The following is a selection of the slides presented during the colloquium. For more information please contact Prof. Nino at [email protected] Thank you!

ProfessorJuanClaudioNino ResearchHighlight: MaterialsDevelopmentforEnergyͲRelatedApplicationsand InvestigationofStructureͲPropertyRelationshipsinActiveCeramics

ResearchInterestsandMethods: • • • • • • • •

MultifunctionalCeramics EnergyMaterials Dielectrics Ionicconductors NuclearMaterials&Detectors Bioceramics BulkCeramicSynthesis ThinFilmDeposition

Inducedcolossalpermittivity(>105)inBaTiO3 usingfastͲfiringsinteringtechniques. Determinedtheoriginofcolossalpermittivityas thecombinationofinterfacialandhopping polarization.

• • • •

SingleCrystalGrowth FiberSynthesis InͲSituFoaming BroadbandDielectric Spectroscopy • ElectrochemicalImpedance Spectroscopy

RepresentativePublications(from110+):

SynergisticActivities:

• H.S.Han,C.Davis,andJ.C.Nino,"VariableRangeHopping ConductioninBaTiO3 CeramicsExhibitingColossalPermittivity",J Phys Chem C 118 [17]9137Ͳ9142(2014) • B.B.Hinojosa,A.Asthagiri,andJ.C.Nino,“EnergyLandscapein frustratedSystems:CationHoppinginPyrochlores,”Appl Phys Lett 103 [2]022901(2013). • B.Neumann,T.Elkins,W.Dreher,H.HagelinͲWeaver,J.C.Nino, andM.Bäumer,“EnhancedCatalyticMethanecouplingusing NovelCeramicFoamswithBimodalPorosity,”Catal.Sci.Technol., 3 89Ͳ93(2013). • L.Li,J.C.Nino,“ProtonͲConductingBariumStannates:Doping StrategiesandTransportProperties,”Int JHydrogenEnergy 38 1598Ͳ1606(2013).

ProfessionalAwardsandHonors: • USDepartmentofState,FulbrightScholar(2014) • FacultyExcellenceAward,MaterialsScienceandEngineering(2012). • UniversityofFloridaResearchFoundationProfessorship(2010Ͳ2013). • InternationalEducatoroftheYear,UniversityofFlorida(2010). • J.BruceWagnerJr.Award,TheElectrochemicalSociety(2009). • CarlStormFellowship,GordonResearchConference(2006). • NSFCAREERAward,NationalScienceFoundation(2005). EditorialandProfessionalSocietyActivities: • JournalofAmericanCeramicSociety:AssociateEditor • JournalofElectroceramics:EditorialBoard • MaterialsResearchSociety:MeetingsAssessmentCommittee(Chair)

ContactInformation: Prof.JuanC.Nino,MaterialsScienceandEngineeringDepartment,UniversityofFlorida,GainesvilleFL32611Ͳ6400 (352)846Ͳ3787;[email protected];http://nrg.mse.ufl.edu

ProfessorJuanClaudioNino CitationReport(June2015snapshotfromWebofScienceTM ) NumberofPeerͲReviewedJournal PublicationsperYear

NumberofCitationsperYear

Highlights: TotaltimesProf.Nino’spublicationshave beencited:2031 Averagecitationsperpublication:20.3 HͲindex:23 Publicationswith100citationsormore:4 (Source:WebofScienceTM Authorreport)

ResearchFundingHighlights • TotalnumberofcontractsandgrantsasPIandcoͲPIsince2004:32 • TotalfundingsecuredincontractsandgrantsasPIandcoͲPIsince2004:$8’500.00(USD) • FundingAgencies: • USDepartmentofEnergy: • USDepartmentofDefense • USNationalInstitutesofHealth • USDefenseTreatReductionAgency • USNationalScienceFoundation • BillandMelindaGatesFoundation • JohnHauckFoundation • FloridaDepartmentofTransportation

• FloridaBoardofGovernors • USNationalAeronauticsandSpace Administration(NASA) • USDepartmentofCommerce

PatentHighlights • J.C.Nino,P.M.Johns,J.E.Baciak,“DopedMaterials,Batteries,andPhotovoltaicCells,”FiledUSPTOOctober18,2013. • M.ͲE.S.HannaandJ.C.Nino,“PluripotentTissueHarvesterandMethodsofManufacturethereof,”FiledUSPTOSeptember13,2013. • F.SoandJ.C.Nino,“MethodandApparatusforImagingUtilizingandUltrasonicImagingSensorArray,”PatentNo.US7,893,474.

ContactInformation: Prof.JuanC.Nino,MaterialsScienceandEngineeringDepartment,UniversityofFlorida,GainesvilleFL32611Ͳ6400 (352)846Ͳ3787;[email protected];http://nrg.mse.ufl.edu

Nino Research Group

Nino Research Group

Advanced Functional Materials Development: An overview of the Nino Research Group at University of Florida

Dr. Juan Claudio Nino Professor and Fulbright US Scholar Materials Science and Engineering, University of Florida 172 Rhines Hall, (352) 846-3787, [email protected]

Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

University of Florida

MSE Department – Rhines Hall

MSE Undergraduate and Graduate Programs are Top Ranked in the USA US News

Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Group Members

Nino Research Group

1. 2. 3. 4.

Jaki Bayless (UG) Elizabeth Delesky (UG) Shinyoung Yeo (G) Jack Kendall (UG)

5. 6. 7. 8.

Soumitra Sulekar (G) 9. Andre Pertuit (UG) 13.Nathan Deng (UG) 17.George Baure, Jr. (G) Hannah Zeffren (UG) 10.Ji Hyun Kim (UG) 14.Janny Pineiro (UG) 18.Marissa Buck (UG) Trey Davis (G) 11.Paul Johns (G) 15.Elvira Mitiukova (G) 19.Mehrad Merh (G) 5 Professor Claudio Nino(UG) – UniValle Physics Colloquium – December 2015 Prof. Juan Claudio Nino Juan 12.Bryce Edwards 16.Jenny Poon (UG)

Nino Research Group

What we do… Performance

? Synthesis & Processing

?

? ?

? Properties

? Structure & Composition

Materials Development for Energy- and Bio-Related Applications & Investigation of Structure-Property Relationships in Active Ceramics Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Research Clusters

Nino Research Group

Electronic Ceramics – Bioceramics – Composites

Electronics

Biomedical

Dielectrics Thin Films Piezoelectrics Thermoelectrics

Electrochemistry

Electrolyte Materials Hydrogen Membranes Heterogeneous Catalysts

Bioactive Fiber Systems Foamed Bioceramic Scaffolds Pluripotent Tissue Harvester

Sensors

Nuclear Energy

Nuclear Fuels Fuel Reprocessing Advanced Cladding Nuclear Batteries

Gamma-Ray Detectors Semiconductors and Scintillators Memristive Neural Networks

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Nino Research Group

Research Activities

Property/Function Dielectrics Piezoelectrics Ferroelectrics Ionic Conductors Semiconductors Mixed Conductors Protonic Conductors Catalysts Nuclear Materials Bioceramics

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X

X X

X

X

X

X

X

X

X

X

X

X

X X

X

X X

X

X

X

X

X

X

X X

X

X

X

X X

X

Application Capacitors Sensors Fuel Cells Rad Detectors Heterocatalysis H2O Remediation Nuclear Fuel Nuclear Batteries Bone Implants Wound Healing

Single Crystals Bulk Foamed Thin Films Coatings Nanofibers Nanoparticles Composites

Material Form/Type

X X

X

X

X

X

X X

X X

X

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Nino Research Group

NRG Collaboration Network

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Nino Research Group

NRG Collaboration Network

USA: Universities MIT Penn State NCSU Col. School of Mines OSU Northwestern Georgia Tech U of Maryland Drexel UWV National Labs ORNL LANL INL SRNL PNNL NIST ANL

EUROPE: Universities EPFL (Switzerland) ETH Zurich (Switzerland) EMPA (Switzerland) U Oslo (Norway) NTU (Netherlands) UPS (France) ECP (France) Sheffield U (England) ICL (England) TCD (Ireland) UniBremen (Germany) Tor Vergata (Italy) ICYV (Spain) National Institutes IJS (Slovenia) IOP ASCR (Czech Republic) INFLPR (Romania)

ASIA: Universities IIT (India) TIT (Japan) Hanyang U (Korea) XJTU (China) SOUTH AMERICA: Universities CeNAT (Costa Rica) UniValle (Colombia) Los Andes (Colombia) UdeA (Colombia) USB (Venezuela) U de Chile (Chile) AUSTRALIA: Universities UNSW (Sydney) U Sydney (Sydney) ANU (Camberra)

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Nino Research Group

Earth

Let me show you three examples of research programs within my group…

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Nino Research Group

Earth

I Li-air batteries Novel Synthesis of Advanced Ionic Conductors

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Nino Research Group

Enhanced Ionic Conductivity of Microwave Processed Li2O-Al2O3-TiO2-P2O5 Glass Ceramics Calvin Davis, Andre Pertuit, and Juan C. Nino Department of Materials Science and Engineering University of Florida Gainesville, FL 32611 Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

Motivation

• The improved commercial viability of lithium ion batteries require electrolytes with enhanced material properties. • Electrolytes need to have higher ionic conductivity at ambient temperatures, low coefficients of thermal expansion, and be nonhygroscopic.

http://www.lithiumion-batteries.com

http://www.sony.net

• Solid state electrolytes can allow for the miniaturization of electrochemical devices. http://www.enerdel.com

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Nino Research Group

Motivation •

Li2O-Al2O3-TiO2-P2O5 glass crystallizes into Li1.3Al0.3Ti1.7(PO4)3 (LATP) with a conductivity on the order of 10-4 S/cm at room temperature and is stable in ambient air conditions.

• LATP is a great candidate for lithium air batteries. Adapted from: P. Knauth, Solid State Ionics, (2009). Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

Glass Ceramics

• Glass ceramics are materials that are easily shaped, have a low coefficient of thermal expansion, and offer unique control over morphology. • Control of the phase transformation allows for the tailoring of materials properties including the conductivity of glass ceramic electrolytes. Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

LATP Composition

• Glass Composition: Li2O-Al2O3-TiO2-P2O5 • Crystalline Composition: Li(1-x)AlxTi(2-x)(PO4)3 • Secondary Phase: AlPO4

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Nino Research Group

Thermal Analysis

• The exothermic peak is indicative of devitrification of the LATP. • Differential scanning calorimetry results show the crystallization begins approximately at 680°C. • Thermogravimetric analysis shows § 2% weight loss at 1000°C which could be indicative of lithium volatilization.

After

Before Crystallization

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Nino Research Group

Conductivity 25

S. Soman et al. J Solid State Electrochem (2012).

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Nino Research Group

Conclusion

• Compared to conventional crystallization at the same temperature, microwave processing lead to a larger average grain size (0.87 μm vs 0.30 μm), suggesting enhances growth kinetics through microwave heating. • LATP crystallized at 1000°C displayed a conductivity of 5.3 x 10-4 S/cm which was approximately 500% higher than LATP crystallized conventionally at the same temperature. • Compositional adjustments to the glass batch showed decreased conductivity for excess phosphorous and deficient aluminum. Excess lithium did show a small increase in conductivity to 7.29 x 10-4 S/cm. Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

Future Work

• Continue to optimize the conductivity of LATP through microwave processing by working with excess lithium batches with the goal of phase purity. • Study the kinetic effects microwave processing has on crystallization in LATP glass ceramics using the Vandermeer model to quantify the stages of dendritic growth. • Study the interfacial stability of LATP with lithium.

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Nino Research Group

Earth

II Colossal Permittivity Controlling Defects and Interfaces to Tailor Properties

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Nino Research Group

Colossal Effective Permittivity in Ceramics: A Story of Defects

Juan Claudio Nino Professor Materials Science and Engineering, University of Florida 172 Rhines Hall, (352) 846-3787, [email protected] Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

Annealing of MWS BaTiO3

H. Han, D. Ghosh, J. L. Jones, and J. C. Nino, Journal of the American Ceramic Society 96, 485 (2013). Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

Annealing of MWS BaTiO3

H. Han, D. Ghosh, J. L. Jones, and J. C. Nino, Journal of the American Ceramic Society 96, 485 (2013). Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

Origin of Colossal Permittivity

1. Interfacial polarization : ‫ڙ‬eff : effective relative permittivity ‫ڙ‬r : relative permittivity of material , Ș (=tb/tg) and ‫ڙ‬BT,λ (as ‫ڙ‬r) are used from the fitting parameters tb : thickness of grain boundary tg : grain size

2. Electrode effect : Novel metal electrodes tend to form Schottky junction with the W. Heywang, J. Mater. Sci. 6, 1214 (1971). surfaces of semiconducting BT ‫ڙ‬electrode = ‫ڙ‬Au – ‫ڙ‬Al 3. Hopping polarization : ‫ڙ‬hopping = ‫ڙ‬total – (‫ڙ‬interfacial + ‫ڙ‬electrode)

MWS BT SPS BT

Interfacial polarization

Hopping polarization

Electrode effect

‫ڙ‬total / tanį @ 1 kHz

56.26 %

26.64 %

17.10 %

3.1 X 104 / 0.03

6.95 %

78.05 %

15.00 %

6.6 X 105 / 0.04

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Nino Research Group

Summary and Outlook

• Colossal effective permittivity (CEP) in “insulating” ceramics can be ascribed to a combination of interfacial polarization at the grain-grain boundary interface (IBLC), electrodesemiconductor interface (SBLC), and polaron hopping effects (small, large, variable range, etc.) • Using data extraction from impedance spectroscopy, a combined universal dielectric response (Jonscher’s UDR) and interfacial polarization (Koop’s IBLC) model can successfully describe the observed dielectric response in CEP compounds. • The question about the mechanisms giving rise to CEP in a particular compound cannot be unequivocally answered due its dependence on processing history. Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

Summary and Outlook

• For example, hopping polarization is dominant polarization mechanism in SPS BaTiO3 ceramics while interfacial polarization is prevailing in MWS BaTiO3 ceramics. • Fast-firing processing conditions can therefore be modified to tailor the contributions of each polarization mechanism and attain optimum performance. • After more than a decade since the colossal permittivity renaissance wthin the electroceramics community, can we actually design high performance devices that take advantage of CEP (e.g. low frequency filters)? • How much electric field tunability is there in the CEP effect? What is the long term degradation of CEP compounds? Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

Earth

III Gamma Ray Detectors Single Crystal Growth and Device Optimization

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Nino Research Group

Enhanced Gamma Ray Sensitivity in Defect Engineered BiI3 Detectors

Paul M. Johnsࢾ, Mary Bliss݈, Kelly Jordanࢾ, James E. Baciakࢾ, and Juan Claudio Ninoࢾ ࢾMaterials

Science & Engineering Department, University of Florida, Gainesville, FL ݈Radiation Detection & Nuclear Sciences, PNNL, Richland, WA Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Why do we need gamma ray detectors? Nino Research Group

Homeland security Industry

Radiology

Image NY Daily News

Image Ortec

Image Wiki Commons

Image Amer. Assc. of Port Auth.

Economic Impact Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

Background

• Desired qualities for gamma-ray radiation detectors include – Compact and lightweight – High energy resolution • Semiconductor detectors have high energy resolution

Gamma Camera Csbiotech

• However, single component semiconductor detectors (ex. Si and Ge) need a bulky external cooling system Compound semiconductor detectors (e.g. HgI2, PbI2, CdZnTe) are widely studied to overcome this.

VACIS Gamma-ray Imaging System www.saic.com/security

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Sb Doped BiI3

Covalent Bridge

Covalent Bridge

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Nino Research Group

Experimental Procedures Growth chamber

Detector performance analysis

Ampoule cleaning and drying

Electrical property analysis

Powder weighing

Detector fabrication

Vacuuming ampoule

Surface treatment

Sealing ampoule

Single crystal growth

Crystal cutting

Structure composition analysis

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Radiation Detection Improvements

Counts (counts/sec)

0.15

0.15

59.5 keV R = 5.94%

Non-superheated SBI

0.10

0.10 Detector thickness: Detector thinckness: 0.6 cm Bias: 135 V

0.05

0.05 ~0.15 cm3 Pixellated

0.00

Counts (counts/sec)

Nino Research Group

0.00 0

200

400

600

800

1000

Channel number Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Summary

• Defect engineering led to high resistivity, low leakage current, high electron mobility resulting in enhanced performance of Sb-doped BiI3 single crystal radiation detectors. • Superheating effective increases the quality of the crystals grown as evidenced by the ability to consistently extract larger and harder crystals with reduced EPD, narrow rocking curve, and higher sheet resistance. • Defect engineered single crystal BiI3 detectors successfully recorded gamma-ray spectra for the first time (~6% resolution, 241Am) from several sources (241Am, 137Cs, 133Ba, 57Co) and configurations (pixelated, Frisch-collar). Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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Nino Research Group

• • • •

Outlook

Growth of larger crystals (> 2 cm3) Characterize and reduce defect traps Manufacture more Frisch collar type detectors Assess effect of radiation damage on performance • Field testing

detector

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Nino Research Group

Nino Research Group

Advanced Functional Materials Development: An overview of the Nino Research Group at University of Florida

Dr. Juan Claudio Nino Professor and Fulbright US Scholar Materials Science and Engineering, University of Florida 172 Rhines Hall, (352) 846-3787, [email protected]

Professor Juan Claudio Nino – UniValle Physics Colloquium – December 2015

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