded in a hexagonal planar geometry to six equivalent Zr atoms. All Zr–Zr bond lengths are 2.92 Å.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Rules for the crystallite size and dislocation density evolution in phases during α-ω transformation in Zr under high-pressure and severe plastic flow

The first in-situ X-ray diffraction (XRD) study of the evolution of the crystallite size and dislocation density in phases during plastic strain-induced phase transformation (PT) is performed utilizing α-ω PT in strongly pre-deformed commercially pure Zr as an important example. Rough diamond anvils (rough-DA) are introduced to intensify all occurring processes during heterogeneous compression of Zr in a diamond anvil cell (DAC). The main rule is found that during α-ω PT the crystallite size and dislocation density in ω-Zr depend solely on the volume fraction of ω-Zr and are independent of pressure, plastic strain tensor, its path, and initial nanostructure. Crystallite size in ω-Zr increases from 10 to 60 nm during the PT, while dislocation density reduces from 1.83×10 15 /m 2 to 0.6×10 15 /m 2 . Rough-DA produce a steady nanostructure in α-Zr before PT with smaller crystallite size and larger dislocation density than smooth-DA, leading to a reduction of the minimum pressure for α-ω PT to a record value 0.67 GPa, 9 times smaller than under hydrostatic loading and 5.1 times lower than the phase equilibrium pressure. In addition to strain, the kinetics of strain-induced PT unexpectedly depends on time. Also, strain-controlled part of kinetics is zero order, in contrast to the first-order kinetics with smooth-DA. The obtained results open a new window for understanding the mutual effects of nanostructure evolution and PT during severe plastic flow in various technological and natural processes. In conclusion, they may bring up economic strategies of producing nanocomposites and single-phase nanostructured materials with optimal properties.

Crystalline size↗
DOE OSTI2025

Effect of Zr and Sc additions on coarsening- and creep resistance of AlSi10Mg fabricated by laser powder bed fusion

Microstructure and creep properties are studied in a eutectic AlSi10Mg alloy modified with Zr and Sc additions (Al-9.8Si-0.32Mg-0.70Zr-0.23Sc, wt%) manufactured through laser powder-bed fusion (L-PBF). Three types of Zr/Sc-bearing powders - elemental, master-alloy, and pre-alloyed - are employed in the fabrication process, with the pre-alloyed powders providing the highest incorporation of Zr and Sc in the Al matrix. Here, the as-printed alloy exhibits a fine cellular Al-Si eutectic structure which fragments and coarsens into micron-sized Si particles during aging at 300 ºC, leading to a steady drop in alloy microhardness between 0.1 and 1000 h. Coarsening of the eutectic Si phase during aging is not measurably affected by Zr and Sc in solid solution, which precipitate during aging and increases strength, compensating weakening from Si coarsening between 1 and 200 h at 300 ºC. Atom-probe analysis in the peak-aged condition (96 h/300 °C) confirms the presence of Al 3 (Sc,Zr) secondary nano-precipitates with an average radius of 1.0 nm and some Si solubility. Micron-sized grains are present throughout the alloy, with ultra-fine-grained regions at the melt pool boundaries, neither of which coarsen during long-term aging at 300 ºC. Under creep conditions at 300 °C, the Zr/Sc-bearing alloy with Al 3 (Sc,Zr) nano-precipitates exhibits power-law behavior, with a high apparent stress exponent (n a = 9) and a high threshold stress (σ th = 43 MPa), exhibiting nearly double the strength of a Zr/Sc-free AlSi10Mg control alloy (σ th = 22 MPa).

36 MATERIALS SCIENCE↗
DOE OSTI2025

Tetragonal structure and uniaxial magnetic anisotropy in the arc-melted (Ce,Zr) 2 (Fe,M) 17 (M = Mo, W, Co) alloys

The tetragonal ThMn 12 -type structure is stabilized in (Ce 1-x Zr x ) 2 T 16 M (x = 0.2 – 0.3; T = Fe or Fe/Co, M = Mo or W) arc-melted alloys. Approximately 5 at% of Mo or W admixture is sufficient to transform the hexagonal Th 2 Ni 17 -type structure of (Ce 1-x Zr x ) 2 Fe 17 into the tetragonal ThMn 12 -type structure of nearly single-phase (Ce 1-x Zr x ) 2 Fe 16 M and/or (Ce 1-x Zr x ) 2 Fe 15 CoM bulk alloys. X-ray Rietveld refinements reveal that Zr and Mo (W) substitute different sites in the tetragonal crystal structure. Zirconium preferentially replaces Ce, whereas Mo (W) substitutes Fe. At room temperature, the tetragonal phases exhibit strong ferromagnetism and a uniaxial magneto-crystalline anisotropy with anisotropy fields of 15 – 17 kOe. These materials possess room-temperature saturation magnetizations of 95 – 105 emu/g and Curie temperature of 420 – 505 K. At some concentrations, concurrent Zr and Mo (W) site occupancy facilitates 1:12 structure formation in bulk alloys with minimal presence of non-magnetic element in the Fe sublattice, thus securing the highest known magnetic moment per Fe atom (∼ 1.37 µ B ) in this type of materials. The intrinsic magnetic characteristics, as well as the absence of critical rare earths (RE), make these compounds interesting for development as low-cost permanent magnets. In conclusion, small Co additions improve the Curie temperature, especially if combined with W.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A CALPHAD-informed approach to modeling constituent redistribution in Zr-based metallic fuels using BISON

Here, a CALPHAD-informed (Computer Coupling of Phase Diagrams and Thermochemistry) constituent redistribution model was developed for Zr-based metallic fuels and incorporated into the BISON fuel performance code. Three uncertain model parameters associated with β and γ phase kinetics were calibrated using integral test data from U-Zr fuel elements irradiated in Experimental Breeder Reactor II. The calibrated constituent redistribution model was shown to predict the behavior of U-Zr fuels with excellent accuracy. Model predictions for U-Pu-Zr fuels were physically reasonable but less accurate. Reduction of uncertainties in the ternary phase transition temperatures and collection of kinetic data for the ζ phase are expected to improve the model’s ternary predictions. Finally, the new model was coupled to existing thermomechanics models in BISON to simulate irradiation of an entire U-Zr fuel element, demonstrating its ability to accurately predict the behavior of U-Zr fuels with realistic geometries and mesh resolutions at the engineering scale.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2023

Irradiation Effects on Stability of δ-UZr2 phase in U-50 wt% Zr Alloy

U-50wt%Zr is a candidate metallic nuclear fuel with potential application in light water reactors due to its excellent thermal properties and high radiation tolerance. The Zr-rich UZr fuels possess greater swelling resistance and fission gas release characteristics compared with U-rich UZr fuels. In this current study, the δ-phase U-50wt%Zr is proton irradiated at room temperature to 1 displacement per atom (dpa) to provide insights on phase stability under irradiation conditions. High resolution characterization of Transmission Electron Microscopy (TEM) and Atom Probe Tomography (APT) characterization techniques are used to elucidate microstructural changes due to irradiation. TEM and APT results show highly oriented bcc β-Zr-rich platelet precipitates nucleating adjacent to α-U phases inside the UZr 2 matrix. Formation of this platelet morphology is characteristic of Widmänstatten structure which can be attributed to a variety of factors such as differences in thermal expansion coefficient between the phases, grain size, alloy composition, and cooling rate. The phases present are distinctly different than those observed through in situ annealing, but irradiation accelerates diffusion and phase separation kinetics. These microstructural changes in U-50wt%Zr are different from those achieved by pure thermodynamic or high temperature heavy ion irradiation experiments. Finally, our work, together with previous ones, highlight the necessity to study the U-Zr phase diagram under non-equilibrium thermodynamics conditions to support this material's deployment as a viable nuclear fuel form.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Minimizing thickness variation in monolithic U-10Mo fuel foil and Zr interlayer during hot rolling: A microstructure-based finite element method analysis

Low-enriched uranium alloyed with 10 wt. % molybdenum (U-10Mo) has been identified as a promising alternative to highly enriched uranium fuel for the United States’ high performance research reactors. The monolithic U-10Mo fuel plate consists of a metallic U-10Mo fuel foil with a 25 µm Zr interlayer and a relatively thick cladding of aluminum alloy 6061. The Zr interlayer is typically applied during the hot co-rolling process, and this process dictates the uniformity of the Zr interlayer. Thickness variation observed in the U-10Mo and Zr interlayer has been attributed to several sources: the initial grain size of the U-10Mo castings, can materials, rolling temperature, inhomogeneous molybdenum content, and porosity in the cast U-10Mo. This thickness variation limits the ability to meet the dimensional specification; thus, a better understanding of the factors causing the nonuniform thickness is needed. In this work, we used a novel, microstructure-based finite element method to model the hot rolling process to address these concerns. Grain microstructures in U-10Mo were tessellated and explicitly considered in the finite element model. Each grain was assigned a random material property to mimic the grain strength variations induced by different grain orientations. Simulations were performed using six steel can thicknesses, four grain sizes, and with or without a Zr interlayer to investigate the influences of those variables on the thickness nonuniformity. The simulation results showed that a thinner steel can and finer U-10Mo grain size reduce thickness variations in both the U-10Mo fuel foil and Zr interlayer. The direct findings from the simulations and analysis can be used to optimize the hot rolling schedule, reduce fabrication defects, and meet the dimensional specifications. The proposed microstructure-based finite element model can be also coupled with experimental microstructure characterization data, images, and models to simulate multi-pass hot rolling.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The structure of low-lying 1 - states in 90,94 Zr from (α,α'γ) and (p,p'γ) reactions

The low-lying dipole strength in the 90,94 Zr nuclei was investigated via (ρ,ρ'γ) at 80 MeV and (α, α', γ) at 130 MeV. The experiments, made at RCNP, used the magnetic spectrometer Grand Raiden for the scattered particles and the array CAGRA with HPGe detectors for the γ-decay. For 94 Zr these are the first data for both reactions and for 90 Zr these are the first data with (ρ,ρ'γ) and the first ones at high resolution for (α, α', γ). The comparison of the present results for the two nuclei with existing (γ, γ') data shows that both nuclear probes produce an excitation pattern different than that of the electromagnetic probes. DWBA calculations were made using form factors deduced from transition densities, based on RPA calculations, characterized by a strong neutron component at the nuclear surface. A combined analysis of the two reactions was performed for the first time to investigate the isoscalar character of the 1 - states in 90,94 Zr. The (ρ,ρ'γ) cross section was calculated using values for the isoscalar electric dipole energy-weighted sum rule (E1 ISEWSR) obtained from the (α, α', γ) data. The isoscalar strength for 90 Zr was found to exhaust 20 ± 2.5% of the EWSR in the energy range up to 12 MeV. In case of 94 Zr, a strength of 9 ± 1.1% of the EWSR was found in the range up to 8.5 MeV. Although an overall general description was obtained in the studied energy intervals, not all proton cross sections were well reproduced using the isoscalar strength from (α, α', γ). This might suggest mixing of isoscalar and isovector components and that this mixing and the degree of collectivity are not the same for all the 1 - states below the particle binding energy.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2020

Zr 6 O 8 Node-Catalyzed Butene Hydrogenation and Isomerization in the Metal–Organic Framework NU-1000

Zirconium-based metal–organic frameworks (Zr-MOFs) have been increasingly studied over the past two decades as heterogeneous catalysts due to their synthetic tunability, well-defined nature, and chemical stability. In contrast to traditional zirconia-based heterogeneous catalysts, the community has assumed that Zr-MOFs are inert catalyst supports that do not participate directly in hydrocarbon transformations, such as olefin hydrogenation and isomerization. Here, we report that the Zr-MOF NU-1000 is capable of catalyzing olefin hydrogenation and isomerization, without any postsynthetic modifications, under a hydrogen atmosphere. We probe H 2 activation over the nodes of NU-1000 via spectroscopic and computational techniques revealing that H 2 dissociation can occur heterolytically across coordinatively unsaturated Zr sites and proximal hydroxide and μ3-oxo ligands. These results, along with catalytic experiments, suggest that H 2 activation results in node-supported zirconium hydrides capable of the hydrogenation and isomerization of 1-butene. When examining rate dependence on the partial pressure of H 2 , we observe first-order dependence for hydrogenation and half-order dependence for isomerization. Half-order H 2 rate dependence is consistent with a mechanism where both fragments of cleaved H 2 are active for 1-butene isomerization, suggesting that heterolytic cleavage generates acidic protons resulting in parallel, acid-, and hydride-catalyzed isomerization pathways. In conclusion, this work shows that Zr-MOFs have more diverse reactivity than the current literature may suggest and opens possibilities for ways in which Zr-MOFs can be used as heterogeneous catalysts and supports.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Tuning Zr 12 O 22 Node Defects as Catalytic Sites in the Metal–Organic Framework hcp UiO-66

Defects in metal–organic frameworks (MOFs) play important roles in MOF reactivity and catalysis. Now, we report evidence of the reactivity and the quantitative characterization of the missing linker defects on the Zr 12 O 22 nodes in the MOF hcp UiO-66 (these are paired Zr 6 O 8 nodes bridged by OH groups) and those on the Zr 6 O 8 nodes of the MOF UiO-66. The defect sites catalyze the ring-opening reactions of epoxides with alcohols, and new sites formed by removal of bridging OH groups on the Zr 12 O 22 nodes also participate in the catalysis. The hcp UiO-66 was synthesized from UiO-66 and from molecular precursors, and, under various synthesis conditions, the nodes incorporated acetate ligands, where linkers were missing, and the number of these ligands was controlled by the synthesis conditions. These ligands are inhibitors of the catalytic reactions, and their removal by reaction with, for example, methanol (to form, for example, methyl acetate) preceded catalysis on the defect sites. The former MOF incorporated more defect sites than the latter, correspondingly being a more active catalyst. The defect sites on the Zr 12 O 22 nodes are 2–6 times more active per site than those on the isolated Zr 6 O 8 nodes, with the node-bridging OH groups increasing the catalytic activity of the neighboring node defect sites because new sites are formed by their removal. In conclusion, the results help point the way to the design and control of catalytic sites on metal oxide-like MOF nodes by tuning of the number and reactivity of the defect sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

The stellar origins of 96 Zr excesses in presolar graphites from the Murchison meteorite

Context. Zirconium-96 is a stable isotope that can be synthesized under different neutron-rich nucleosynthetic conditions. Astrophysical models predict its production to occur in various stellar environments: from low-to-intermediate-mass asymptotic giant branch (AGB) stars to massive stars and core-collapse supernovae. Aims. Detections of 96Zr excesses, in combination with other isotopic measurements from presolar grains can provide unique constraints on its stellar origin. Presolar grains are microscopic particles found in primitive Solar System materials, which formed in stellar winds and supernova ejecta. The isotopic composition of each grain can provide us a snapshot of the nucleosynthetic processes that took place during the parent star’s lifetime. Methods. In this study, we measured the stable isotopes of C, N, O, Mo, Zr, and Ru in high-density presolar graphite grains from the Murchison meteorite and found four grains that contain positive isotopic anomalies in 96 Zr carried by their internal subgrains. We analyzed multi-element isotopic datasets from each grain to explore the source of the observed 96 Zr excesses. Results. Comparisons with stellar models indicate that two grains likely condensed in an intermediate-mass AGB star with initial metallicity of Z ≤ 0.014. Their 96 Zr/ 94 Zr ratios also match those predicted for born-again AGB stars undergoing a very late thermal pulse and rapidly accreting white dwarfs. After comparing the relative populations of the aforementioned dust-producing stars, we propose rapidly accreting white dwarfs as a new, and more likely, stellar source for one of the presolar grains. The remaining two grains could have originated in the supernova ejecta of massive stars, due to correlated excesses in the p-nuclides, 92, 94 Mo. Thus, grains with 96 Zr anomalies can have a variety of stellar origins, in agreement with theoretical studies. Conclusions. Our study highlights the importance of multi-element analysis in constraining the types of stars where presolar grains have condensed. These data will help improve our understanding of various nucleosynthesis processes in different stellar phases.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2020

Bi aliovalent substitution in Li 7 La 3 Zr 2 O 12 garnets: Structural and ionic conductivity effects

We report on the synthesis of cubic-phase garnet-type solid-state electrolytes based on Bi-doped Li 7 La 3 Zr 2 O 12 (LLZO). Bi aliovalent substitution of Zr in LLZO utilizing the Pechini processing method is employed to synthesize Li 7-x La 3 Zr 2-x Bi x O 12 compounds. A strong dependence of the ionic conductivity on Bi content is observed, and under our synthesis and sintering conditions, a >100-fold increase over the un-doped sample is observed for x=0.75. Cubic-phase Li 6 La 3 Zr 1 BiO 12 compounds are generated upon annealing in air in the temperature range 650 °C-900 °C. In contrast, in the absence of Bi, the cubic garnet phase of Li 7 La 3 Zr 2 O 12 is not formed below 700 °C and a transformation to the tetragonal phase is observed at similar to 900 °C for this un-doped compound. The role of Bi in lowering the formation temperature of the garnet cubic phase and in the ionic conductivity improvements is investigated in this work. We ascribe the effect of Bi-doping on ionic conductivity increments to changes in Li + -site occupancy and lattice parameters and the reduction in the formation temperature for the cubic-phase formation to rate enhancements of the solid-state reaction. To identify the site occupancy of Bi in the garnet structure, we employ synchrotron extended x-ray absorption fine structure spectroscopy. Our results indicate that Bi additions occupy the Zr-type sites exclusively, to within the accuracy of the measurements.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Single-Crystal Diffuse Neutron Scattering Study of the Dipole-Octupole Quantum Spin-Ice Candidate Ce 2⁢ Zr 2 ⁢O 7 : No Apparent Octupolar Correlations Above 𝑇 = 0.05 K

The insulating magnetic pyrochlore Ce 2 ⁢Zr 2 ⁢O 7 has gained attention as a quantum spin-ice candidate with dipole-octupole character that arises from the crystal-electric-field ground-state doublet for the Ce 3+ Kramers ion. This dipole-octupole character permits both spin-ice phases based on magnetic dipoles and those based on more-exotic octupoles. This work reports low-temperature neutron diffraction measurements on single-crystal Ce 2 ⁢Zr 2⁢ O 7 with 𝑄 coverage both at low 𝑄, where the magnetic form factor for dipoles is near maximal, and at high 𝑄, covering the region where the magnetic form factor for Ce 3+ octupoles is near maximal. This study was motivated by recent powder neutron diffraction studies of other Ce-based dipole-octupole pyrochlores, Ce 2 ⁢Sn 2 ⁢O 7 and Ce 2 ⁢Hf 2 ⁢O 7 , which each showed temperature-dependent diffuse diffraction at high 𝑄, interpreted as arising from octupolar correlations. Our measurements use an optimized single-crystal diffuse scattering instrument that allows us to screen against strong Bragg scattering from Ce 2 ⁢Zr 2 ⁢O 7 . The temperature-difference neutron diffraction reveals a low-𝑄 peak consistent with dipolar spin-ice correlations reported in previous work, and an alternation between positive and negative net intensity at higher 𝑄. These features are consistent with our numerical-linked-cluster calculations using pseudospin interaction parameters previously reported for Ce 2 ⁢Zr 2⁢ O 7 , Ce 2 ⁢Sn 2 ⁢O 7 , and Ce 2 ⁢Hf 2 ⁢O 7 . Importantly, neither the measured data nor any of the NLC calculations show evidence for increased scattering at high 𝑄 resulting from octupolar correlations. We conclude that at the lowest attainable temperature for our measurements (𝑇 = 0.05 K), scattering from octupolar correlations in Ce 2 ⁢Zr 2 ⁢O 7 is not present in the neutron diffraction signal on the level of our observation threshold of around 0.1% of the low-𝑄 dipole scattering. We compare these results to those obtained earlier on powder Ce 2 ⁢Sn 2 ⁢O 7 and Ce 2⁢ Hf 2⁢ O 7 , and to low-energy inelastic neutron scattering from single-crystal Ce 2 ⁢Zr 2 ⁢O 7 .

36 MATERIALS SCIENCE↗