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Powder Diffraction Opportunities at

Brookhaven’s Light Source II

E. Dooryhee – dooryhee@bnl.gov

5th NYU X-Ray Workshop Wednesday, June 2018

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Soft X-Ray Scattering & Spectroscopy 2-ID: Soft Inelastic X-ray Scattering (2017) 21-ID: Photoemission-Microscopy Facility (2017) 22-BM: Magneto, Ellipso, High Pressure IR (2018) 23-ID-1: Coherent Soft X-ray Scat (2015) 23-ID-2:Coherent Soft X-ray Spectr & Pol (2015/2016)

Complex Scattering 10-ID: Inelastic X-ray Scattering (2015) 11-ID: Coherent Hard X-ray Scattering (2015) 11-BM: Complex Materials Scattering (2016) 12-ID: Soft Matter Interfaces (2017)

Diffraction & In Situ Scattering 4-ID: In-Situ & Resonant X-Ray Studies (2017) 27-ID: High Energy X-ray Diffraction (2022) 28-ID-1: Pair Distribution Function (2018)

28-ID-2: X-ray Powder Diffraction (2015)

Hard X-Ray Spectroscopy 6-BM: Beamline for Mater. Measurements (2017) 7-BM: Quick X-ray Absorption and Scattering (2016) 7-ID-1: Spectroscopy Soft and Tender (2017)

7-ID-2: Spectroscopy Soft and Tender (2017) 8-ID: Inner Shell Spectroscopy (2017)

Imaging & Microscopy 3-ID: Hard X-ray Nanoprobe (2015) 4-BM: X-ray Fluorescence Microscopy (2017) 5-ID: Sub-micron Res X-ray Spec (2015) 8-BM: Tender X-ray Absorption Spectroscopy (2017) 9-ID: Bragg Coherent Diffractive Imaging (2022?) 18-ID: Full-field X-ray Imaging (2018)

Structural Biology 16-ID: X-ray Scattering for Biology (2016) 17-ID-1: Frontier Macromolecular Cryst (2016) 17-ID-2: Flexible Access Macromolecular Cryst (2016) 17-BM: X-ray Footprinting (2016) 19-ID: Microdiffraction Beamline (2017)

NSLS-II Beamline Portfolio

Brookhaven National Lab

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Soft X-Ray Scattering & Spectroscopy 2-ID: Soft Inelastic X-ray Scattering (2017) 21-ID: Photoemission-Microscopy Facility (2017) 22-BM: Magneto, Ellipso, High Pressure IR (2018) 23-ID-1: Coherent Soft X-ray Scat (2015) 23-ID-2:Coherent Soft X-ray Spectr & Pol (2015/2016)

Complex Scattering 10-ID: Inelastic X-ray Scattering (2015) 11-ID: Coherent Hard X-ray Scattering (2015) 11-BM: Complex Materials Scattering (2016) 12-ID: Soft Matter Interfaces (2017)

Diffraction & In Situ Scattering 4-ID: In-Situ & Resonant X-Ray Studies (2017) 27-ID: High Energy X-ray Diffraction (2022) 28-ID-1: Pair Distribution Function (2018)

28-ID-2: X-ray Powder Diffraction (2015)

Hard X-Ray Spectroscopy 6-BM: Beamline for Mater. Measurements (2017) 7-BM: Quick X-ray Absorption and Scattering (2016) 7-ID-1: Spectroscopy Soft and Tender (2017)

7-ID-2: Spectroscopy Soft and Tender (2017) 8-ID: Inner Shell Spectroscopy (2017)

Imaging & Microscopy 3-ID: Hard X-ray Nanoprobe (2015) 4-BM: X-ray Fluorescence Microscopy (2017) 5-ID: Sub-micron Res X-ray Spec (2015) 8-BM: Tender X-ray Absorption Spectroscopy (2017) 9-ID: Bragg Coherent Diffractive Imaging (2022?) 18-ID: Full-field X-ray Imaging (2018)

Structural Biology 16-ID: X-ray Scattering for Biology (2016) 17-ID-1: Frontier Macromolecular Cryst (2016) 17-ID-2: Flexible Access Macromolecular Cryst (2016) 17-BM: X-ray Footprinting (2016) 19-ID: Microdiffraction Beamline (2017)

NSLS-II Beamline Portfolio

Brookhaven National Lab

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Science Enabling Powder Diffraction

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In situ and time-dependent X-ray experiments on complex samples and functional samples in variable environmental conditions (p, T, gas) structure evolution, phase transformation (Materials, Chemical, Hard condensed Matter, Environmental, Engineering, Earth Sciences)

Higher energy: 30-70 keV

• High-Z or bulk samples (minimized absorption and … damage)

• Enables transmission measurements (more “forgiving”)

• Through cells (e.g. furnace), devices (e.g. coin or pouch cells). In most cells (e.g. DACs), 2 range is limited by window opening; higher coverage of the reciprocal space (Q range).

High-throughput, combinatorial and screening

Complexity in materials (e.g. “bad” crystals), where short range order (PDF) deviates from long range order (XRD) towards thin films, nanostructures, amorphous samples

Nominal beam size 0.6 x 0.05 mm2 (meant for powder averaging) or smaller for phase 1D/2D mapping

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NSLS-II 28-ID General User program

• Materials Science

– Batteries (e.g. Li-ion Cathode materials), electrochemistry

– Xtreme conditions e.g. supercritical CO2, corrosive atm., HP

– Solid State Chemistry, crystallization, synthesis (hydrothermal, MW)

– Gas sorption, catalysis (porous minerals, hydrates, MOFs)

– Thermal expansivity, phase diagrams (e.g. HT ceramics as thermal barrier coating in space technology)

– Nuclear Science (structural or fuel materials, irradiation, wastes)

– nanostructures and NPs, thin films, pharmaceuticals or organic

• Physics: multiferroics, antiferromagnets, semi-cond or HTc supra-cond

• and also Engineering, Environmental, Earth Sciences…

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In Situ and Operando Conditions

A large variety of OTS or custom sample cells: • Lamp furnace (RT- 2000°C) • Flat plate furnace (RT- 1500°C) • Hot air blower (RT - 1000°C) • Gas flow reactors and flexible coil heater

for capillaries( RT-1300) • High pressure reaction cell (up to 400°C

& 1500psi) (gas, hydrothermal) • Cryostream (80K - 500K) • He cryostat (10K – 500K) • Multi-purpose cell (oxidative or corrosive gases, 3D

stress, vertical and axial loads up to 20 lbs) • Microwave furnace • Electric Flash Sintering • Colloidal Nano Synthesis reactor • 1,100 ton hydraulic press (~25 GPa, 2000K)

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Quadrupole Lamp Furnace (RT - 2,000°C)

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In-situ, high temperature oxidation studies of HfB2 composites

P. Sarin, Univ. of Oklahoma

Develop oxidation-resistant HfB2 and HfB2-SiC

composites as emerging Ultra High Temperature

Ceramics (UHTC) for applications beyond

2000°C (thermal protection for atmospheric re-

entry vehicles )

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Large Volume Press

Partnership with COMPRES and Stony Brook U.

Unique High Pressure Multi-Anvil Facility

1,100-ton Multi-Anvil Press w/ DT-25 Tooling

Area Detector for XRD, Point Gray Camera Imaging

Differential deformation and acoustic velocity

Science Drivers: in situ close to Lower Mantle Conditions Materials properties at High P, T Elasticity, Anelasticity, Plasticity, Rheology, Equation of State Synthesis and Properties of Novel and Functional Materials

9 Robot

XRD Experimental Endstation

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PDF Experimental End-Station

Optics Conditioning Module

Detector Bridge

Sample Table

Detector 1 Detector 2

SAXS Tube

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PDF Experimental End-Station

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5.11Å

4.92Å

4.26Å

3.76Å

2.84Å

2.46Å

1.42Å

Pair distribution function (PDF) gives the probability of finding two atoms separated by a distance r.

Pair Distribution Function (PDF)

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Carbon buckyballs

PDF : a Short-to-Medium Range Order Probe

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• Nanoscale structural fluctuations in strongly correlated materials.

• Catalysts in-situ or operando

• Local structure of batteries and fuel cells during charging and discharging cycles.

• Structure-property relationships in functional nanomaterials.

• Defects and changes in the local structure of irradiated materials

• Evolution of the crystal structure during synthesis of materials

Pair Distribution Function (PDF)

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Structural model fit to Ni standard PDF data (1.25 – 30) Å

Goodness-of-fit (Rw) = 2.4 %

Structural model fit to Ni standard PDF data (1.25 – 100) Å

Goodness-of-fit (Rw) = 3 %

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Significance and Impact UCNC = an important class of nanoscale materials due to their capacity to convert near-IR into near-UV or visible light (bioanalysis, medical therapy, or display technologies).

Shining Light on Upconverting Nanocrystals

D. Hudry et al. Chem. Mater., 2016, 28.

Research Details NaGdF4:Yb:Er nanocrystals (10 nm) in organic

media show limited distortions relative to their bulk counterpart 𝑃6 crystal structure. Effect of size dispersity and structural ordering (SRO, LRO) on optical properties

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Significance and Impact Given the wide-ranging applications of MOFs in gas storage, separation, and catalysis, understanding the formation of MOFs with atomic scale precision is key to optimizing the synthesis of future MOFs.

Scientific Achievement The initial stages of nucleation and growth of Metal Organic Frameworks (MOFs) were studied for the first time using in-situ X-ray Pair Distribution Function (PDF) analysis at NSLS-II.

Research Details MOF ZIF-8 was synthesized and measured in-situ during the initial stages. PDF analysis reveals structural intermediates in the transition from nanocrystal clusters to large crystals.

Tracking the Early Stage Growth of Metal Organic

Frameworks

Work was performed in part at Brookhaven National Laboratory

M. TERBAN, D. BANERJEE, S. GHOSE, B. MEDASANI, A.L SHUKLA, B. LEGG, Y. ZHOU, Z. ZHU, M. SUSHKO, J. YOREO, J. LIU, P. THALLAPALLY, S. BILLINGE. NANOSCALE 10, 4291-4300 (2018).

During the initial growth of MOFs, various building block units are formed: 2-MeIm (1), oxygen-coordinated zinc (2), NO3

−(3). They come together to form the ZIF-8 crystal (4). The elements are carbon (brown), nitrogen (blue), oxygen (red), and zinc (silver).

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In Situ Structural Evolution of Li-ion battery materials

Time and temperature resolved in situ XRD analysis of Ni-rich Layered metal oxides (LiNi1-xMxO2; M=Co,Mn…) helps understanding the structural chemistry and phase evolution during the synthesis, thus enabling rational design of novel battery materials.

Feng Wang, J. Bai, BNL

J Xu, et. Al. Chem. Commun., 52, 4239-4242 (2016).

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1615.51514.51413.51312.51211.51110.5109.598.587.576.565.554.543.532.52

80,000

75,000

70,000

65,000

60,000

55,000

50,000

45,000

40,000

35,000

30,000

25,000

20,000

15,000

10,000

5,000

0

-5,000

-10,000

LNCO 100.00 %

Refinement of XPD high-quality data on LiNi0.8Co0.2O2

• Ni-rich layered oxides (LiNi1-xMxO2, M = Co, Mn) are important cathode materials for Li-ion batteries because of their high capacity and low cost.

• A range of LiNi1-xMxO2 samples prepared with different conditions (compositions, sintering temperature and time, gas flow) were characterized using XPD.

• Figure shows an XRD pattern (green) taken on LiNi0.8Co0.2O2 heated at 800°C for 5 hours in O2 flow. The structural refinement (red) indicates that the material assumes a R-3M layered structure with a 2% mixing of Ni+2 in the Lithium layer.

Feng Wang, J. Bai, BNL

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Full XRD patterns of LiNi1/3Co1/3Mn1/3O2 during 30C charging. .

High-rate Charging induced Structural Changes of Cathode for Lithium-ion Batteries Xiao-Qing Yang, BNL For expanding lithium-ion batteries from

widely used in consumer electronics to large-scale applications such as electric vehicles, hybrid electrical vehicles and clean energy storage, the rate capability and energy density are two important properties. To this purpose, the structural changes of the electrode materials during high rate cycling in real time are studied at XPD under operando conditions.

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Significance and Impact Delivered capacity (mAh/g) in Li/AgxMn8O16 electrochem cells is multiplied by 7 when x is changed from 1.6 to 1.2.

Tunnel structure enables insertion and deinsertion of ions and small molecules.

Structure defects in AgxMn8O16, includes atomic displacement, oxygen vacancies, and variations in Mn valence state. A significant difference in surface oxygen vacancies was determined, that may facilitate Li+ migration for low Ag content material.

Research Details The combined use of local (atomic imaging, nanodiff, electron energy-loss spectroscopy) and bulk (SR x-ray diffraction - NSLS-II XPD, thermogravimetric analysis) methods confirm the structure and elucidated the role of oxygen vacancies on battery performance.

Structural Defects of Hollandite 1D Nanorods

LIJUN WU, FENG XU, YIMEI ZHU, ALEXANDER B. BRADY, JIANPING HUANG, JESSICA L. DURHAM, ERIC DOORYHEE, AMY C. MARSCHILOK, ESTHER S. TAKEUCHI, KENNETH J. TAKEUCHI, ACS NANO, 2015, 9(8), 8430-8439.

2 µm

5 µm

2 µm

A

f

[00

1]

[-110] [010]

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Scientific Achievement For the first time scientists successfully employed in-situ X-ray PDF to monitor the atomic-level defect structure of TiO2 during the Electrical Flash Sintering process.

Significance and Impact Compared to thermal treatments at high temperatures, Electrical Flash shortens the time (a few seconds) for sintering the ceramic powder into dense TiO2 and lowers the process temperature.

Research Details

• Flash Sintering proceeds through an incubation step, before the onset of a rapid, nonlinear increase of the current flowing through the specimen under constant applied voltage. The whole process takes less than 50s.

• In situ Pair Distribution Function analysis reveals unusual large displacements of the O atoms.

• This may signal an “elastic softening” of the lattice, as defects accumulate in large quantities during sintering.

Sintering Mechanism of TiO2 during Electrical Flash Sintering

Work was performed at Brookhaven National Laboratory

B. YOON, D. YADAV, R. RAJ, S. GHOSE, P. SARIN, D. SHOEMAKER; J AM CERAM SOC. 1-7 (2017)

sample

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In-Situ Synthesis: High temperature Flux Growth of

Superconductors Materials by design

Hua He, Daniel E. McNally and Meigan C. Aronson. PNAS 2018 Stony Brook University/BNL – University of Texas

Goal: In-Situ high temperature growth of BaCoS2 ,BaCoSO from BaO and CoS and

observe the evolution of diffraction patterns as temperature changes. Both BaCoS2

and BaCoSO are Mott insulators.

Measurements: In situ, up to 11000C using a Quadruple Lamp Furnace, 52 keV beam

Prof. Kriven designed Quadruple Lamp Furnace Vacuum Sealed Sample Capillary

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High temperature growth of BaCoSO from BaO and CoS: evolution of the diffraction patterns as temperature changes.

- RT: starting materials BaO, Co1-xS, and

Co4S3 phases

- RT to 500C: intermediate phases of BaS

and CoO

- 500C to 700C: only BaCoSO phases

- Above 1100 C: BaCoSO melts

- Cooling <1100 C: BaCoSO recrystallizes

Powder diffraction patterns at representative temperatures

BaCoSO (131) peak. The crystallite size and phase fraction of BaCoSO increases as temperature increases from 700 C to 900 C.

In-Situ Synthesis: High temperature Flux Growth of

Superconductors Materials by design

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The size and concentration dependence of doping was studied in copper(I) sulfide (Cu2S) NCs through a redox reaction with iodine molecules (I2), which formed vacancies accompanied by a localized surface plasmon response. X-ray spectroscopy and X-ray diffraction (XRD) reveal transformation from Cu2S to Cu-depleted phases, along with CuI formation. Greater reaction efficiency was observed for larger NCs. This behavior is attributed to interplay of the vacancy formation energy, which decreases for smaller sized NCs, and the growth of CuI on the NC surface, which is favored on well defined facets of larger NCs.

ORIAN ELIMELECH ET.,AL., ANGEW. CHEM. INT. ED. 2017, 56, 10335

Size dependence of doping by Vacancy Formation

in Cupper Sulfide NCs

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Cr55Al232−δ [δ = 2.70(6)] exhibits high hardness at room temperature as well as low thermal conductivity and excellent oxidation resistance at 973 K, with an oxidation rate comparable to those of softer, denser benchmark materials. The origin of these promising properties can be traced to competing long-range and short-range symmetries within the pseudo-icosahedral crystal structure as determined by X-ray diffraction Analysis, suggesting new criteria for future materials research.

(a) An optical microscope image of a microhardness indentation in the (001) face of a Cr55Al232−δ crystal.

(b) The temperature dependence of the thermal conductivity κ

An overlay of powder x-ray diffraction measurements and determined lattice constants, performed at T = 300K(blue), 473K(green), 773K(red), and 973K (black) as indicated.

R. ROSA et al. PHYSICAL REVIEW MATERIALS 2, 032401(R) (2018)

Pseudo-icosahedral Cr Aluminide as a material for

High-Temperature Protective Coating

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Reactor Pressure Vessel embrittlement

Aging and material degradation (e.g. brittle fracturing of structural materials) could impact life extensions for current fleet of nuclear reactors Dislocation motion is inhibited by radiation induced nanoprecipitates - leading to brittle fracture Understand the role of chemistry and environmental conditions on the formation of nanoprecipitates Advanced X-ray techniques to characterize the nanoprecipitates in RPVs.

Displacement cascade

Nanoprecipitates

Embrittlement

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• Phase ID: ferritic matrix, austenite, cementite

• Volume fraction • Lattice parameters • Grain or domain size Irradiated: • Retained austenite transforms

after irradiation • Cementite grains decreases in

size • Large changes in background

imparted to presence of T3-Mn6Ni16Si17 and T6- Mn2Ni3Si

Evidence for the Formation of Nano-Precipitates

SPROUSTER ET AL. SCRIPTA MATER., 113(1), 18-22 (2015)

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Consult https://wiki-nsls2.bnl.gov/beamline28ID2/

Before using NSLS-II x-ray beams, make sure all “homework” is performed with your home (Bruker) machine!

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PORT: 28-ID-2

SOURCE: damping wiggler

ENERGY RANGE: 40 – 70 keV

ENERGY RESOLUTION: ΔE/E ≈ 10-3

SPATIAL RESOLUTION: 100 μm (V) × 500 μm (H) to mm

BEAMLINE STATUS: open to users since 2015

TECHNIQUES: • X-ray Powder Diffraction (XRD). • Pair Distribution Function Analysis

(PDF). • Small Angle X-ray Scattering (SAXS).

ENDSTATION DETAILS: • 3-circle diffractometer.

• near-field (higher Q coverage) and far-field (higher Q resolution) 2D diffraction.

• 10K - 2000°C; gas flow reactors and reaction cell (400°C, 1500psi); multi-purpose cell; microwave furnace; 1,100 ton hydraulic press (~25 GPa, 2000K).

• Robotic Sample changer (capillaries, flat plates).

Eric Dooryhee Sanjit Ghose

X-ray Powder Diffraction (XPD)

Jianming Bai

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Techniques

Pair Distribution Function (PDF) Beamline, 28-ID-1

• Atomic Pair Distribution Function

• Small-Angle X-ray Scattering

• Wide Angle X-ray Scattering

• Two large area detectors

• (80-500) K cryostream and

• (10 – 500) K Liquid He cryostat coupled to (0-

5) T superconducting magnet

• Gas handling system

• PORT: 28-ID-1

• SOURCE: damping wiggler

• ENERGY RANGE: 39, 64, 75 and 117 keV

• ENERGY RESOLUTION: ΔE/E ≈ 10-3

• SPATIAL RESOLUTION: ~ 0.1 (V) X 0.25(H) mm

Beamline characteristics

• Science commissioning (SC) (75 keV):

2018-2. 17 SC proposals, 14 accepted.

• GU Operations and SC (75 keV): 2018 – 3

Science user programs

Milinda Abeykoon

End station