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Welcome to Materials Day 2019 Materials Day at Penn State is sponsored by the Materials Research Institute. MRI is composed of over 270 materials-related faculty and their research groups at University Park and Commonwealth campuses. MRI operates four open user facilities for modeling and synthesis, nano- and micro-fabrication, materials characterization, and 2D crystal synthesis. The latter, the Two-Dimensional Crystal Consortium – Materials Innovation Platform, is a recent national user facility supported by the National Science Foundation (DMR-1539916). This year’s topic addresses a perennial issue in university research: How do researchers translate their discoveries in the lab to a point that they can be transitioned into the marketplace where they can benefit society? This dilemma has been dubbed “the valley of death.” In our keynote address by 3D Vice President for Corporate Research Greg Anderson, and in the six breakout sessions, industry and academic experts will offer their solutions with input from audience participants. We want to thank our main sponsors Morgan Advance Materials, Corning Inc, Murata, and Imerys. Enjoy the conversations, keynote address and reception, and the interactive poster sessions. And vote for your favorite poster at the morning and afternoon sessions.
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Table of Contents Agenda……………………………………………………………………………………………………………………………….. 3-5 Campus Map and Event Floor Plans…………………………………………………………….……………………… 6-8 Keynote GREG ANDERSON, Vice President, Corporate Research Lab 3M Company BIO and ABSTRACT…………………………………………………………………………………………………….………… 9 Industry Tabletops………………………………………………………………………………………………….…………… 10 Breakout Sessions……………………………………………………………………………………………………………… 11-16 About the Industry Tours & CrowdCompass App ………………………………….………………………….……..17 Poster List by Research Category……………………………………………………………………………….……. 18-28 Poster List with Authors and Abstracts (AM SESSION)…………………………………………………….….......29 Poster List with Authors and Abstracts (PM SESSION)………………………………………………….…..........59
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Agenda
Tuesday, October 29 All agenda items for Tuesday will be in the Nittany Lion Inn 8:00 a.m. Registration 9:00 a.m. – 11:00 a.m. Poster Session A & Industry Tabletop Displays [Ballroom]
Posters will be presented by many of the Materials Research Institute faculty groups and provide an interactive opportunity to get a snapshot of the breadth of research in materials at Penn State.
10:00 a.m. - 11:00 a.m. Live polling to vote for your favorite poster in Poster Session A
11:00 a.m. KEYNOTE [Ballroom] “Mind the Gap”
Greg Anderson, Vice President, Corporate Research Lab 3M Company (See page 9 for bio and abstract)
12:00 p.m. Lunch [Boardroom A & B] 1:00 p.m. – 3:00 p.m. Poster Session B & Industry Tabletop Displays [Ballroom]
Posters will be presented by many of the Materials Research Institute faculty groups and provide an interactive opportunity to get a snapshot of the breadth of research in materials at Penn State.
2:00 p.m. - 3:00 p.m. Live polling to vote for your favorite poster in Poster Session B 3:00 p.m. – 6:00 p.m. Reception [Boardroom A & B]
State of the Materials Research Institute Clive Randall, professor of materials science and engineering and the director of the Materials Research Institute
Research Centers Overviews Interact with Each Research Center Materials Matter at the Human Level: Funded Proposal Announcement Best Posters Awards Faculty Announcement Winner of the Core Facility Support
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Agenda (continued)
Wednesday, October 30 All agenda items for Wednesday will be in the Millennium Science Complex 8:00 a.m. Registration Coffee and pastries will be provided [3rd Floor Commons] 8:30 a.m. – 10:00 a.m. Breakout Sessions
“Cold Sintering” [N-308A/B] – Jon Paul Maria professor of materials science and engineering – Ram Rajagopalan professor of materials science and engineering
"Quantum Biosensing” [W-306A/B] – Sahin Ozdemir associate professor of engineering science and mechanics – Mauricio Terrones Distinguished Professor of Physics, Chemistry and Materials Science and Engineering
10:15 a.m. – 11:45 a.m. Breakout Sessions
“5G and Beyond” [N-308A/B] – Rongming Chu associate professor of electrical engineering – Mike Lanagan professor of engineering science and mechanics
"Sustainability in Materials Design: Polymer Innovation from Molecules to Market” [W-306A/B] – Erik Foley Instructor, Sustainability Strategy
12:00 p.m. Awards and Lunch [3rd Floor Commons]
Rustum and Della Roy Innovations in Materials Awards PPG Millennium Café Pitch Competition Winners’ Presentations
Best Posters will be on display
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Agenda (continued) 1:30 p.m. – 3:00 p.m. Breakout Sessions
"Glass Technologies and Coatings for Display Applications” [N-308A/B] – Roman Engel-Herbert associate professor of materials science and engineering – John Mauro professor of materials science and engineering
" Energy Harvesting and Storage” [W-306A/B] – Shashank Priya Associate Vice President for Research – Chris Rahn professor of mechanical engineering
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Keynote Speaker Tuesday, October 29 | 11:00 a.m. – 12:00 p.m.
Greg Anderson Vice President, Corporate Research Lab 3M Company
Mind the Gap Bio Greg Anderson is the Vice President of 3M’s Corporate Research Lab. The Corporate Research Lab is responsible for development and deployment of new technology across the global 3M R&D organization. Greg joined 3M in 1993 as a research chemist in the Adhesive Technologies Center, Corporate Research Lab. Greg was part of the Corporate R&D organization working on multiple adhesive platforms before transferring to Business Group R&D organizations and product commercialization. With almost 25 years of product and technology development, Greg has had the opportunity to work with many of 3M’s customers, iconic products and in multiple markets. Working with customers to understand their product and performance needs has been critical input for the development of differentiated new products. Focused on driving high impact growth, Greg works with his teams to identify and drive new opportunities based on new capabilities. Greg has a M.B.A. in Marketing from the University of St. Thomas, M.S. in Organic Chemistry from the University of Minnesota, and a B.S. in Chemistry from Hamline University. He is currently active on two University Advisory Boards. Abstract 3M’s Corporate Research Laboratory (CRL) is a unique group that helps connect technologies to opportunities through the stewardship of 51 Technology Platforms, advanced capabilities and a goal to create sustainable competitive advantage for 3M. Organized globally into 4 laboratories, CRL takes a multi-disciplinary approach to transfer technology solutions in collaboration with our business partners to our customers. Portfolio management, technology development processes and external research ecosystems (including University partnerships) are critical components for a healthy pipeline of new opportunities.
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Industry Tabletops
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Morgan Advanced Materials
Phillip Armstrong [email protected]
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Corning
Nicholas Smith [email protected]
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Thermo Fisher Scientific
Jim Smith [email protected]
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Park Systems
Gilbert Min [email protected]
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CAMECA
Matt Pietrucha [email protected]
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PPG Industries
Nathan Silvernail [email protected]
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Ferro
Robert Hodder [email protected]
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Kurt J. Lesker Company
Joe DeMaio [email protected]
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Protochips
Jordan Moering [email protected]
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MRI’s Virtual Lab Tours
Materials Research Institute
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Breakout Session: Wednesday, October 30 | 8:30 a.m. – 10:00 a.m.
Cold Sintering
Location: MSC N-308A/B
Abstract Cold sintering is an exciting new powder processing technology that provides an opportunity to process a spectrum of traditional and functional materials at extremely low temperatures. This breakout session will assemble participants from industry and academia to share their perspective on potential opportunities and future developments, and to engage in a lively discussion on cold sintering. Some of the major breakthroughs and application spaces for cold sintering ceramics, metals, composites, and polymers will also be discussed.
Session Chairs
Jon Paul Maria - professor of materials science and engineering, The Pennsylvania State University Ram Rajagopalan – professor of materials science and engineering, The Pennsylvania State University
Panelists
v Clive Randall – Director, Materials Research Institute, professor of materials science and engineering,
The Pennsylvania State University
v Ram Rajagopalan – professor of materials science and engineering, The Pennsylvania State University
v Steve Feldbauer – Director, Research and Development, Abbot Furnace Company
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Breakout Session: Wednesday, October 30 | 8:30 a.m. – 10:00 a.m.
Quantum Biosensing
. Location: MSC W-306A/B
Abstract Detecting and quantifying chemical and biological substances, as well as detecting external stimuli in different physical processes, more accurately is of relevance to safety, security and medicine. Therefore, sensors with improved detection limits, sensitivities, and high accuracy are required. Recent studies have shown that the principles of quantum physics can be harnessed to develop emergent sensors and measurement devices – known as quantum sensors- that perform better than conventional sensors. Quantum sensors have been demonstrated for precision measurement of frequencies, magnetic fields, electrical fields, temperatures, displacements and refractive indexes. Quantum sensing is expected to find applications in biology for monitoring single molecules, neurons, and biological processes with improved spatial, spectral and time resolution. The research of quantum sensing involves cross-disciplinary efforts, requiring expertise in physics, biology, chemistry, quantum information science, materials science and engineering, for developing novel sensors and for identifying and tackling key challenges in these fields. This session will explore the current status of quantum sensing and expected applications and will provide attendees an opportunity to understand the challenges ahead and future opportunities. Session Chairs Sahin Ozdemir – associate professor of engineering, science, and mechanics, The Pennsylvania State University Mauricio Terrones – Distinguished Professor of Physics, Chemistry and Materials Science and Engineering, The Pennsylvania State University
Panelists
v Benjamin Lawrie – Research Scientist, Oak Ridge National Laboratory
v Marco Lanzagorta – Research Physicist, Navy Research Labs
v Kevin Cox – Physicist, Army Research Labs
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Breakout Session: Wednesday, October 30 | 10:15 a.m. – 11:45 a.m.
5G and Beyond
Location: MSC N-308A/B
Abstract
Fifth Generation (5G) wireless networks will need extensive spectrum sharing and carrier frequencies up to the millimeter-wave range, creating opportunities for new materials and devices. Semiconductor, ferroelectric and piezoelectric materials are crucial for making active and passive RF components capably of operating at higher frequencies, with lower power loss and greater tunability. The breakout session will be an opportunity for participants from industry, government labs and academia to share their perspectives on future directions for 5G materials.
Session Chairs
Rongming Chu – associate professor of electrical engineering, The Pennsylvania State University Mike Lanagan – professor of engineering science and mechanics, The Pennsylvania State University
Featured Speaker Michael Hill – Technical Director, Skyworks
Panelists
v Jon Paul Maria - professor of materials science and engineering, The Pennsylvania State University
v Thomas Neuberger – Director, High Field Magnetic Resonance Imaging Facility,
The Pennsylvania State University
v Rongming Chu – associate professor of electrical engineering, The Pennsylvania State University
v Tarun Chawla – Technical Manager, Business Development, RemCom
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Breakout Session: Wednesday, October 30 | 10:15 a.m. – 11:45 a.m.
Sustainability in Materials Design: Polymer Innovation from Molecules to Market Location: MSC W-306A/B
Abstract
This session will explore polymer innovation and redesigning plastics and composites for recovery and reuse. The redesign of plastics will require new materials but also new consumer behaviors. This unique cross-disciplinary panel will feature chemical engineering, business marketing and consumer behavior, and leaders from industry.
Session Chair
Erik Foley – Director, Center for the Business of Sustainability, Smeal College of Business, The Pennsylvania State University
Panelist:
v Karen Winterich –professor, Frank and Mary Smeal Research Fellow, The Pennsylvania State University
v Enrique Gomez – professor of chemical engineering, The Pennsylvania State University
v Alicyn Rhoades – associate professor of engineering, plastics engineering technology,
The Pennsylvania State University
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Breakout Session: Wednesday, October 30 | 1:30 p.m. – 3:00 p.m.
Glass Technologies and Coatings for Display Applications
Location: MSC N-308A/B
Abstract
Displays have become a vital part in effectively interacting with large data sets, representing one of the most important human interfaces to information. New glass technologies and coatings are needed for the diverse application space of displays, and their device integration demands new materials and processes. The breakout session will be an opportunity for participants from industry, government labs and academia to share their perspectives on future directions for glass technologies and coatings for display applications.
Session Chairs
John Mauro –professor of materials science and engineering, The Pennsylvania State University Roman Engel-Herbert –professor of materials science and engineering, The Pennsylvania State University
Moderator
v Carlo Pantano – Distinguished Professor Emeritus of Materials Science and Engineering,
The Pennsylvania State University
Panelists
v Nicholas Smith – Research Associate, Thin Films and Surfaces, Corning, Incorporated
v Chris Giebink – associate professor of electrical engineering, The Pennsylvania State University
v John Mauro –professor of materials science and engineering, The Pennsylvania State University
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Breakout Session: Wednesday, October 30 | 1:30 p.m. – 3:00 p.m.
Energy Harvesting and Storage
Location: MSC W-306A/B
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Abstract
Industry 4.0 is driving the development of new generation of smart factory and infrastructure. Similarly, Internet of things (IoT) is driving the development of connected devices and automated systems. Billions of these IoT devices will require new power sources such as energy harvesters and high power/energy density storage devices such as hybrid batteries and capacitors. Energy harvesting from freely available environmental sources such as vibrations, waste heat, sunlight, wind, ocean waves, etc. has shown significant promise in meeting the requirements for the power sources. This session will provide overview of the research advancements made within the National Science Foundation (NSF) Industry – University Cooperative Research Center for Energy Harvesting Materials and Systems (CEHMS) in addressing the needs for electrical power generation and storage. Currently, Virginia Tech and Columbia University are the official sites of CEHMS. Penn State is in the process of becoming an official site. This session will also introduce the attendees to research programs being conducted at CEHMS across all the three partner institutions, technology roadmap, and emerging technology focus areas.
Session Chairs Shashank Priya– Associate Vice President for Research, The Pennsylvania State University Chris Rahn– professor of mechanical engineering, The Pennsylvania State University
Panelists
v Lei Zuo – ASME Fellow, CEHMS Director, Virginia Tech
v Humin Yin – CEHMS Director, Columbia
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About the Industry Tours Visitors to Materials Day from off campus had the opportunity to sign up for one of the tours described below. We also welcome all attendees to take a moment to view the series of posters in our ongoing Materials at Penn State Historical Poster Project. Millennium Science Complex Opened in 2011, the Millennium Science Complex is the largest research building on campus at just under 300,000 sq. ft. User facilities include the basement-level Materials Characterization Laboratory, Nanofabrication Facility and Two-Dimensional Crystal Consortium labs on the first floor, and numerous shared labs throughout the North wing. Materials at Penn State Historical Poster Project The field of materials research is woven from many strands – metallurgy, ceramics, polymer science, physics, chemistry, chemical engineering, electrical engineering, geosciences, the list goes on. The Materials at Penn State Historical Poster Project intends to capture significant people and events related to the illustrious history of materials discovery at this university. Tour all 15 metal-print posters in the ongoing series will be on display in the Millennium Science Complex.
CrowdCompass App for Mobile Devices Download the CrowdCompass AttendeeHub app from your preferred App Store, find “Materials Day 2019” and click “Login”. Enter your First and Last Name and you will verify your account by using your email used at registration. Confirm your email by entering the verification code and you’ll have access to all the important event updates, features, connections, live polling, and more!
CrowdCompass Online for Laptop Go to event.crowdcompass.com/materialsday19 and login as mentioned above.
About Poster Voting We will open a live poll via the CrowdCompass App on Tuesday, October 29 during both Poster Sessions. Instructions on how to vote will be easily accessible from the App. If you want to vote but not via CrowdCompass, visit the voting box at the registration desk outside the Nittany Lion Ballroom during each Poster Session. LIMIT: One vote per attendee per session.
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Poster Listing by Research Category (AM session) Materials Characterization – AM Session Total: 8
1-am. The High Field MRI Facility at PENN STATE
T. Neuberger
2-am. Infrared Spectroscopy for Materials Characterization
T. J. Zimudzi, J. J. Stapleton
3-am. Expanded Capabilities towards Characterizing Mechanical Behavior at MCL
B.A. Last, M. Tilton
4-am. Exploring the Nanostructure World of Materials: A Transmission Electron Microscopy Study
K. Agueda Lopez, S. Bachu, A. Chmielewski, D. Hickey, L. Miao, P. Moradifar, M. Tabatabaei, N. Alem
5-am. Mechanical Characterization and Manufacturability Analysis of Metal Additively Manufactured
Compliant Metamaterial
J. B. Khurana, C. McCartney, L. D. Bobbio, C. Britt, M. Frecker, A. M. Beese
6-am. Thin Film Electrical Characterization Capabilities for Semiconductors, Ferroelectrics & Dielectrics
J.Long, S. Perini, A. Meddeb, W. Zhu
7-am. Characterization of Glass Surface in Aqueous Corrosion with Spectroscopic Techniques and Spectral
Features Interpretation for Silicate Glass Network with Vibrational
H. Liu, S.H. Hahn, D. Ngo, T.M. Gross, S.H. Kim
8-am. Biomechanics and 3D strain mapping in mandible bone
Y. Zhou, C. Gong, M. Hossaini-Zadeh, J. Du
Computer Simulation and Modeling – AM Session Total: 2
9-am. Using Deep Image Colorization to Predict Microstructure-Dependent Strain Fields
P. M. Khanolkar, A. Abraham, C. McComb, S. Basu
10-am. Computation and Synthesis of Two-dimensional Electronically Functional Material
Y. Lu, M. Terrones, S. B. Sinnott
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Biomaterials and Medical Devices – AM Session Total: 5
11-am. Cell Sheet Engineering for Regeneration of the Ligament-Bone Interface
L.M. Berntsen, D.J. Hayes
12-am. The Center for Lignocellulose Structure and Formation (CLSF)
A DOE-funded Energy Frontier Research Center
D. J. Cosgrove
13-am. Disentangling loosening from softening: insights into plant cell wall structure
T. Zhang, H.Tang, D. Vavylonis, D.J. Cosgrove
14-am. Development of Osteopromotive poly (octamethylene citrateglycerophosphate) for Enhanced Bone
Regeneration
Q. K. Li, Y.He, C. Ma, D. Xie, L. Li, Y. Zhao, D. Shan, S. K. Chomos, C. Dong, J. W. Tierney, L. Sun,
D. Lu, L. Gui, J. Yang
15-am. Comparative Morphology of the Dimorphic Leaf Glands in Carnivorous Butterworts (Pinguicula L.)
K. Nolan, K. Bocklund, T. Renner
Nanomaterials and Nano- and Microfabrication – AM Session Total: 7
16-am. Shubnikov de Hass Oscillations to the Quantum Limit at (111) Oriented SrTiO3 Interfaces
Z. Wang, S. Kumari, A. Heltman, Q. Li
17-am. Micro- and Nanoengineering Soft Materials for Environmental & Biomedical Applications
A.Sheikhi
18-am. Defect Mediated Selective Hydrogenation of Nitroarenes on Nanostructured WS2
A. J. Darling, Y. Sun, R. E. Schaak
20-am. A Simple Theory for Binding-Driven Molecular Chemotaxis
K. T. Krist, W. G. Noid
21-am. RF Mediated Release of Fluorophores from Magnetic Nanoparticles by Hysteretic Heating
J. Casey, M.Abu-Laban, J. Becca, B. Rose, K. Strickland, J. Bursavich, J. McCann, C. N. Pacheco, A. Attaluri,
D.J. Hayes
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22-am. Confinement Heteropitaxy: Next Generation 2D Materials for Sensing and Quantum Applications
N. Briggs, A.Vera, S. Rajabpour, T. Bowen, A.D.L. Fuente Duran, B. Bersch, Y.Wang, N. Nayir, K. Wang, C. Dong,
S. Subramanian, J. Jiang, R. Koch, M. Kolmer, J. Zhu, E. Rotenberg, A.-P. Li, A.C.T. van Duin, V.Crespi, J. Robinson
23-am. Tailoring of Nanocomposites with Triaxial Magnetic Field Assembly for Multi-functional Properties
Y. Atescan, R. B. N. Branco, K. Oyama, Namiko Yamamoto
Materials Processing and Manufacturing – AM Session Total: 13
24-am. Universal In-Situ Substitutional Doping of Transition Metal Dichalcogenides by Liquid Precursor-Based
Chemical Vapor Deposition
T. Zhang, K. Fujisawa, F. Zhang, M. Liu, M.C. Lucking, R.N. Gontijo, Y. Lei, H. Liu, K. Crust, T. Granzier-Nakajima,
H. Terrones, A.L. Elías, M. Terrones
25-am. Low Temperature Densification and Opportunity to Create New Materials by the Cold Sintering Process
The Cold Sintering Team
26-am. Cold Sintering Process for Development of all Solid-state Li Batteries
J.-H. Seo, A. Ndayishimiye, W. Lee, R. Fair, Y. Leng, C.-Y. Wang, R. Rajagopalan, E. D. Gomez, T. E. Mallouk,
C. A. Randall
27-am. Role of Poly(N-vinylpyrrolidone) in Controlling Ag+ Reduction Kinetics during Ag Nanostructures
Formation
S. Jharimune, Z. Chen, R. Pfukwa, B. Klumperman, R. M. Rioux
28-am. Carbon Nanoparticle Geometry Drives Nucleation in the Crystallization of PA 66
A. M. Gohn, B. Kindle, A. M. Rhoades
29-am. Rapid-Injection as a Facile and Versatile Processing Method for Preparing Nanostructured
Polymeric Materials
C. Lang, M. Kumar, R.J. Hickey
30-am. Fast, Low-Skilled, and Flexible Building Assembly (NOW!):
Revisiting the Joint-Based Universal Building System
E. Andrzejewski
31-am. Material Synthesis, Characterization, Device Development and Testing Capabilities at the Applied
Research Laboratory’s Electronic Materials and Devices Department (EMDD)
D. Snyder, J. Fox, D. Rearick, R. Lavelle, R. Cavalero, R. Ray, B. Huet, J. Kronz, T. Mirabito, M. Pagan, N.
Christie, C. Wirick
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32-am. Additive Manufacturing of Reinforced Silicones
L. Peeke, M. Hickner
33-am. Textured Piezoelectric Ceramics – A 20 year Journey from Innovation to Commercial Implementation
G. L. Messing, B. Watson, M.J. Brova, R. L. Walton, E. Kupp, M.Fanton, R.J. Meyer
34-am. Controlling Dendrite Growth in Lithium Metal Batteries through Forced Advection
M.N. Parekh, C.D. Rahn, D.L. Koch, L. A. Archer
35-am. Polymer Science in the Pester Research Group
M. Li, M. Fromel, K. Bell, A. Masucci, S. Freeburne, D. Ranaweera, M. Sundy, R. Crisci, V. Patel, C. W. Pester
36-am. Designing of New Precursor (Poly-Pitch) for Carbon Fiber Production
H. Li, J.V. Sengeh, W. Zhu and M. Chung
Electronic/Photonic Materials and Devices – AM Session Total: 10
37-am. Integrated Spectrometers Based on Metasurface-Dressed Waveguides
T Y. Ding, Y. Duan, X. Chen, X. Guo, X. Ni
38-am. Optoelectronically Optimized Nonhomogeneous Thin-Film Solar Cells
F. Ahmad and A. Lakhtakia
39-am. PVA-Zinc water soluble electrode
Y.Gao
40-am. Thin Film Transistors for Flexible and Large Area Applications
A. V. Gupta, S. Lee, T. Liu, M. M. Tendulkar, Q. M. Tran, S. H. Yoo, A. Dangi, J. N. Kim, X. Zhang, E. D. Gomez, E.
W. Gomez, J. M. Redwing, S. Trolier-McKinstry, T. N. Jackson
41-am. Waveguide-Fed Metasurfaces for Free-Space Light Manipulation
X. Guo, Y. Ding, X. Chen, Y. Duan and X. Ni
42-am. Structural Coloration by Cascading Total Internal Reflection and Interference at Microscale
Concave Interfaces
A.E. Goodling, S. Nagelberg, B. Kaehr, C.H. Meredith, S. Cheon, A.P. Saunders, M. Kolle, L.D. Zarzar
43-am. Structural Design for Stretchable Antennas for Strain Sensing and Energy Harvesting
J. Zhu, J. J. Fox, N. Yi, H. Cheng
44-am. Influence of Doping on the Performance of Solid Polymer Electrolyte for Lithium-ion Batteries
S. C.V. Ram, J.Maranas
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45-am. Simulation Study on High-Q GaN Varactors for mm-wave Applications
J.Song, S.-W. Han, R.g Chu
46-am. Power Electronics Wide-Bandgap Materials
S.A. Suliman
Humanitarian – AM Session Total: 3
47-am. Humanitarian Engineering: Towards Developing Sustainable Composite Bricks by Cold-sintering Process
S.H. Bang, A. Ndayshimiye, E. Obonyo, C.A. Randall
48-am. Self-Healing Odor Barrier for Waterless Toilets
B.B. Boschitsch, H. Feldstein, L. Wang, T.-S. Wong
49-am. Graphene-enhanced Raman Spectroscopy for Detection of Biomolecules
*A. Silver, D. Han, S. Huang
Convergence of Materials and Life Sciences – AM Session Total: 2
51-am. Microtomy at Huck Microscopy Facility
G. Ning
52-am. Memory and Learning in Biomolecular Soft Matter for Low-power, Brain-Like Computing
*J.S. Najem
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Poster Listing by Research Category (PM session) Materials Characterization – PM Session Total: 4
53-pm. Materials Characterization Laboratory (MCL)
MCL Staff
54-pm. Thermo-Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) capabilities at Materials
Characterization Lab
E. Bazilevskaya
55-pm. Optical Characterization of TMDCs-Graphene Heterostructures for Next-generation
Opto-electronic Systems
X. Li, M. Blades, B. Huet, T. Choudhury, J. M. Redwing, S. V. Rotkin
56-pm. Novel nano-structured bio-based poly(ε-caprolactone) (PCL)/tung oil blends prepared via in-situ
compatibilization and cationic polymerization
S. A. Madbouly
Computer Simulation and Modeling – PM Session Total: 10
57-pm. Quantum Dynamics in Graphene
J.O. Sofo, B.R. Green, J.L. Robbins
58-pm. Computational Materials System Design
J.P.S. Palma, Z.-K. Liu
59-pm. Machine Learning Assisted Selection of Process Parameters for Controlling Microstructural Properties
in Additive Manufacturing
S. Mondal, A. Ray, A. Basak
60-pm. A Two-stage Optimization Procedure for the Design of an EAP-actuated Soft GRIPPER
W. Zhang, A. Saad, J. Hong, Z. Ounaies, M. Frecker
61-pm. Dabo group: Materials Optimization and Simulation for Energy Applications
Y Xiong, M Burgess, S. Baksa, C Chandler, W Chen, J Fanghanel, J Goff, N Hall,
F. Marques dos Santos Vieira, I. Dabo
62-pm. Understanding Ferroelectric Properties of BaTiO3 using ReaxFF Reactive Force Fields
D. Akbarian, D.E. Yilmaz, A.C. van Duin
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63-pm. µ-pro: Phase-Field-Based Package for Modeling and Simulating Materials Microstructure and Properties
X. Cheng, T. Yang, B. Wang, J. Wang, Y. Ji, R. Wang, L.-Q. Chen
64-pm. Understanding, Prediction, and Design of Materials -- Guided by Multiscale/Mesoscale Computation
X. Cheng, T. Yang, Y. Ji, Z. Liu, B. Wang, Y. Shi, R. Wang, C. Dai, Y. Tan, J. Zorn, D. Fontino, F. Xue, J. Wang,
Y. Wang, L.-Q. Chen
65-pm. ReaxFF: A Predictive Tool for Low Cost Carbon Fiber
S. Rajabpour, Zan Gao, Q. Mao, M. Khajeh Talkhoncheh, B. Damirci, M. Kowalik, X. Li, A.C.T. van Duin
66-pm. Electrochemical Double Layer and Size Effects on Platinum Nanoparticle Dissolution Using COMB3 and
Continuum Electrolyte Models
J. Goff, S. Sinnott, I. Dabo
Biomaterials and Medical Devices – PM Session Total: 5
67-pm. Sustainable and Functional Protein Fibers and Films
H. Jung, C. Skidmore, S. Sayin, Y. Kikuchi, H. Zhu, Be. Allen, M. Demirel
68-pm. Intra-operative Composite Tissue Bioprinting for Craniomaxillofacial Reconstruction
K.K. Moncal, H. Gudapati, K.P. Godzik, D.N. Heo, E. Rizk, D. Ravnic, H.B. Wee, D.F. Pepley, V. Ozbolat, G. Lewis, J.
Z. Moore, R. Driskell, I.T. Ozbolat
69-pm. In vitro Efficacy in Treating Metastatic Triple Negative Breast Cancer in Bone via a Targeted Calci
Phosphosilicate Nanoparticle (CPSNPs) Encapsulating Modified 5-Fluro-Uracil
C. Gigliotti, B. Adair, J. Snyder, N. Gigliotti, W. Loc, J-K Liu, J.H. Adair, A. Mastro
70-pm. Acoustic Characterization of Polymeric Membrane and Coatings Provides Environmental Impacts on
Mechanical Properties
B.D. Vogt
71-pm. Aspiration-assisted Bioprinting
B.Ayan, I.T.Ozbolat
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Nanomaterials and Nano- Microfabrication – PM Session Total: 8
72-pm. Adaptive Thermal Composites
H. Jung, C. Skidmore, S. Sayin, Y. Kikuchi, H. Zhu, B. Allen, M.Demirel
73-pm. 2DLM: The Center for 2-Dimensional and Layered Materials
M. Terrones, J. Robinson
74-pm. Plasmonic Metalattices
L. Kang, P. Mahale, Y. Liu, N. N. Nova, A. Glaid, T. E. Mallouk, J. Badding, D. Werner, N. Alem
75-pm. Liquid-Liquid Phase Separation in Nanoscale Particles
M.A. Freedman
76-pm. Two-Dimensional Material Synthesis via Chemical Vapor Deposition (CVD), Chemical Vapor Transport
(CVT) and Physical Vapor Transport (PVT) Processes
J. Kronz, B.Huet, R. Lavelle, J. Fox, R. Cavalero, T. Mirabito, M.Pagan, N. Christie, D. Snyder
77-pm. Abnormal Interlayer Coupling in Janus MoSSe/MoS2 Heterostructures
K. Zhang, Y. Guo, H. Wang, A.A. Puretzky, D. Geohegan, J. Kong, X. Qian and S. Huang
78-pm. Surface-Initiated Ring-Opening Metathesis Polymerization as a Route to Versatile and Complex
Nanocomposite Materials
J. LaNasa, R.J. Hickey
79-pm. Seeded Growth of Metal Nitrides on Noble Metal Nanoparticles to Form Complex
Nanoscale Heterostructures
R.W. Lord, C.F. Holder, J.L. Fenton, R.E. Schaak
Materials Processing and Manufacturing – PM Session Total: 12
80-pm. Shear Flow-induced Nucleation of Poly(ether ether ketone)
J. Seo, A. M. Gohn, R.P. Schaake, A.M. Rhoades, R. H. Colby
81-pm. Crosslinked Polymer-Graphene Composite Membranes for High-Performance Dewatering of Bio-energy
Relevant Aqueous Streams
O. Agboola M. Lu and M. Hu
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82-pm. “Structural Instability” Induced High-performance NiFe Layered Double Hydroxides as Oxygen Evolution
Reaction Catalysts for pH-near-neutral Borate Electrolyte
Y. Dong, S. Komarneni
83-pm. Atomic Layer Deposition of and on Transition Metal Dichalcogenides
T. N. Walter, A. J. Mughal, O. Cook, K. A. Cooley, S. Lee, X. Zhang, M. Chubarov, J.M. Redwing, T.N. Jackson, S. E.
Mohney
84-pm. Nano- and Micro-structure Engineering of Superalloy and Ceramic Composites by
Field Assisted Sintering
J. Dai, C.I. Lin, J. Singh, N. Yamamoto
85-pm. Atomic Layer Deposition of Metals and Metal Nitrides
B. Liu, B. Rainer
86-pm. Early Age Microstructural Differences of Tricalcium Aluminate and Gypsum Pastes from
Hydration in Microgravity
P.J. Collins, R.N. Grugel, A. Radlińska
87-pm. New Frontiers for Cold Sintering: Instrumentation to Functional Materials
R.D. Floyd, S.M. Lowum, J.P. Maria
88-pm. Characterization of Atypical Martensite Behavior in NiTiNb Alloys
R. W. LaSalle, Dr. R.F. Hamilton
89-pm. Production of Graphene and Conductive Carbon Black Analogue Using Advanced Microwave
Plasma Technology
R.R Kumal, A.Gharpure, A Mantri, K.Zeller, G. Skoptsov, R.V. Wal
90-pm. Advanced Additive Manufacturing of Metals for Emerging Energy Applications
T.A. Palmer
91-pm. Solid Sorbent Development for CO2 Capture
X.X. Wang, R. Zhang, S.M. Liu, C.S. Song
Electronic Photonic Materials and Devices – PM Session Total: 12
92-pm. Low-Temperature Sputtered Gallium Nitride (GaN)
J. Nordlander, K. Ferri, R. Collazo, Z. Sitar, J.-P. Maria
93-pm. Center for Self-Assembled Organic Electronics
E.Gomez, J. Asbury, S. Milner, G. Galli, Z. Bao, A. Salleo, B.Ganapthysubramanian, M.Toney, I. McCulloch
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94-pm. Strategies for the manipulation of the Transport Properties of Ion Exchange Membranes
C. Capparelli, M. A. Hickner
95-pm. Oligomeric Ruthenium Dye for the Improved Efficiency of Water-Splitting Dye-Sensitized Solar Cells
C. Gray, T. E. Mallouk
96-pm. New Polymer-Based Materials for Triboelectric Energy Conversion and Harvesting
J. Dhanani, X. Zhao, Z. Ounaies, O. Rashwan
97-pm. Synthesis of ZnSe Mn2+ Doped Nanoparticles for Tuning Charge Carrier Lifetimes
K.M. Schlegel, J. Asbury
98-pm. Achromatic Metalenses with Inversely Designed Random-Shaped Meta-Atoms
X. Zhang, H. Huang, X. Guo, X. Ni
99-pm. Optics Device Fabrication in the Nanofab
C. Eichfeld
100-pm. Advanced Electroactive Materials and Devices
Q. M. Zhang, Xin Chen, T. Zhang, H. Xi, Q. Zhang, X. Jian, Q. Yang
101-pm. Synthesis of 2D Semiconductors for Sensing and Electronics
R. Torsi, A. Kozhakhmetov, B. Jariwala, N. Simonson, R.Zhao, J. Robinson
102-pm. Functional Electroceramics
S Troiler-McKinstry, K. Coleman, D. Wang, C. Cheng, L. Jacques, N. Bishop, T. Liu, J.I. Yang, W. Zhu, S. Shetty, B.
Akgun, S. Gupta, M. Hahn, T. Peters, P. Tipsawat, S. Aman, D. Hama, S.W. Ko, D. Koh, V. Kovocova, B. Jones, M.
Ritter, B. Gibble, D. Moses, K. Sterling
103-pm. Epitaxial Growth and Morphology Change of Organic Single-crystalline Heterojunctions on Graphene
Z. Guo, A.L. Briseno, S.C.B. Mannsfeld, A. Baca, E.D. Gomez
Humanitarian – PM Session Total: 3
104-pm. 3D Printing of PDMS Microfluidic Device by Nanoclay-reinforced Pluronic F-127 as Sacrificial Material
K. Zhou, B. Ayan, I.T. Ozbolat
105-pm. Scale-up of Moringa-coated Filters for Water Treatment by Varying Packing Fractions of
Sustainable Materials
D. Velegol
106-pm. Development of Clay-based Mixture Design for 3D Printing of Tiny Homes
A. Al-Qenaee, A. Memari, J. Duarte, S. Nazarian, A. Radlinska, M. Hojati
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Convergence of Life and Materials Sciences – PM Session Total: 4
107-pm. Cross-Species Inspired Patterned Slippery Surfaces for Fog Harvesting
L. Wang, J. Wang, R. Wang, T.-S. Wong
108-pm. Non-symmetric Pinning of Topological Defects in a Living Nematic
N. F.Morales, A. Sokolov, M.M. Genkin, I.S. Aranson
109-pm. Ultra-Low Power Biomimetic Sensors
Das Research Group at Penn State Authors: A. Dodda, S. Das, A. Sebastian, A. Oberoi, D.S. Schulman, D.E.
Buzzell, S. Abstract
110-pm. Fabrication of a Vascularized Tumor Microenvironment for Immunotherapy
M. Dey, E.Karhan, C. Tastan, D. Unutmaz, I.T. Ozbolat
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Poster Session A (AM): Poster Listing with Abstract
1-am The High Field MRI Facility at PENN STATE The Huck Institutes of the Life Sciences T. Neuberger
Magnetic Resonance Imaging (MRI) is one of the major imaging modalities in Life Sciences. In Material Sciences it is still not utilized as much as it could be. With the development of new MRI techniques, it is getting more attention in the materials world in recent years. It is e.g. used to study battery degeneration, image defects in 3D printed objects, monitor moisture distribution in drying concrete, and image materials like teeth. Right now, we are working to expand our capabilities to include MR Rheology, a technique that will allow us to perform rheological experiments and characterize e.g. complex fluids, including polymer solutions, liquid crystals, colloidal suspensions and emulsions that do not have to be transparent.
In this work, we will present current projects that are conducted in cooperation with faculty from several departments and highlight MR techniques that could be used to support new research projects.
The High Field Magnetic Resonance Imaging Facility at the Pennsylvania State University comprises two high field preclinical imaging systems. A 7 tesla Bruker Biospec for preclinical imaging and spectroscopy. It has 4 receiver channels, X-nuclei capabilities and the latest available software. The second system is a 14 tesla microimaging system from Agilent. With its four receiver channels and the X-nuclei capabilities it is the perfect tool for MR microscopy and other applications.
2-am Infrared Spectroscopy for Materials Characterization T.J. Zimudzi, J.J. Stapelton
Infrared spectrometry is useful for the identification of both organic and inorganic compounds. Aggregates of atoms (or functional groups) such as C=O, -NO2, C-N, and C-F; just to name a few, are all associated with characteristic infrared absorptions. Thus, infrared spectrometry is ideal for the identification of functional groups present within a sample. FT-IR capabilities within the MCL are geared towards the analysis of solids (organic, inorganic, and biological) in a variety of forms to include fibers, thin films, microtome cuts, particles, powders, coatings, residues, monolayers, and monolithic solids. The MCL also has capabilities to analyze liquids and gas adsorption phenomena. With the recent acquisition of an infrared microscope MCL now has FT-IR mapping/imaging capabilities along with the capacity to perform infrared microanalysis on samples down to ~10 microns in size.
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3-am Expanded Capabilities towards Characterizing Mechanical Behavior at MCL B.A. Last, M. Tilton
The Materials Characterization Lab (MCL) in the Millennium Science Complex is opening a new mechanical testing facility this fall that will allow users to characterize mechanical properties and behaviors across a wide range of materials. Through an extensive equipment acquisition, users will now have access to multiple new instruments including a fully automated microindenter; a thermomechanical analyzer (TMA); two load frames; and a 3D digital image correlation (DIC) system. The two loads frames will have multiple load cells for accommodating soft and hard materials and multiple grips for conducting tension, compression, or 3- and 4-point bend testing. Additional accessories include a fluid bath, a moderate temperature chamber, a high-temperature furnace, and video extensometers. A new wire electron-discharge machine (wire EDM) for sample preparation and an existing dynamic mechanical analyzer (DMA) are also available.
4-am Exploring the Nanostructure World of Materials: A Transmission Electron Microscopy Study K. Agueda Lopez, S. Bachu, A. Chmielewski, D. Hickey, L. Miao, P. Moradifar, M. Tabatabaei, N. Alem
The world has a tremendous demand for innovative materials, that can facilitate travel, communications, business, education, and safety. Consequently, we aim to explore the nanostructure world of materials to design and utilize materials for our future endeavors. Exploring and understanding the effect of atomic structures of defects, vacancies, interfaces, grain boundaries and domain walls on the chemical, physical and electronic properties of materials is a crucial step in material nano-engineering. While crystal structure of materials has been a well-studied subject, little is known about their local atomic and chemical structure, sub-Angstrom structural distortions, and their stability and transition dynamics under extreme conditions. This presentation will show the structurally-driven chemical, physical and electronic properties by probing the atomic bonding, registry and chemistry using a variety of electron microscopy imaging and spectroscopy techniques. The group uses atomic-resolution aberration-corrected transmission electron microscopy (TEM) to visualize and manipulate the atomic structure, electronic structure, bonding, and chemistry in a wide variety of nanocrystals atom-by-atom in both static and dynamic mode. Our efforts include investigating grain boundaries and alloys of two-dimensional (2D) transition metal dichalcogenides (TMDs), electronic and structural characterization of diamondoid carbon nanothreads and ultra-wide bandgap oxide materials, mapping of electromagnetic hotspots associated with localized surface plasmons resonance in metalattice materials. In addition, we present how ferroelectricity polarization emerges across domain walls and interfaces in single phase and hybrid complex oxide systems.
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5-am Mechanical Characterization and Manufacturability Analysis of Metal Additively Manufactured Compliant Metamaterial
J. B. Khurana, C. McCartney, L. D. Bobbio, C. Britt, M. Frecker, A. M. Beese
Metamaterials consisting of cellular arrays of contact-aided compliant mechanisms (C3Ms) can absorb large amounts of energy during quasi-static compression or impact scenarios. These mechanisms exhibit nonlinear stiffness after contact is established within the cell, allowing for large energy absorption per unit mass. With ongoing development of metamaterial design and additive manufacturing, it is essential to characterize manufacturability and mechanical performance to enhance computational design tools. Using the laser powder bed fusion additive manufacturing (AM) process, metamaterial lattices consisting of 3D C3M unit cells are fabricated from Inconel 718. The mechanical response of manufactured 3D C3M metamaterials is characterized through compression testing. A range of metamaterials of varying size, wall thickness and contact gap width are manufactured. Digital image correlation is used to measure local strains in the C3M lattice to understand the mode of energy absorption and compare with mechanical simulations. Further, failure modes for C3M lattice design are highlighted and tends for manufacturability are observed. C3Ms with large wall thickness and largest manufactured size are found to absorb the most strain energy, but also exhibit the highest peak stress. The strain distribution and deformed shape of the lattice is found to be dependent on localized buckling within the cell. Manufacturability and performance are highly dependent on scan strategies used in AM process. By combining design guidelines for mechanical performance and manufacturability using metal additive manufacturing, predictable metamaterial behavior and improved C3M performance can be achieved.
6-am Thin Film Electrical Characterization Capabilities for Semiconductors, Ferroelectrics & Dielectrics J.Long, S. Perini, A. Meddeb, W. Zhu
The MCL Electrical Characterization Lab offers a comprehensive set of measurement techniques and equipment to better understand your materials and devices. Measurements include parametric tests (CV, IV and reliability), impedance spectroscopy (1mHz to 10’s MHz), dielectric displacement, resistivity (Four Point Probe, Van der Pauw) and Hall Mobility. Probe stations offer light shields, vacuum, nitrogen atmosphere and temperatures from 10⁰K to 570⁰K.
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7-am Characterization of Glass Surface in Aqueous Corrosion with Spectroscopic Techniques and Spectral Features Interpretation for Silicate Glass Network with Vibrational Spectroscopies H. Liu, S.H. Hahn, D. Ngo, T.M. Gross, S.H. Kim
Glass surface is important because it significantly affects the performance of glass. To better understand the surface structure of glass, techniques like vibrational spectroscopies were applied to provide structural information. On the other hand, many glass properties were determined by glass material at very near surface. For example, corrosion of glass takes place at interaction of outmost layers of silicate network with hydrous species. In this poster, two studies are summarized, where structural interpretation and corrosion behavior of glass were investigated.
The initial surface condition of glass varies with the preparation condition and has a large impact on its reactivity. Aqueous corrosion behavior of international simple glass (ISG) was investigated with sample prepared by polishing only, and polishing then annealing. It was found that in mild corrosion condition, the effect of initial surface states is significant in affecting the corrosion behavior while in severe condition, the effect was minor.
Vibrational spectroscopies like IR and Raman were used extensively to understand glass structure. However, the interpretation of spectral features is not fully established and some widely used band assignments are lack of justification. In this study, vibrational spectroscopy interpretation was carried out for a series of sodium silicate glass with assistance of MD simulation. It shows that the dominant band shift in Si-O stretch of IR spectra can be correlated with averaged bond length change in glass network, not change of bond angle suggested in a few earlier works. In addition, MD simulation results show inconsistency to Raman spectra with previous assignment in determining Qn species and ring size distribution. That arises the questioning for adequacy of previous band assignments in Raman.
8-am Biomechanics and 3D strain mapping in mandible bone
Y. Zhou, C. Gong, M. Hossaini-Zadeh, J. Du
In-situ mechanical test was coupled with micro-CT to investigate the effect of alveolar bone socket geometry and implant anchorage on bone-implant contact interface and the resulting strain distributions in bone. Compressive axial load was added to top of tooth to simulate chewing process, and then the central tooth was extracted, and dental implants were placed immediately. The same compressive load was added to bone-implant complexes. Using image processing and digital volume correlation, the displacement and strain field inside mandible bone are calculated. Strain distribution within bone-implant complex was compared with strain within bone-periodontal ligament-tooth complex. Limited contact area between bone and implant was observed, while in natural mandible, the periodontal ligament (PDL) acts as medium of force transfer and cushions the load effect. The results are rendered in 3D, and clinical implications of the results are discussed.
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9-am Using Deep Image Colorization to Predict Microstructure-Dependent Strain Fields P. M. Khanolkar, A. Abraham, C. McComb, S. Basu
The microstructure of a material governs mechanical properties such as strength, toughness and others. Various finite element method (FEM) software packages are used to perform structural analyses such as predicting the flow of strain or strain fields in a microstructure. Engineers frequently operate these software packages to evaluate mechanical behavior and predict failure. Even though these FEM software packages provide highly accurate analyses, they are computationally intensive, taking a significant amount of time to produce a solution. The time required by the FEM software packages to achieve accurate results largely depends on microstructure details and mesh resolution, thus providing a trade-off between fidelity and computation time. This research proposes the use of Deep Learning algorithms to achieve a significant reduction in the time required to predict high-accuracy strain fields in a two-dimensional microstructure with defects. Synthetic data was generated using an FEM software package, producing images of defect-ridden microstructure (black and white) and corresponding images of strain fields (colored). The deep neural network was trained to predict the strain field based upon the microstructure. The coefficient of determination, along with the mean squared error, were used as the performance metrics to validate the accuracy of the predictions made by the neural network. Training and testing on 500 datasets respectively, each containing microstructures with different defect-layouts, resulted in effective prediction of strain fields in microstructures approaching 95% accuracy in less than half of a second. In contrast to traditional FEM software packages, it is observed that the time required by the deep neural networks for providing predictions depends majorly on the network architecture rather than the quantity and size of defects in the microstructure, without compromising the accuracy. This work presents a foundation for developing deep neural networks to conduct structural analyses, thus reducing the exclusive use of computationally demanding FEM software and augmenting the analytical capabilities of scientists and engineers.
10-am Computation and Synthesis of Two-dimensional Electronically Functional Materials Y. Lu, M. Terrones, S. B. Sinnott
Two-dimensional materials offer a platform that allows the creation of heterostructures with a variety of properties. Many of these materials are stable at ambient conditions, and we have come up with strategies for handling those that are not. Surprisingly, the properties of such 2D materials are often very different from those of their 3D counterparts. By combining chemical vapor deposition and first-principles calculations in 2D crystal interfaces, the interfacial structure, electronic properties, growth mechanisms, electromechanical behaviors, and doping engineering are investigated. The findings have implications for the use of 2D materials in high-performance and energy-efficient devices.
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11-am Cell Sheet Engineering for Regeneration of the Ligament-Bone Interface L.M. Berntsen, D.J. Hayes
Repair of ligament remains a challenge due to failure to regenerate the ligament-bone interface as a functionally graded tissue. Adipose-derived mesenchymal stem cells represent a single autologous cell source with the potential to differentiate into multiple cell types for regeneration of complex tissue interfaces. There have been promising results for tissue engineering of ligament and bone from mesenchymal stem cells with phasic scaffolds, but integration of tissue layers remains a challenge. To achieve better integration of layers, cell sheets are being explored as a scaffold-free alternative for tissue engineering. Cell sheets enable growth and harvesting of cells without disrupting the extracellular matrix and cell-cell junctions. When stacked, cell sheets form a quasi- three-dimensional layered tissue construct. In this study, ASC cell sheets are differentiated into osteogenic and ligamentogenic progenitors and cocultured in stacks to form an integrated tissue construct towards regeneration of the ligament-bone interface. Human adipose-derived mesenchymal stem cells (ASCs) were cultured on thermally responsive methylcellulose and PNIPAAm polymers and harvested as intact cell sheets via spontaneous detachment at room temperature. ASCs in cell sheets were committed to ligamentogenic and osteogenic lineages with chemical induction medium for two weeks. Cell sheets were then stacked and cultured together in basal growth medium for an additional week and compared to basal growth medium controls. Cell sheets were analyzed for mineralization with OsteoImage. Histology of cell sheet sections and immunofluorescence were used to analyze integration of cell sheet layers and protein expression. Gene expression was quantified with RT-PCR. Cell sheets cultured in ligamentogenic medium showed upregulation of scleraxis, tenascin-c and collagen types I and III compared to basal medium controls after two weeks, with upregulation of tenomodulin three weeks post induction. Cell sheets cultured in osteogenic medium had increased expression of RUNX2 and osterix, with positive staining for hydroxyapatite after three weeks. After one week co-culture, ligamentogenic-osteogenic stacked cell sheets maintained expression of scleraxis and tenomodulin with increased positive staining for mineralization when compared to basal growth medium and ligamentogenic controls. Histology showed integration of cell layers into a single tissue construct. Adipose-derived mesenchymal stem cells cultured in cell sheets were differentiated into progenitors of ligament and bone. Co-cultured ligamentogenic-osteogenic cell sheets exhibited markers for both tissue types with integration of tissue layers. Further study will improve our understanding of the interactions between ligamentogenic and osteogenic cells that influence regeneration and repair of the ligament-bone interface.
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12-am The Center for Lignocellulose Structure and Formation (CLSF) A DOE-funded Energy Frontier Research Center
D. J. Cosgrove
Other Senior Personnel: Penn State University: Charles Anderson; Enrique Gomez; Esther Gomez; Ying Gu; Seong Kim; Tracy Nixon; Ming Tien. North Carolina State University: Candace Haigler; Yaraslova Yingling. University of Virginia: Jochen Zimmer. Oak Ridge National Lab: Hugh O’Neill. University of Rhode Island: Alison Roberts. University of Texas at El Paso: James Kubicki. Massachusetts Institute of Technology: Mei Hong. University of Chicago: Gregg Voth. University of Cambridge (U.K.): Paul Dupree.
Plant cell walls (CWs, also known as cellulosic biomass or lignocellulose) are among the most complex and diverse materials on Earth. These hierarchical structures represent an abundant and renewable source of valuable biomaterials and bioenergy, presenting untapped transformative opportunities for engineering them for new purposes while simultaneously providing lessons on how to mimic these complex living materials with specific, tunable properties. CLSF’s mission is to develop a detailed nano- to meso-scale understanding of plant cell walls, from cellulose microfibril formation to the assembly of microfibrils with other CW components to form versatile plant CWs. This research - at the nexus of physics, chemistry and biology - forms the foundation for future efforts to optimize the structures and utility of plant CWs, which are essential to plant life and comprise a large-scale source of renewable biomaterials and bioenergy.
The new CLSF goals build upon notable advances made in the past funding period and include:
1. Combine multiple state-of-the-art methods of electron microscopy with neutron and X-ray scattering, computational modeling and biochemistry to solve the structure and catalytic mechanism of recombinantly-expressed plant cellulose synthases (CesAs) and native cellulose synthesis complexes (CSCs).
2. Manipulate active CesA assemblies in vitro and in vivo to learn how artificial and native CSCs are assembled and how microfibril structure depends on CSC structure. Use these new experimental platforms to test computational models of CSC and microfibril assembly.
3. Develop new experimental and quantitative methods for assessing microfibril organization in CWs and use them to uncover the physical mechanism(s) of microfibril bundling.
4. Extend newly developed CLSF methods and results to analyze the physical basis of microfibril-matrix interactions in dicot and grass CWs and study the structural, physical and mechanical consequences of altering these interactions in primary and secondary CWs.
5. Develop new biological systems (e.g., the developing Arabidopsis inflorescence stem and xylem-transdifferentiation in transgenic seedlings and protoplasts) to study the processes of microfibril bundling, 1o CW assembly and maturation, and 2o CW formation.
These goals require the development of novel approaches, experimental platforms and advanced instrumentation. Through complementarity, the five
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goals will synergistically produce key insights for potential ways to achieve analogous control of other materials and for ways to tune CW assembly for specific properties in the materials and energy fields. Overall success with even a subset of these goals will enable a quantum leap in understanding how plants assemble these complex hierarchical structures.
13-am Disentangling loosening from softening: insights into plant cell wall structure T. Zhang, H.Tang, D. Vavylonis, D.J. Cosgrove
How cell wall elasticity, plasticity, and time-dependent extension (creep) relate to one another, to plant cell wall structure and to cell growth remain unsettled topics. To examine these issues without the complexities of living tissues, we treated cell-free strips of onion epidermal walls with various enzymes and other agents to assess which polysaccharides bear mechanical forces in-plane and out-of-plane of the cell wall. This information is critical for integrating concepts of wall structure, wall material properties, tissue mechanics, and mechanisms of cell growth. With atomic force microscopy we also monitored real-time changes in the wall surface during treatments. Driselase, a potent cocktail of wall-degrading enzymes, removed cellulose microfibrils in superficial lamellae sequentially, layer-by-layer, and softened the wall (reduced its mechanical stiffness), yet did not induce wall loosening (creep). In contrast Cel12A, a bifunctional xyloglucanase/cellulase, induced creep with only subtle changes in wall appearance. Both Driselase and Cel12A increased the tensile compliance, but differently for elastic and plastic components. Homogalacturonan solubilization by pectate lyase and calcium chelation greatly increased the indentation compliance without changing tensile compliances. Acidic buffer induced rapid cell wall creep via endogenous α-expansins, with negligible effects on wall compliances. We conclude that these various wall properties are not tightly coupled and thus reflect distinctive aspects of wall structure. Cross-lamellate networks of cellulose microfibrils influenced creep and tensile stiffness whereas homogalacturonan influenced indentation mechanics. This information is crucial for constructing realistic molecular models that define how wall mechanics and growth depend on primary cell wall structure.
14-am Development of Osteopromotive poly (octamethylene citrate glycerophosphate) for Enhanced Bone Regeneration
Q. K. Li, Y.He, C. Ma, D. Xie, L. Li, Y. Zhao, D. Shan, S. K. Chomos, C. Dong, J. W. Tierney, L. Sun, D. Lu, L. Gui, J. Yang
The design and development of bioactive materials that are inherently conducive for osteointegration and bone regeneration with tunable mechanical properties and degradation remains a challenge. Herein, we report the development of a new class of citrate-based materials with glycerophosphate salts, β-glycerophosphate disodium (β-GP-Na) and glycerophosphate calcium (GP-Ca), incorporated through a simple and convenient one-pot condensation reaction, which might address the above challenge in the search of suitable orthopedic biomaterials. Tensile strength of the resultant poly (octamethylene citrate glycerophosphate) POC-βGP-Na and POC-GP-Ca was as high as 28.2±2.44 MPa and 22.76±1.06 MPa, respectively. The initial modulus ranged from 5.28±0.56 MPa to 256.44±22.88 MPa. The mechanical properties and degradation rate of POC-GP could be controlled by varying the type of salts, and the feeding ratio of
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salts introduced. Particularly, POC-GP-Ca demonstrated better cytocompatibility and the corresponding composite POC-GP-Ca/hydroxyapatite (HA) also elicited improved osteogenic differentiation of human mesenchymal stem cells (hMSCs) in vitro, as compared to POC-βGP-Na/HA and POC/HA. The superior in-vivo performance of POC-GP-Ca/HA microparticle scaffolds in promoting bone regeneration over POC-βGP-Na/HA and POC/HA was further confirmed in a rabbit femoral condyle defect model. Taken together, the tunability of mechanical properties and degradation rates, together with the osteopromotive nature of POC-GP polymers make these materials, especially POC-GP-Ca well suited for bone tissue engineering applications.
15-am Comparative Morphology of the Dimorphic Leaf Glands in Carnivorous Butterworts (Pinguicula L.)
K. Nolan, K. Bocklund, T. Renner
In angiosperms, plant carnivory is one of the most unique adaptations to limited nutrient availability. With highly modified leaves, carnivorous plants are capable of attracting, trapping and digesting prey to supplement nutrients not readily available in the environment. The family Lentibulariaceae (Lamiales) is exclusively carnivorous and includes the genus Pinguicula (butterworts) that is sister to two remaining genera, Genlisea (corkscrew plants) and Utricularia (bladderworts). My research seeks to establish Pinguicula as a model system for understanding the evolution of carnivory in the Lentibulariaceae, given the ease to grow the genus in culture and for the simplicity of its trapping system – a basic flypaper trap based on sticky glands. An investigation of the dimorphic glands found on the surface of the carnivorous leaves of four Pinguicula species will be presented. The delicate nature of Pinguicula leaves, due to a lack of lignin, made traditional electron microscopy difficult. The abrasive nature of specimen fixation protocols was damaging to the leaf tissue and glandular structures. Using cryo-SEM, however, leaf tissue and glandular structures were left intact. Morphological studies will help to illuminate the structure and function of the glands and also lend character states useful for resolving the Pinguicula phylogeny. In addition to morphology, gene expression studies combined with genome sequencing will help to elucidate the diversity of gene families important for carnivory in Pinguicula.
16-am Shubnikov de Hass Oscillations to the Quantum Limit at (111) Oriented SrTiO3 Interfaces Z. Wang, S. Kumari, A. Heltman, Q. Li
Two-dimensional electron systems at SrTiO3 (STO) surfaces and interfaces have attracted much attention due to their fascinating properties. Among them (111)-orientated STO is of special interest since the similarity between (111) surface of cubic lattice ABO3 and graphene offers a promising prospect to realize novel topological phases. Until now, however, most studies on SrTiO3 (STO) based 2D electron systems focus on the (001) orientation, whereas investigations on high mobility STO (111) systems are relatively rare. Here we created two-dimensional electron systems in STO (111) orientation with high mobility over 15000 cm2V-1s-1 and low carrier density at the level of 1013 to 1014/cm2. Interface engineering was utilized to modulate the sample dimensionality and properties. Shubnikov-de Hass (SdH) oscillations was systematically studied and Quantum Hall like behavior was revealed at STO (111) interface. Rxx exhibits SdH oscillations with 1/B periodicity and minima at the same positions as the plateau-like structures in Rxy,
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suggesting the observation of the quantum Hall effect. Moreover, the 2D electron system reaches the lowest Landau level in high pulsed magnetic field measurements up to 60 T.
17-am Micro- and Nanoengineering Soft Materials for Environmental & Biomedical Applications A. Sheikhi
Soaring population growth, supply and demand imbalance, shortage of ready-to-use remedies, and urbanization have imposed unprecedented challenges to satisfying the world’s essential needs for water, healthcare, food, and energy. I aim to address some of the quintessential challenges of the 21st century in water treatment and precision medicine by designing conceptually novel sustainable material platforms based on micro- and nanoengineering the most abundant natural bioproducts. My overarching goal is to provide transformative and/or translational solutions based on highly renewable resources that can set the stage for the adoption of affordable, widespread technologies with immediate benefits for humans and ecosystems. In this poster, I will first detail how nanoengineering the most abundant biopolymer in the world, cellulose, has led to the invention of the first biomass-based, environmentally friendly threshold (ppm level) antiscaling additives and scale-resistant membranes. I will introduce a fundamentally novel family of nanocelluloses, named hairy cellulose nanocrystals, and explain how they overcome the limitations of current nanocelluloses, cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs), to open new horizons in water remediation and blood purification. Then, I will explain how silicon, the most abundant mineral in soil, can form nanoscale layered silicates (nanoclay) with unique structure-property relationships that provide reversible colloidal binding. I will introduce nanoclay-polymer composite hydrogels to address several unmet clinical needs, such as minimally invasive aneurysm treatment and reversible birth control. Finally, I will elucidate how microengineering gelatin (a derivative of the most abundant protein in the body, collagen) yields an injectable, bio-orthogonal hydrogel platform with orthogonal stiffness and porosity that is impossible to create using bulk hydrogels. This class of microfluidic-enabled modular hydrogels may pave the way towards 3D bioprinting thick tissues and developing the next generation of disease models. Together, these materials show the power of harnessing nature’s building blocks to produce functional soft matter. Colloidal particles, polymers, gels, foams, dispersions, and emulsions created from these abundant resources can leverage eminent, cost-effective technologies for improving the quality of modern life.
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18-am Defect Mediated Selective Hydrogenation of Nitroarenes on Nanostructured WS2
A. J. Darling, Y. Sun, R. E. Schaak
Transition metal dichalcogenides (TMDs) have emerged as a promising class of materials that exhibit unique, tunable properties that are amenable for catalytic applications. This class of materials has shown promise for hydrogenation reactions, particularly due to the near-zero energy of hydrogen to TMD edge sites. However, TMD catalysts for these reactions often require the use of metal promotors, and mechanistic insights remain limited. Recently, we have shown that colloidally synthesized promotor free WS2 nanostructures are able to serve as an ideal platform to investigate how selectivity and activity can be achieved in 2D materials. These few-layer nanosheets are able to selectively hydrogenate substituted nitroarenes to their corresponding aniline derivatives, and can be recycled with little decrease in catalytic activity, demonstrating the versatility of this catalyst for the synthesis of complex aniline molecules. Microscopic and computational studies provide insight to the role of sulfur of defects on both the basal plane and edge sites of these materials as the origin of this functional group selectivity.
20-am A Simple Theory for Binding-Driven Molecular Chemotaxis K. T. Krist, W. G. Noid
Chemotaxis is the directed motion of a particle in response to a gradient of chemical concentration. Over the past 15 years, researchers have recognized the utility of chemotaxis for designing micro- and nanoscale motors that can move and perform specific tasks in the absence of an externally applied field. Such autonomous devices hold great promise for applications in targeted drug delivery, chemical sensing and separations, and environmental remediation. While there exists a significant body of experimental and theoretical literature on the self-propulsion of synthetic micromotors, the directed motion of small molecules in solution remains relatively unexplored. We propose a simple equilibrium theory that predicts that molecular chemotaxis can be driven by the chemical potential gradient that arises from thermodynamically favorable interactions between two co-solutes.
We consider a one-site reversible binding interaction between a probe molecule and ligand. Using the McMillan-Meyer treatment of imperfect dilute solutions and macromolecular binding theory, we derive the effective chemical potential for each co-solute. The form of the chemical potential reveals two competing driving forces: diffusion from high to low concentration due to Fick’s 2nd Law, and a tendency for molecules to move towards their unbound binding partners. This second force is thermodynamic in nature and arises from the binding free energy. By invoking the Einstein relation and assuming the system is in the overdamped regime, the Fokker-Planck (FP) equation for the time evolution of each co-solute is determined.
To simulate the chemotactic behavior of the probe, we replicate the geometry of a three-inlet one-outlet microfluidic channel used in molecular chemotaxis experiments. The concentrations are initialized such that the probe is localized in the center third of the “channel” and the ligand is introduced from the left. The FP equation is numerically integrated to determine the final concentration profiles of probe and ligand for a given channel residence time. To quantify the behavior of probe in response to the ligand, we measure the “chemotactic shift”
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(µ) by calculating the average horizontal position of the probe with and without ligand and taking the difference. We observe that the plot of µ as a function of ligand concentration resembles a titration curve, with the equivalence point corresponding to a ligand concentration that approximately equals the dissociation constant Kd. When a second ligand binding site is introduced, the chemotaxis of the probe is significantly enhanced. We expect that our model is general enough to describe any chemotactic system where the overdamped regime and local equilibrium are valid assumptions.
21-am RF Mediated Release of Fluorophores from Magnetic Nanoparticles by Hysteretic Heating
J. Casey, M.Abu-Laban, J. Becca, B. Rose, K. Strickland, J. Bursavich, J. McCann, C. N. Pacheco, A. Attaluri, D.J. Hayes
This study explores the use of differential heating of different sized and composition nanoparticles for heteroplexed temporal controlled release of conjugated fluorophores from the surface of nanoparticles. By exploiting differences in size and composition of nanoparticles (MFe2O4 (M= Fe, Co)), we were able to control the amount of hysteretic heating occurring with distinct sets of magnetic nanoparticles using the same alternating magnetic field radio frequency (AMF-RF). Using thermally labile Retro-Diels-Alder linkers conjugated to the surface of nanoparticles, the fluorescent payload from the different nanoparticles disengaged when sufficient energy was locally generated during hysteretic heating. The microscopic localized heating (<60°) from the different nanoparticle compositions, caused the Retro-Diels-Alder reaction at different times resulting in higher release rates of fluorophores from the CoFe2O4 vs the Fe3O4 nanoparticles. 1H, 13C NMR, ESI-MS, and SIMS characterized the thermally responsive fluorescent linkers used in this study; the Diels Alder Cycloadducts were modeled using DFT computations.
22-am Confinement Heteropitaxy: Next Generation 2D Materials for Sensing and Quantum Applications N. Briggs, A.Vera, S. Rajabpour, T. Bowen, A.D.L. Fuente Duran, B. Bersch, Y.Wang, N. Nayir, K. Wang, C. Dong, S. Subramanian, J. Jiang, R. Koch, M. Kolmer, J. Zhu, E. Rotenberg, A.-P. Li, A.C.T. van Duin, V.Crespi, J. Robinson
Atomically thin, two-dimensional (2D) metals hold promise for next-generation quantum and optoelectronic technologies. However, realizing atomically-thin metals which are also air-stable requires new approaches to materials synthesis and stabilization. One such approach involves the intercalation of epitaxial graphene (EG) layers grown on silicon carbide (SiC) substrates. Specifically, elemental species can be intercalated to the interface between EG layers and SiC, where they form few-atom-thick films. The overlying EG layers serve as a protective cap, preventing exposure of the atomically-thin metal films to ambient conditions. Here, we introduce the process used to synthesize 2D metals, which we term Confinement Heteroepitaxy (CHet) and demonstrate a range of metals that have been successfully stabilized in 2D form. The metal films may be realized over 100s of microns and are stable in ambient for up to 9 months. Furthermore, these materials exhibit a range of properties including superconductivity with enhanced transition temperatures relative to bulk, large nonlinear optical susceptibility, and long surface plasmon lifetimes. The CHet process paves the way for new approaches to 2D materials synthesis via exploitation of material interfaces, and enables materials that may be used in technologies ranging from quantum electronics to biological sensing.
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23-am Tailoring of Nanocomposites with Triaxial Magnetic Field Assembly for Multi-functional Properties
Y. Atescan, R. B. N. Branco, K. Oyama, Namiko Yamamoto
Precise structuring of nanoparticles with controllable interfaces is critical to provide tailorable polymer nanocomposites (PNCs) with enhanced anisotropic properties (mechanical, electrical, thermal, actuation, etc.). The active assembly of nanoparticles using magnetic fields is a potential fabrication method to tailor PNCs with small field strength and thus power, ease of process, and patterning capability. This study aims to evaluate 1) the effectiveness of uniaxial, biaxial and triaxial nanoparticle assemblies using oscillating magnetic fields and 2) the structure-property relationship of two nanocomposite systems: magnetoelastomers (MEs) and carbon nanotube (CNT)-PNCs.
MEs are composite materials consisting of magnetically responsive particles (nano- to micro-scale) suspended or arranged in non-magnetic elastomer matrices. As a class of smart materials, the rheological and magnetostrictive properties of MEs can be altered rapidly and anisotropically by applying a non-contact external magnetic field. Due to their controllable stiffness, sensing and actuation behaviors, MEs have potential applications in vibration control, soft robotics and deployable structures. In this study, nanoparticle structures are magnetically assembled, and their 2D/3D structures are studied and correlated with the MEs’ actuation behaviors. Ferrimagnetic gamma-phase iron oxide nanoparticles (γ-Fe2O3, ~25 nm diameter) and an elastomeric matrix (Polydimethylsiloxane, PDMS, Elastomer RT 604A/B, mass ratio 9:1, 800 cP at RT) are selected for this study. 2D/3D structured MEs are fabricated with low magnetic flux density (<300 G), low frequency (0-1 Hz) and phase shift (0-180 degree) by using a triaxial Helmholtz coil experimental set-up. The resulting nanoparticle structures are characterized using microCT scans to determine assembly feature sizes, inter-nanoparticle distances, and more.
Introducing CNTs to PNCs can increase thermal and electrical conductivity, mass-specific strength, and stiffness, thus providing many potential applications in aircraft and spacecraft. However, CNTs are difficult to disperse and organize within viscous matrices. Applying a magnetic field can potentially organize CNTs in a similar manner as the above iron oxide nanoparticles, but CNTs need to be magnetized in order to respond to the magnetic field. In this work, CNTs are grown using chemical vapor deposition, coated with nickel for magnetization, and functionalized with diazonium salts for improved dispersion. These CNT-PNCs will be prepared as nano-sized prepregs in the future, to be integrated into carbon fiber reinforced plastics.
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24-am Universal In-Situ Substitutional Doping of Transition Metal Dichalcogenides by Liquid Precursor-Based Chemical Vapor Deposition T. Zhang, K. Fujisawa, F. Zhang, M. Liu, M.C. Lucking, R.N. Gontijo, Y. Lei, H. Liu, K. Crust, T. Granzier-Nakajima, H. Terrones, A.L. Elías, M. Terrones
Both doping and heterostructures lie at the heart of modern semiconductor technologies. Therefore, for two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs), the controlled doping and heterostructures formation are of high significance. Recent studies have indicated that, by substitutionally doping semiconducting 2D TMDs materials with a judicious selection of dopants, the electrical, optical, magnetic and catalytic properties can be effectively tuned. Furthermore, seamless lateral stitching of TMDs with dissimilar compositions enables the formation of atomically thin in-plane heterojunctions, endowing them with great potential for electronic and optoelectronic applications. In light of this, it is desired to develop a reliable doping method for TMDs that can be potentially suitable for a wide range of dopants, as well as an efficient route for creating in-plane heterostructures between two dissimilar TMDs. Herein, inspired by the sol-gel process, we reported a swift approach for achieving substitutional doping and the formation of heterostructures of monolayer semiconducting TMDs, based on a solution precursor-based chemical vapor deposition (CVD) technique. This method relies on the spin-coating and high-temperature sulfurization of aqueous solutions containing water-soluble host material and dopant precursors. Various transition metal atoms, such as Fe, Re and V, have been incorporated in the lattice of semiconducting TMD monolayers, such as WS2 and MoS2, so as to form iron (Fe)-doped WS2, rhenium (Re)-doped MoS2, and more complex material systems such as vanadium (V)-doped in-plane WxMo1-xS2-MoxW1-xS2 heterostructures, among others. We envisage that our developed approach is universal and could be extended to incorporate a variety of other elements into 2D semiconducting TMDs, which may enable novel applications such as electronics and spintronics at the 2D limit.
25-am Low Temperature Densification and Opportunity to Create New Materials by the Cold Sintering Process
The Cold Sintering Team
CSP (cold sintering process) is the process where inorganic powders are densified in the presence of a transient liquid phase at a phase fraction typically between 1 -10 vol%. During CSP, the liquid phase becomes the medium for mass transport. Recently, a broad number of ceramic compositions that can undergo a cold sintering were reported by Randall et al.: binary, ternary, and quaternary compositions from oxide, bromide, chloride, fluoride, phosphate, and carbonate chemistries. In most cases, temperature and pressure typically span respectively the range between 25°C - 300°C and 1 atm - 500 MPa. Besides energy-efficiency, the interest and utility of CSP is amplified by an expanded ability to integrate across conventional material classes, providing novel methods to assemble composites and join materials. In fact, it creates opportunities to combine materials that previously would chemically react, decompose, or volatilize, thus allowing the development of unique bulk materials, multilayers, and thick films. The constituent materials can encompass inorganics, nanomaterials, biomaterials, polymers, quantum dots, 2-D materials, liquid crystals, phosphors, Metal-Organic Frameworks (MOFs), etc., and create new multifunctionality within new composite and device designs.
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26-am Cold Sintering Process for Development of all Solid-state Li Batteries J.-H. Seo, A. Ndayishimiye, W. Lee, R. Fair, Y. Leng, C.-Y. Wang, R. Rajagopalan, E. D. Gomez, T. E. Mallouk, C. A. Randall
All-solid-state lithium batteries have been attractive as a next generation energy storage device with the number of advantages such as high energy density, enhanced safety and possibility of lithium metal anode. However, the fabrication process of the all solid-state is still very challenging due to the high temperature sintering process in the range of 800 ~ 1200 °C required to densify the solid electrolyte layer and composite electrode layers.
Recently, an extremely low temperature ceramic sintering process, Cold Sintering Process, for sintering of ceramics and ceramic-based composites was proposed. This process is a very promising process which enables to save energy and cost and avoid any problematic reactions during the sintering process by lowering the sintering process. Basically, highly densified structures are developed through a mediate dissolution-precipitation process in transient aqueous conditions at low temperature during cold sintering process. Various kind of materials having high density using cold sintering process were successfully demonstrated including a highly densified Li-ion cathode materials fabricated by the cold sintering process at 180 ~ 240 °C. Moreover, it was reported that the LiFePO4-based binder-free thin composite cathode cold sintered can deliver very high volumetric capacity density, rate performance and cyclability.
It is proposed that the cold sintering process can be employed to fabricate highly densified electrode and electrolyte layers for all solid-state batteries. We believe that the cold sintering process would be very effective method to densify the microstructures of each layers and improve the contacts between them to achieve high electrochemical performance, e.g., the ionic conductivity, gravimetric and volumetric energy density, of the all-solid-state Li batteries. Specifically, the cold sintering process enables to improve the intimate contacts between active materials, conductive carbon and solid electrolyte particles as well as sinter the solid electrolyte layer at a low temperature.
In this presentation, it will be discussed how to apply the cold sintering process to develop the all solid-state Li batteries. Several examples of the cold sintered composite for all-solid-state Li batteries including their microstructures, properties and electrochemical performances will be shown.
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27-am Role of Poly(N-vinylpyrrolidone) in Controlling Ag+ Reduction Kinetics during Ag Nanostructures Formation
S. Jharimune, Z. Chen, R. Pfukwa, B. Klumperman, R. M. Rioux
Poly(N-vinylpyrrolidone) (PVP) is ubiquitously used in shape-controlled polyol synthesis of metal nanoparticles (NPs). Among the various systems using PVP, polyol synthesis of Ag nanocubes (NCs) has emerged as one of the most common systems, where PVP is considered as the structure-directing agent, and glycolaldehyde (GA), an oxidation product of ethylene glycol (EG) as the reducing agent for Ag+ at elevated temperature. While several reports indicate molecular weight (Mw) and monomer concentration (Cm) of PVP impact the final shape of NPs, a universal agreement on the role of PVP is thus far lacking. Recent experimental studies from our group indicate the differential heat of adsorption of PVP to (100) versus (111) facets is too small to predict a cube over an octahedron via a thermodynamic Wulff construction. We further demonstrate chloride (Cl¯) added as HCl is the structure-directing agent in the synthesis of Ag NCs. However, PVP influences the final shape of Ag NPs beyond stabilization since changes in monomer concentration (Cm) or molecular weight (Mw) impact shape, suggesting PVP may influence the rate of reduction leading to kinetically preferred shapes even in the presence of Cl¯.
We demonstrate PVP acts both as the dominant reducing agent, where the end groups are responsible for influencing Ag+ reduction kinetics. We constructed an experimental phase diagram for the formation of Ag NCs by varying the PVP Cm and Mw at constant temperature and Cl¯ concentration. Between the upper boundary (related to the role of PVP in Ag+ reduction) and the lower boundary (related to a required minimum amount of PVP for stabilization) of the phase diagram, any combination of PVP Cm and Mw, can yield uniform Ag NCs. Optical studies of Ag+ reduction at different PVP Cm and Mw show direct dependence of Ag+ reduction to the molar ratio of PVP/Ag and a decreased rate with higher Mw at constant Cm. These combined results suggest PVP rather than EG or GA plays a dominant role in the reduction of Ag+ and the reducing power is enhanced in presence of more PVP end-groups. Although, the PVP end-group/Ag+ ratio is well below stoichiometry, we demonstrate using ion selective electrodes, Ag+ reduces auto-catalytically after the initial reduction by PVP end-groups. In order to further investigate the complex mechanism of Ag+ reduction by PVP, we synthesized end-groups specific PVP polymers with a precise control over the average Mw. Experimental results indicate, end groups are indeed responsible for influencing Ag+ reduction kinetics; PVP with –OH end groups generate kinetically-preferred Ag NPs (nanorods) while those with –CHO end groups form Ag NCs. Overall this work provides key insights into understanding the role of PVP in influencing reduction kinetics of Ag+, and thereby the shape of Ag NPs during polyol synthesis.
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28-am Carbon Nanoparticle Geometry Drives Nucleation in the Crystallization of PA 66
A. M. Gohn, B. Kindle, A. M. Rhoades
A systematic investigation to determine the influence of geometry on the nucleating efficiency of nanoparticles and the resultant crystallization kinetics of polyamide 66 (PA 66) is presented. Using standard differential scanning calorimetry (DSC) and fast scanning calorimetry (FSC), isothermal and non-isothermal crystallization kinetics were analyzed. The high nucleating efficiency of these nanoparticles were determined at manufacturing-relevant temperatures and rates. It was found that the carbon nanotubes (2D) were the most efficient nucleators, followed by graphene nanoplatelets (1D), and finally C60 fullerene spheres (3D). In recent works by Okada et al1, it was found that the natural shape of a polymer nucleus is of 2D geometry, leading to the conclusion that the favored geometry is that of the natural polymer nuclei.
1 K. Okada, K. Watanabe, I. Wataoka, A. Toda, S. Sasaki, K. Inoue, M. Hikosaka, Size distribution and shape of nano-nucleus of polyethylene simultaneously determined by SAXS, Polymer 48 (2007) 382–392.
29-am Rapid-Injection as a Facile and Versatile Processing Method for Preparing Nanostructured Polymeric Materials C. Lang, M. Kumar, R.J. Hickey
Accessible and robust methods for preparing materials from block copolymers are of significant interest due to their wide-spread applications ranging from uses in everyday products such as pressure-sensitive adhesives, coatings, non-woven fabrics, and packaging, to materials for highly-engineered products such as organic electronics, separation membranes, therapeutic administration and regenerative medicines. Traditional methods for colloidal block copolymer self-assembly are often costly and time-consuming due to the lengthy preparation procedures or requirements in specialized set-ups. These complexities have been a major hurdle for large-scale applications and commercialization of block copolymer self-assembly based materials.
Here we report a universal and quantitative method for preparing nanostructured block copolymer materials using rapid-injection processing. Various structures (micelles, worms, microgels, vesicles, and hydrogels) can be prepared using rapid-injection processing by changing the initial polymer composition and concentration. Specifically, the final state of the system is found to be related to the initial polymer concentration relative to c*, which allows rational design and tailor of the self-assembly products.
Furthermore, the rapid-injection processing technique is translatable for printing, fiber formation, and coating complex three-dimensional objects. The well-defined and hierarchically-ordered structure of the produced materials allows one to create plasmonic nanocomposites and hydrogels exhibiting structural color. Additionally, hydrogels prepared using rapid-injection display superior mechanical properties compared with those made from conventional methods. This work may lead to applications in different technologically relevant areas such as drug delivery, artificial muscle, regenerative medicine, and soft robotics, in which structure and mechanical property precision are essential.
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30-am Fast, Low-Skilled, and Flexible Building Assembly (NOW!): Revisiting the Joint-Based Universal Building System E. Andrzejewski
Today, we exist in a world that desperately needs efficient, cost effective, and fast building solutions to address a housing demand created by population growth, natural disasters, refugees and displaced people. We need building solutions that require less skill, ones that can be assembled faster, and are more adaptable to the varying needs of individual living. Inspired and informed by Wachsmann's work, and in response to contemporary needs, the Clip System, detailed in this thesis, was designed to make an assembly system that relies exclusively on jointing hardware, tools, and panels. While this process began with an analysis of Wachsmann's universal principles and critique of the General Panel Corporation, a revised set of principles were developed for the Clip System: 1) Efficient, 2) Unskilled, 3) Mobile, 4) Flexible/ Adaptable, 5) MultiUse.
What follows is a report on the development of the clips, tools and panels as architectural elements that can be used to produce architectural assemblies at various scales, from a pavilion or single-family dwelling, to a large-span vault.
Rather than designing an entire system, this new joint could provide a builder of any experience level with enough intuitive understanding to assemble a structure from pre-designed panels. As part of an “open” system, these low-skilled individuals would be able to apply the system to assemble a building that met their individual needs. Additionally, this new joint could be applied to panels made from recycled or reused materials. This would allow individuals to transform any material, from waste or new, into usable panelized building elements that can be assembled, dissembled, revised, and re-assembled.
How can revisiting Wachsmann’s “universal joint” and the failures of prefabrication of the past lead to the development of a new joint and panel open building system which allows for low-skill, fast assembly, and flexible reuse of material and modification?
31-am Material Synthesis, Characterization, Device Development and Testing Capabilities at the Applied Research Laboratory’s Electronic Materials and Devices Department (EMDD) D. Snyder, J. Fox, D. Rearick, R. Lavelle, R.Cavalero, R. Ray, B. Huet, J. Kronz, T. Mirabito, M.Pagan, N. Christie, C. Wirick
The Penn State Applied Research Laboratory’s Electronic Materials and Devices Department (EMDD) has developed a vertically integrated capability from material synthesis through device fabrication and testing for DoD and commercial applications related to piezoelectric transducers, RF and power electronic systems, Chem/Bio sensors and IR detectors.
This poster describes the range of crystal growth techniques, material synthesis capabilities, material characterization methods, device design and fabrication capabilities and device testing used to support internal research projects and industrial collaborations. Recently expanded capabilities for ceramics processing and two-dimensional materials will be highlighted.
A series of specific examples of prototype materials and devices currently under development including wide bandgap, ultra-wide bandgap semiconductors, organic semiconductors, single crystal and textured ceramic piezoelectric transducers, two dimensional materials, FETs, IR and radiation detectors, SiC diodes, semiconductor diodes and MEMs structures will be presented.
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32-am Additive Manufacturing of Reinforced Silicones L. Peeke, M. Hickner
Additive manufacturing is a technology that has been rapidly transitioning from experimental laboratories into the garages of hobbyists and onto the factory floors of some of the biggest industry titans. This renaissance in manufacturing is brought about by the versatility that the manufacturing technique gives to the consumer. In this layer by layer manufacturing process, new innovative, custom, and efficient designs can be implemented into the product catalogs and production lines of these companies.
In our research, we focus on processing existing industry materials, which are currently non-traditional materials for additive manufacturing, with the intent of overcoming the existing bottle neck and introducing them into this growing field. Specifically, we evaluate the necessary mechanical equipment and the corresponding material properties to effectively additively manufacture silicone and other thermosetting polymers. Given the underlying anisotropic weakness that additive manufacturing introduces into parts, a large focus of this research is to develop machines that can also reinforce the silicone with engineered thermoplastic meshes. By having complete design control over the silicone and thermoplastic reinforcement, we have the ability to tailor these material’s mechanical strength and then characterize the overall improvement that comes from the samples.
33-am Textured Piezoelectric Ceramics – A 20-year Journey from Innovation to Commercial Implementation
G. L. Messing, B. Watson, M.J. Brova, R. L. Walton, E. Kupp, M.Fanton, R.J. Meyer
Fabrication of high-quality textured ceramics by template grain growth (TGG) was first discovered in 1997 and patented for textured piezoelectric ceramics in 2003. The application of TGG to piezoelectric ceramics has paralleled the generational evolution of single crystal piezoelectrics. Generation TII textured piezoelectric ceramics, produced in the Department of Materials Science and Engineering at Penn State, were shown by an industry collaborator to have superior underwater bandwidth relative to like-composition single crystals. In contrast to single crystal growth, TGG manufacturing of textured ceramics by tape casting is less costly, scaleable to 100 – 100,000 parts per order, leads to superior compositional and property uniformity, and results in mechanically robust plates of 13 cm square by 0.85 cm thick. For the last three years the Applied Research Laboratory at Penn State has teamed with the Department of Materials Science and Engineering to transition basic research on TGG fabrication of Generation TIII and TIV ternary perovskite piezoelectrics to industry users. The new pilot scale manufacturing facility built at the ARL Freeport, PA enables the prototyping of 100 – 10,000 part lots for delivery to industry partners. The poster will show the challenges in scaling up the university scale TGG process, involving powder synthesis, tape casting, stacking, lamination, binder removal, and sintering, to deliver high quality compositional and part-to-part property uniformity.
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34-am Controlling Dendrite Growth in Lithium Metal Batteries through Forced Advection
M.N. Parekh, C.D. Rahn, D.L. Koch, L. A. Archer
Instabilities during metal electrodeposition create dendrites on the plating surfaces. In high energy density lithium metal batteries (LMBs) dendrite growth causes safety issues and accelerated aging. In this poster,
analytical models predict that dendrite growth can be controlled and potentially eliminated by small advective flows normal to the surface of lithium metal electrode. Electrolyte flow towards the Li metal electrode lowers the dendrite growth rate, overpotential, and impedance. Flow in the opposite direction, however, enhances the dendrite growth. For every current density, there exists a critical velocity above which dendrite growth can be totally eliminated. The critical velocity increases almost linearly with increasing current density. For typical current densities and inter-electrode separation, the critical velocity is very small, indicating the potential for practical application.
35-am Polymer Science in the Pester Research Group M. Li, M. Fromel, K. Bell, A. Masucci, S. Freeburne, D. Ranaweera, M. Sundy, R. Crisci, V. Patel, C. W. Pester
The Pester group is at the forefront of polymer research for development of specialized polymeric materials and advanced synthetic strategies. Projects include growth of uniform and patterned surface-tethered macromolecules (polymer brushes) for advanced material generation, use of surface-grafted photoredox catalysts for efficient polymer synthesis, and production of bottlebrush polymers for biomedical applications. Our work has led to new oxygen-tolerant techniques to modify surfaces using visible light and we are currently advancing photolithography to improve cost-effectiveness and allow for complex modification on a wide range of substrates. Further, we are currently exploring the surface-initiated growth of two chemically distinct brushes to pursue the ability to engineer surfaces which respond reversibly to external stimuli. We are leveraging Near Edge X-ray Absorption Fine Structure (NEXAFS) Spectroscopy, Resonant Soft X-ray Reflectivity (RSoXR), and Spectroscopic Ellipsometry to determine important factors including stability of surface initiators and grafting density of polymer brushes. Additional work in the group involves the development of a surface-grafted photoredox catalyst-based approach for light-mediated controlled radical polymerization. This approach can mitigate challenges in polymer synthesis including contamination by free-flowing metal catalysts. Finally, the effects of polymer topology and chemical structure on the mechanical and electrical properties of bottlebrush polymers are being studied. Understanding these effects will be instrumental in designing specialized materials for biomedical applications. These projects have the potential to significantly advance the fields of polymer chemistry and materials science and provide exciting new applications of polymer materials.
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36-am Designing of New Precursor (Poly-Pitch) for Carbon Fiber Production
H. Li, J.V. Sengeh, W. Zhu, M. Chung
Carbon fiber (CF) is an essential high performance (high strength and lightweight) structural material for many high-tech and high-value applications, including aerospace and energy relative areas. Among all the precursors tested to date, it has been established that the polyacrylonitrile (PAN) based precursor is the dominate choice (>70%) in fabricating carbon fibers with high mechanical strength compared to other types of precursor-based carbon fibers. Despite its unique properties, PAN precursor has many downsides with low carbonization yield (~50%) and high cost of polymer and solution fiber-spinning process. There are also health concerns from the gases released during the conversion and fiber processing. Besides PAN, pitches derived from petroleum are also used in CFs production as a type of inexpensive precursor but with a smaller market occupation than PAN because of their high processing cost and energy consuming.
In this study, we designed a new type of petroleum pitch-based precursor, containing polymer backbones from a polyolefin, that combines the advantages of both PAN and petroleum pitch. From our study, we found i.) the polyolefin modified pitch (poly-pitch) has higher carbon yield that can reach more than 70%; ii.) the poly-pitch is melt-spinnable with its viscoelastic properties, and iii.) the stabilization process on the poly-pitch fibers can be finished in the absence of oxygen, which usually increases the complexity of the whole process. The combination of high carbon yield and melt-processing offers a great chance that our designed carbon fiber precursors may lead to a low-cost carbon fiber with superior mechanical properties.
37-am Integrated Spectrometers Based on Metasurface-Dressed Waveguides Y. Ding, Y. Duan, X. Chen, X. Guo, X. Ni
It has been demonstrated that a metasurface – an optically thin artificially engineered nanostructure – consisting of nanoantennas can control light wavefront in free space. Here, we show that metasurfaces on waveguides can modify phase of the wave propagating inside waveguides and hence can be used for controlling the phases of both external scattered light and internal guided waves. Combining the phase dispersion of the metasurface and the intrinsic mode dispersion of the waveguide, light waves with different wavelengths can be routed to different spatial locations in a compact volume. We designed and experimentally demonstrated two types of fully integrated ultra-compact spectrometers based on this metasurface-dressed waveguide. The devices are designed based on silicon photonic integrated waveguides and the metasurfaces can consist of all-dielectric structures, which are compatible with modern silicon micro-fabrication technology.
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38-am Optoelectronically Optimized Nonhomogeneous Thin-Film Solar Cells F. Ahmad, A. Lakhtakia
Photovoltaic solar cells are an eco-friendly source of energy. The key challenge in photovoltaics is to deliver high conversion efficiency at low cost. Thin-film solar cells are a promising alternative to wafer-based crystalline silicon solar cells with significantly reduced material consumption and the promise of reduced manufacturing cost. However, there are a couple of major concerns inhibiting widespread adoption of thin-film solar cells: (i) scarcity and cost of rare materials such as indium in CIGS and tellurium in CdTe, (ii) low efficiencies such as of a-Si and CZTSSe solar cells. New strategies are required to overcome these concerns. We investigated new thin-film solar-cell designs to incorporate optoelectronically optimized bandgap grading of semiconductor layers and periodically corrugated backreflectors along with the back-surface passivation. Our coupled optoelectronic optimization predicts that tailored bandgap grading can significantly improve efficiency, thereby promoting widespread adoption of thin-film solar cells as local energy sources as well as for multi-gigawatt sources incorporated in national and international energy grids. Another hindrance with large-scale adoption of solar cells is their black or blue appearance that makes them aesthetically very different from traditional rooftops that either comprise burned-clay tiles or composite-material shingles. Rooftop solar cells may become more acceptable if they are colored, e.g., red. To overcome this problem, we studied the red colored solar cells for different thin-film materials with either homogeneous or nonhomogeneous. Our optoelectronic optimization predicts that efficiency gain by the bandgap grading, etc., is more than enough to swallow efficiency reduction by rejection of red photons.
39-am PVA-Zinc water soluble electrode
Y. Gao
Wearable and flexible electronics become more and more important in human healthcare sensing and monitoring. Polyvinyl alcohol (PVA)-Zinc water soluble electrode is a simple on-skin patch that can detect temperature, human electrocardiogram (ECG) and electromyography (EMG) signal. It is a gel-free, one-time-use, and biodegradable patch that can accurately sensing cardiac ECG signal and muscular EMG signal. Polyvinyl alcohol is a water-soluble synthetic polymer. It is nontoxic and can be used as wound dressing in drug delivery. Instead of metal deposition process, here we take advantage of photonic sintering approach to transfer Zinc nanoparticles into one connected metal layer with high electric conductivity. Zinc is chosen because of its low melting temperature. Good adhesion between PVA-Zinc patch and human skin are achieved with the help of water droplets before sticking. Partially dissolved PVA substrate then have a low contact impedance which means a good conformal contact with human skin for ECG & EMG signal sensing.
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40-am Thin Film Transistors for Flexible and Large Area Applications
A. V. Gupta, S. Lee, T. Liu, M. M. Tendulkar, Q. M. Tran, S. H. Yoo, A. Dangi, J. N. Kim, X. Zhang, E. D. Gomez, E. W. Gomez, J. M. Redwing, S. Trolier-McKinstry, T. N. Jackson
Thin film transistors (TFTs) are widely utilized in the display industry as select devices for pixel data and also have potential for 3D ICs and for flexible and large area electronic applications. We are studying ZnO TFTs as an enabling technology for flexible and large area electronics. We utilize plasma enhanced atomic layer deposition (PEALD) to deposit uniform ZnO films under 200 ºC that yield high-performance devices. This allows ZnO TFTs to be fabricated on a variety of substrates, including glass and flexible polymeric materials. Electronics on non-planar substrates is an interesting opportunity area, and we have developed an approach for curved substrate photolithography that uses flexible masks and a modified mask aligner. Using this tool, we are able to fabricate ZnO TFTs on curved substrates with good uniformity and electrical characteristics very similar to devices fabricated on flat glass. We are developing low-cost, sensitive, and selective electronic biosensors based on ultra-thin-channel ZnO TFTs combined with microfluidics, micro-heaters, and lipid membranes. We have characterized the changes in electrical characteristics for ZnO TFTs functionalized with lipid monolayers. Using gated devices allow for the biomolecule-related charge to be deconvolved from effects due to leakage, surface states, or electronic transport. We have demonstrated ZnO TFTs with drive currents >250 mA/mm and mobilities >80 cm2/V×s for 5 µm channel length ZnO TFTs passivated with N2O PEALD Al2O3. Devices with channel lengths of 2 to 50 m show large mobility and drive current increases with N2O PEALD Al2O3 passivation. Large drive current and high large signal mobility indicate the results are not due to contact effects or measurement artifacts. The high performance of these devices is of interest for 3D ICs and other applications. We have developed flexible inorganic piezoelectric thin-film based ultrasonic transducers on a few micron thick polyimide substrates using lead zirconate titanate (PZT) films deposited by chemical solution deposition. Because the PZT films require a high-temperature (700ºC) crystallization step, the devices are first fabricated on high temperature substrates and then transferred to the polyimide. The flexible transducers show improved dielectric properties compared to devices on rigid substrate due to a reduction in substrate clamping effects. Pitch-catch and pulse-echo measurements have been successfully demonstrated for the flexible transducers. The development of polymeric substrate based PZT thin-film transducer devices provides a path towards novel applications in the medical field. Two-dimensional transition metal dichalcogenide (2D-TMD) based TFTs are also of interest for flexible electronics and 3D integration. Using metalorganic chemical vapor deposition (MOCVD), we deposited 2D-TMD materials at 400 ºC. We fabricated flexible double-gate WSe2 TFTs and top-gate β- In2Se3 TFTs. Double-gate WSe2 TFTs had improved output conductance and higher drain current than single-gate devices. β-In2Se3 TFTs had field-effect mobility ~1 cm2/Vs and Ion/off ratio >106. The low processing temperature for WSe2 and β- In2Se3 devices broadens the 2D-TMD device application space.
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41-am Waveguide-Fed Metasurfaces for Free-Space Light Manipulation
X. Guo, Y. Ding, X. Chen, Y. Duan and X. Ni
Integrated photonics offers a promising platform for a wide range of applications including: telecommunications, optical sensing, optical information processing, optical quantum computing, and many others. In order to fully exploit the benefits of integrated photonics, it is crucial to have an interface that can flexibly couple light between photonic integrated devices and the exterior environment. However, current approaches based on edge coupling and grating coupling have limited functions. On the other hand, metasurface - an ultrathin artificial surface consists of sub-wavelength structures also known as meta-atoms - has revolutionized the manipulation of light by locally imposing abrupt and controllable changes to optical properties. Combining metasurfaces with integrated photonics, we established a fully integrated platform where meta-atoms have direct control over the coupling between the guided and scattered free-space waves, and experimentally demonstrated complex functions, such as off-chip beam steering, focusing, and direct orbital angular momentum (OAM) beam lasing. Our study enables multifunctional photonic integrated devices for communications, remote sensing, displays, and etc.
42-am Structural Coloration by Cascading Total Internal Reflection and Interference at Microscale Concave Interfaces
A.E. Goodling, S. Nagelberg, B. Kaehr, C.H. Meredith, S. Cheon, A.P. Saunders, M. Kolle, L.D. Zarzar
Structural color is created by the interaction of light with physical structures and is commonly seen in hard materials with high refractive index contrast and nanoscale periodicity such as diffraction gratings or thin films. Recently, we have observed structural coloration from microscale concave interfaces of oil-oil complex droplets suspended in an aqueous surfactant solution, where the color originated from the three-phase contact line via total internal reflection (TIR). We were able to model the observed color and found that light propagating by TIR along the interface can have different numbers of reflections and thus different path lengths which leads to interference and iridescent color. The requirements to achieve this effect include a transition from a high to low refractive index and a microscale geometry to support multiple TIR, allowing generation of structural color in a multitude of different materials and geometries. We were able to capture the projected color onto a translucent dome and match the patterns to a model to predict the effect of size, shape and illumination angle on the observed color. From the dependence on shape, we were able to pattern an image by stabilizing the droplets with a light sensitive surfactant that would vary the shape as the droplets were subjected to blue or UV light to pattern images with different colors. We were also able to further replicate this geometry into a wide range of shapes and materials. For example, we have seen this effect in complex liquid droplets, solid particles, water drops condensed on substrates with low wettability, and solid elastic surfaces. These simple geometric requirements provide new opportunities for fabricating, designing, and controlling structural color, enabling use of such structural coloration in materials where it previously would have not been possible. Probing how this affect can be further improved by looking at how light interacts with the materials geometry to produce specified color patterns can broaden the use of this mechanism, allowing for a low cost, disposable system for a vast variety of applications from colorimetric sensing to dynamic camouflage.
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43-am Structural Design for Stretchable Antennas for Strain Sensing and Energy Harvesting J. Zhu, J. J. Fox, N. Yi, H. Cheng
Practical application of flexible and stretchable electronics has been hindered by ineffective communication of the large volume of data generated by sensors and the high-power consumption to process them. In order to address this challenge, the wireless technology that includes Bluetooth, near field communication (NFC) and inductive coupling has been exploited for the data transmission and wireless powering in real time due to the compactness of devices along with the remarkable processing capacity with minimal power consumption. Compared with batteries and supercapacitors, these wireless transmission modules obviate the need for replacement thus are durable, which is especially important for implanted devices. In addition to wireless transmission of data and power, this technology has also been used extensively as a remote interrogation for strain sensing, chemical signal detection, monitoring of crack propagation, among many others. For instance, inductive coils in ocular contact lenses allow wireless monitoring of the intraocular pressure and the glucose concentration in the tear by measuring the resonance frequency shift and reflection magnitude in the reflection curve, respectively. However, it should be noted that though the NFC technology is associated with data security, it is limited to work up to only several centimeters.
As an alternative, radio frequency antennas that enable long-range operation have attracted increasing attention, especially for flexible and stretchable sensors. Because of the availability of various commercial radio frequency chips in miniaturized form, there is a huge potential in both research and future commercialization. The recent development of flexible and stretchable antennas for bio-integrated electronics has been briefly summarized and the representative strategies include the use of textile, liquid metal, graphite film, composite elastomer with conductive fillers, and structural design of conventional materials. As the conductive textile, liquid metal and conductive composite are also associated with low electrical conductivity, the resulting antenna has a low efficiency.
In this work, we have demonstrated the exploration of two representative stretchable structures in designing and fabricating the stretchable, mechanically reversible microstrip antennas from conventional metallic materials: deformed wavy structure created from the use of the pre-strain strategy and the initially meshed structure made of serpentine connections. The demonstrations presented in this study are obtained by a simple cutting method, but the designs could easily be applied to the other advanced manufacturing methods such as laser patterned porous graphene. The prediction of the radiation properties of both designs from the simulation is verified by the experiment with reasonably well agreement. Due to the tunable dependence of the resonance frequency shift on the tensile strain, the resulting stretchable microstrip antenna is also demonstrated as a class of novel strain sensors that could enable wireless communication by using the technique of wireless interrogation. Further, by employing simple laser fabrication techniques, stretchable wideband dipole antennas have been proposed. We anticipate that integration with optimized rectifying circuits, our proposed dipole antennas are suitable for electromagnetic energy harvesting.
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44-am Influence of Doping on the Performance of Solid Polymer Electrolyte for Lithium-ion Batteries S. C.V. Ram, J.Maranas
Polyethylene oxide (PEO) based solid polymer electrolytes (SPEs) are an attractive alternative to the flammable liquid/gel electrolytes currently used in rechargeable lithium ion batteries. In addition to improving safety, SPEs could allow the use of Lithium metal anode (3860 mAh/g) which has higher specific energy than commercially used lithium graphite anode (372 mAh/g). This increase in specific energy would greatly improve the range that an electric car can travel before recharging. However, SPEs suffer from low Li+ ion conductivity. In an amorphous polymer, the conductivity is linked to PEO segmental motion; In order to increase the segmental motion, we must reduce the glass transition temperature (Tg). Unfortunately, this increase in polymer dynamics reduces the mechanical strength of SPE. PEO6-LiClO4 (PEO6) complex is a tunnel-like PEO/salt co-crystal [Figure] which conducts Li+ based on a mechanism that decouples conductivity and segmental motion of the polymer. The studies conducted on PEO6 used very low molecular weight PEO. At this molecular weight, the polymer has very low mechanical stability. In SPEs with high molecular weight PEO, conduction through PEO6 is unfavorable as the tunnels fold to form lamellar structures and increase the conduction pathway. Our group has used cellulose Nano whiskers to stabilize the PEO6 structure for ultra-high molecular weight PEO. In spite of the stabilization, conductivity (~10-6 S/cm) is still below what is required for practical application.
Inspired from ceramics, we dope PEO6 with small amounts of anions or cations to increase the conductivity of the SPE. We vary the size of the anion, and cation to create defects in the PEO6 crystal lattice. We observe up to an order of magnitude increase in the conductivity of doped samples compared to the undoped ones. Interestingly, the increase in conductivity is not correlated with the decrease in Tg of the SPEs [Figure]. We further investigate the influence of doping on the crystalline structure and polymer dynamic using X-Ray (Wide-angle X-ray scattering) and neutron scattering (QENS) techniques.
45-am Simulation Study on High-Q GaN Varactors for mm-wave Applications
J.Song, S.-W. Han, R.g Chu
Varactors, with its definition of devices with tunable capacitance by applied voltage, are enabling components for reconfigurable RF systems. The performance of a varactor could be characterized by its Q-factor and tuning ratio, a large Q-factor and high tuning ratio is preferred for better performance. In this work, we seek to develop new varactor designs suitable for mm-wave applications through simulation study. There are two main innovations in our design. One was the use of fin structure, in which the electrodes were placed on two opposite sidewalls of the mesa structure instead of one on top and the other at the bottom or next to the mesa. This design could eliminate the extrinsic series resistance in conventional varactor diode designs, and a substantially increased Q-factor. The other was the use of multichannel structure. The structure was composed of multiple AlGaN/GaN heterojunctions with high-mobility 2D electron gas. The high-mobility electron gas helped lowering the intrinsic series resistance, thereby further improving the Q-factor.
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46-am Power Electronics Wide-Bandgap Materials
S.A. Suliman
Power electronics aims at efficient energy conversion. At the heart of power electronics are solid–state switches known as Power Semiconductor Devices, PSD.
PSD switches have to deliver high currents in the ON-switch-state and withstand high voltages in the OFF-switch-state. Moreover, PSD have to operate at a high temperature environment, and at high frequency. The starting generation of power devices was based on crystalline silicon substrates; the latter is the workhorse material of digital technology.
The demanded features of today’s-generation of PSDs include high current/high voltage/high temperature/high frequency operations. Hence, the design of PSD is an engineering feat. On the materials for PSDs, crystalline silicon, which is the workhorse of digital technology, is the material of the earlier generations of PSDs, the and demanded features of today’s PSDs. Wide band gap semiconductor materials are superior to silicon in the power/energy applications. Crystalline growth and processing of wide bandgap semiconductor materials presents challenges in a similar manner to silicon in its earlier phases of its evolutionary track.
47-am Humanitarian Engineering: Towards Developing Sustainable Composite Bricks by Cold-sintering Process
S.H. Bang, A. Ndayshimiye, E. Obonyo, C.A. Randall
Concrete is the second most consumed commodity on Earth after water and the single most widely used material in the world. Although concrete has been used for millennia, dating back to ancient Egypt, its enormous carbon footprint has received increasing attention for finding sustainable solutions Due to its vast quantity, concrete production contributes 5% of annual anthropogenic global CO2 emission, followed by electricity and heat production. The cement manufacturing process requires significant amount of energy to reach the reaction temperature up to 1500 °C, and the principal mineral phase of CaO is the result of CaCO3 decomposition, which also contributes to the CO2 production.
According to the United Nation’s 2019 world population prospects, the world population will reach 9.7 billion in 2050. It is expected that there will be an accompanying exponential grown in the demand for concrete for housing and infrastructure. Thus, sustainable construction practices must be pursued in order to maintain the quality of life for expanding population and to minimize anthropogenic CO2 emission. However, designing a new concrete mixture is a fine balancing act, as the new formulation must satisfy not only material property requirements, but also be readily compatible with existing construction practices as mandated by building codes. Because concrete is the most widely used material, reducing its carbon footprint could potential result in transformative impact with respect to sustainability, cost effectiveness as well as availability and adaptability to suit a wide spectrum of performance requirements across different socio-economic groups.
The two most common methods to manufacture bricks are clay firing and cement hydration. By reducing the process temperature and the amount of required cement without sacrificing performance, the sustainability of producing the building materials can be improved. The authors are exploring the potential of addressing the existing needs for a more sustainable brick manufacturing process
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through the use of a low–temperature powder densification technique, namely cold sintering. Several unique characteristics of the cold sintering revolve around open system (non-hydrothermal), short sintering time and low process temperature, which allows to design new ceramic–polymer composite material systems. Under the cold sintering condition, which employs transient liquid phase and uniaxial pressure, the cement hydration kinetics is expected to change.
The current study focuses on material selection and its densification at the laboratory scale. As the minimum haul distance should be considered during the brick material design phase, we seek to improve both the sustainability and cost of raw materials through researching the use of locally-accessible raw materials. To date, calcium silicate rock sample from Kenya and research-grade sodium alginate from brown algae demonstrated potential for densification at 150 °C. The relative density reached 90% within 30 minutes of the cold sintering. The material selection is not limited to the rock from specific region. A methodology has emerged for optimizing the performance of our proposed sustainable composite bricks - concurrently investigating the cement hydration and sintering effects, which will enhance the understanding of the composite’s structure - property relationship.
48-am Self-Healing Odor Barrier for Waterless Toilets B.B. Boschitsch, H. Feldstein, L. Wang, T.-S. Wong
In 2011, the Bill & Melinda Gates Foundation initiated the “Reinvent the Toilet Challenge” to bring sustainable sanitation solutions to the 2.5 billion people who lack access to safe and affordable sanitation. Teams that were supported by the grant have since developed a variety of waterless toilets in response to the challenge. One fundamental problem that has not yet been addressed is the generation of unpleasant odor in these toilets. Making waterless toilets attractive from an olfactory perspective is an important factor towards addressing open defecation practiced by ~1.1 billion people (as of 2015). In the developed world, commercial products such as Poo-Pourri have been developed to block the unpleasant odor in toilets by forming an impermeable oil layer on the water surface. However, such an approach will not be applicable for waterless toilets. Recently, our research group has developed a self-healing liquid membrane that allows large objects to pass through while retaining small objects. Here, we propose to use a self-healing liquid membrane to significantly decrease the rate of diffusion of chemicals relevant in waterless toilets, which would be an inexpensive solution towards addressing the odor/waste management issue in waterless toilets. Detailed experimental results and characterizations will be presented in the meeting.
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49-am Graphene-enhanced Raman Spectroscopy for Detection of Biomolecules *A. Silver, D. Han, S. Huang
Graphene is a two-dimensional (2D) material consisting of a single sheet of sp2 hybridized carbon atoms laced in a hexagonal lattice, with potentially wide usage as a Raman enhancement substrate, or termed graphene-enhanced Raman scattering (GERS), making it ideal for sensing applications. GERS improves upon traditional surface-enhanced Raman scattering (SERS), combining its single-molecule sensitivity and spectral fingerprinting of molecules, and graphene’s simple processing and superior uniformity. This enables fast and highly sensitive detection of a wide variety of analytes. Accordingly, GERS has been investigated for a wide variety of sensing applications, including chemical- and bio-sensing. Here, we present GERS label-free detection of several biologically important molecules. Enhancement factors (EF) of up to 30x for hemoglobin are observed on graphene, with certain Raman modes showing selective enhancement. Additional biomolecules examined include serotonin, cortisol, and glutamic acid. We also demonstrate a possible method for detection of large proteins adsorbed on graphene via their effect on the visible graphene modes.
51-am Microtomy at Huck Microscopy Facility
G. Ning
Microtomy is an essential technique for slicing bulky samples into sections thin enough prior to imaging these specimens under a microscope. Staff members of the Huck Microscopy Facility in the basement of MSC provide microtomy services with its state-of-the-art instrumentation and high precision skills. The services include sectioning biological and material samples into sections of different hardness, samples that are embedded and non-embedded, and samples at ambient and cryogenic temperatures; sections can be cut in a range of thickness from several ten microns to several ten nanometers. This poster outlines the microtomy services provided by the Huck Microscopy Facility and presents examples of its application at convergence of biological and material sciences.
52-am Memory and Learning in Biomolecular Soft Matter for Low-power, Brain-Like Computing *J.S. Najem
The brain carries out complex cognitive and computing tasks by optimizing energy efficiency, information processing, communication, and learning in massively parallel, dense networks of highly interconnected neurons. To cope with its ever-changing surrounding, the brain is able to grow neurons, synapses, and connections—owing to its plastic nature. At the molecular and cellular levels, synaptic plasticity and neuronal excitation are the main mechanisms underlying these processes. Therefore, the ability of next-generation computing devices, robots, and machines to autonomously sense, process, learn, and act in complex and dynamic environments while consuming very little power will require approaches to computing and sensing that are inherently brain-like. Reproducing these features using traditional electronic circuit elements is virtually impossible, requiring the design and fabrication of new hardware elements that can adapt to incoming signals and remember processed information. These elements should be scalable, biomimetic, and preferably ionic to achieve energy consumption levels approaching those in the brain. While a major effort is being invested in developing inorganic materials that could emulate synaptic and neural functionalities, I believe that an overlooked, yet high-reward, pathway to success is through development of biomolecular materials with the composition, structure, and switching mechanisms of actual biological synapses and neurons. Here, I describe two-terminal, biomolecular memcapacitors and memristors, consisting of highly insulating 5 nm-thick lipid bilayers assembled between two
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water droplets in oil. These devices exhibit memcapacitance that is nonlinearly dependent on the applied voltage as well as hysteresis in the charge due to voltage-driven, reversible changes in the area and thickness of the bilayer membrane. This is the first demonstration of a memcapacitor in which capacitive memory results from geometrical changes in a lipid bilayer membrane. We also show that the incorporation of voltage-activated alamethicin and monazomycin peptides in these devices results in variable ionic conductance across the membrane and memristive behavior. We discuss how these devices exhibit learning through synaptic plasticity, and how to implement them in online learning applications. These results serve as a foundation for a new class of low- cost, low-power, soft mem-elements based on lipid interfaces and other biomolecules for applications in neuromorphic computing which could have major implications on the robotics and computing fields.
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Poster Session B (PM): Poster Listing with Abstract
53-pm Materials Characterization Laboratory (MCL)
MCL Staff
The Materials Characterization Laboratory (MCL) is a user facility with world class analytical capabilities and staff. The molecular spectroscopy lab within MCL, has a broad range of capabilities (optical microscopy, Raman, FTIR, & Spectrophotometers) and in situ cells to help on a variety of projects. This poster will present in greater detail some of the capabilities related to the Raman spectroscopy tool.
54-pm Thermo-Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC) capabilities at Materials Characterization Lab
E. Bazilevskaya
Materials Characterization Lab (MCL) in the Materials Research Institute provides several characterization tools for thermal analysis of materials. Differential Scanning Calorimetry (DSC) measures temperatures and heat flows associated with thermal transitions in a material. Properties measured by the TA Instruments Q2000 include glass transitions, phase changes, melting, crystallization, product stability, cure/cure kinetics, and oxidative stability. The modulated DSC (MDSC) functionality in the Q2000 provides increased sensitivity to weak transitions and separates complex transitions into simpler individual transition components. Equipped with a refrigerated cooling system, the temperature range in the DSC Q2000 extends from -90 to 400°C.
Thermo-Gravimetric Analysis (TGA) measures weight changes in a material as a function of temperature (or time) under a controlled atmosphere with the added capacity of mass spectrometry (MS) for the identification of evolved gaseous species. It is mainly used to determine the composition of materials and to predict their thermal and oxidative stability. Two TGA instruments are currently available at MCL: (1) Discovery TGA Q5500 coupled with Discovery MS that operates from room temperature to 1000 °C and allows qualitative chemical determination of evolved gases (mass/charge from 1 to 300) giving information about reactions in real time; (2) SDT Q600 that provides a simultaneous measurement of heat flow (DSC) and weight change (TGA) on the same sample in the temperature range from 25 to 1500°C.
The purpose of this poster is to show the capabilities and utilization of the above-mentioned equipment to solve research problems. The instruments are located in N-007 Millennium Science Complex.
55-pm Optical Characterization of TMDCs-Graphene Heterostructures for Next-generation Opto-electronic Systems X. Li, M. Blades, B. Huet, T. Choudhury, J. M. Redwing, S. V. Rotkin
Van der Waals heterostructures have gained large attention in recent years due to unique combined properties of constituent 2D materials, which provides a potential platform for developing novel highly multifunctional nanoscale optoelectronics or electronics devices. This also brings up the necessity of thorough understanding the interactions (mechanical and electronic) between different layers of composite 2D materials, in order to effectively tune the heterostructure for specific electronic and/or photonic properties.
Graphene, with its impressive properties, such as high intrinsic mobility, high transparency, high thermal conductivity and large tensile strength, has already gained recognition in 2D community. In particular, thermally grown epitaxial
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graphene on SiC is considered a promising candidate for microelectronic devices. Combining more than one layer together in twisted bilayer graphene, extreme bandstructure modulation has been demonstrated by tuning twist angle. TMDCs –another group of 2D materials known to have direct bandgaps – are promising materials for heterogeneous integration with graphene.
Here we build and study two multilayer materials: heterostructures of CVD grown WSe2 on epitaxial graphene and transferred twisted bilayer graphene. The effect of strain and doping on graphene is well known to result in a shift of the G and 2D Raman peak positions. By using Raman spectroscopy, extracting graphene signal from Raman maps, and analyzing the correlation between different peak parameters, we determine the strain level due to the lattice mismatch between TMDCs and graphene. Possible role of underlying graphene to the growth of TMDCs is also studied. For that purpose, we apply scattering-type scanning near-field optical microscope (s-SNOM) which is a versatile tool to resolve nanoscale optical features of the 2D heterostructures with high resolution down to 10 nm. Capability to control the growth and properties of graphene-TMDC stack opens horizons for developing the next-generation electronic and opto-electronic systems.
56-pm Novel nano-structured bio-based poly(ε-caprolactone) (PCL)/tung oil blends prepared via in-situ compatibilization and cationic polymerization
S. A. Madbouly
The phase morphology and crystallization kinetics of novel nano-structured bio-based poly(ε-caprolactone) (PCL)/tung oil blends prepared via in-situ compatibilization and cationic polymerization were investigated as a function of composition using scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), respectively. The cationic polymerization of tung oil in a miscible solution of PCL produced novel semi-interpenetrating polymer networks (IPNs) with nano-scale morphologies. The average particle size of the dispersed nan-omorphology was observed for PCL/tung oil 30/70 blend (100 nm). The non-isothermal crystallization kinetics of PCL in the blends was strongly influenced by the tung oil thermoset, i.e.; the kinetics of non-isothermal crystallization process was greatly inhibited in the blends with compositions of PCL<50 wt%. This finding suggested that the high concentration of thermoset, tung oil could significantly restrict the dynamics of the PCL chain segments, thereby slow down the non-isothermal crystallization process. On the other hand, a considerable acceleration in the non-isothermal crystallization kinetics was observed for PCL/tung oil 50/50 wt% blend. The crystallization kinetics was analyzed as a function of composition at different cooling rates based on modified Avrami approach.
57-pm Quantum Dynamics in Graphene
J.O. Sofo, B.R. Green, J.L. Robbins
Abstract: Our group studies materials physics with a variety of quantum mechanical and computational methods, with an emphasis on graphene and other 2D materials. Here we present research on graphene dynamics in (1) conductivity with vacancy and substitutional disorder and (2) spin- & valley-ordered Landau level phases. These both build on graphene’s potential for next-generation electronics.
(1) We seek to calculate the DC-conductivity of graphene with substitutional disorder of nitrogen atoms. We treat conductivity at the level of linear response with the Kubo-Greenwood formalism. Great care must be taken in deriving the DC limit of Kubo-Greenwood conductivity due to unphysical effects of finite size at
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zero-frequency. We currently seek to evaluate the Kubo-Greenwood conductivity of substitutionally disordered graphene supercells by both direct diagonalization and the Kernel Polynomial Method.
(2) A plethora of ordered phases - ferromagnetic, valley-polarized, antiferromagnetic, and more - have been predicted or observed in bilayer graphene. We reveal that phase transitions are driven by a balance between single-particle dynamics and interactions, and that applied pressure modulates these transitions.
58-pm Computational Materials System Design
J.P.S. Palma, Z.-K. Liu
The thermodynamic stability of different phases in multicomponent systems at various conditions has been of interest for many decades; from design of structural alloys to current semiconductor industries. Specific scenarios in which phase stability has come of interest is in additive manufacturing of alloys applied in corrosive marine environments, high temperature stability of metal/thermoelectric interfaces, and stability of intermetallic catalysts. This poster presents a brief introduction of the tools applied to solve these issues and the Phases Research Laboratory at the Department of Materials Science and Engineering.
The CALculate PHAse Diagram (CALPHAD) method has been an efficient approach in predicting the thermodynamic stable phases in multicomponent systems given temperature, total pressure and composition. However, the accuracy of the predictions is strongly tied with the accuracy of the description of Gibbs free energy at different conditions. The demand for accurate thermochemical data is experimentally expensive due to limited resources and complicated experimental designs. First-principles calculations based on Density functional theory (DFT) has proven to be a reliable tool in predicting thermochemical data at 0K with temperature dependence when experimental data was absent.
However, when developing a thermodynamic database there is always an innate amount of uncertainty in the data used to fit the Gibbs energy functions. The Extensible Self-optimizing Phase Equilibria Infrastructure (ESPEI) software gives the advantage of quantifying the uncertainty of phase boundaries predicted from the thermodynamic database and providing experimentalists with an insight on where more data is needed.
59-pm Machine Learning Assisted Selection of Process Parameters for Controlling Microstructural Properties in Additive Manufacturing
S. Mondal, A. Ray, A. Basak
Controlling the thermal gradient (G) and solidification velocity (R) is instrumental in achieving the desired microstructure in additive manufacturing (AM) processes. During layer-by-layer deposition, if the process parameters are not appropriately controlled as the scan progresses, the melt pool geometry undergoes substantial changes due to significant dumping of heat into the specimen. Moreover, it is difficult to maintain the desired G/R ratio in the part during the build process as mandated by the microstructural requirements. For example, process parameters chosen for maintaining a G/R value for a columnar microstructure, if not controlled properly, can cause the final microstructure to be preferentially equiaxed towards the end of the scan as the meltpool grows in size. As a possible solution to this problem, a physics-informed machine learning (ML) assisted
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modeling and optimization framework was explored in this work. An analytical heat transfer model is employed for predicting the thermal distribution in a directed energy deposition process for faster computation. Thereafter, a surrogate-assisted statistical learning and optimization architecture involving Gaussian Process-based modeling and Bayesian Optimization is employed for finding the optimal set of process parameters as the scan progresses, subject to the constraint of maintaining a desired percentage of columnar growth during the build. The results indicate that ML-based modeling and optimization techniques can help in procuring a-priori estimates of how the process parameters need to be changed during an AM process for controlling a desired microstructure in a part.
60-pm A Two-stage Optimization Procedure for the Design of an EAP-actuated Soft GRIPPER
W. Zhang, A. Saad, J. Hong, Z. Ounaies, M. Frecker
An increasing range of engineering applications require soft grippers, which use compliant mechanisms instead of stiff components to achieve grasping action, have high conformability and exert gentle contact with target objects compared to traditional grippers. In this study, a three-fingered gripper is first designed based on a notched self-folding mechanism actuated using an electrostrictive PVDF-based terpolymer. Then the design optimization problem is formulated, where the design objectives are to maximize the free deflection ∆_free and the blocked force F_b. A computationally efficient two-stage design optimization procedure is proposed and successfully applied in the gripper design. NSGA-II is adopted as the optimization algorithm for its capacity to deal with multi-objective optimization problems and to find the global optima with high design variables and large design domains. In stage one, computationally less expensive analytical models are developed based on Bernoulli-Euler beam theory and Castigliano’s theorem to calculate ∆_free and F_b. Utility function is applied to determine the best design in the last generation of stage one. In stage two, 3D FEA models are developed, using the dimensions determined by the best design from stage one, to investigate effect of the shape of segment surfaces on the design objectives. Overall, the proposed two-stage optimization procedure is successfully applied in the actuator design and shows the potential to solve a wide range of structural optimization problems.
61-pm Dabo group: Materials Optimization and Simulation for Energy Applications Y Xiong, M Burgess, S. Baksa, C Chandler, W Chen, J Fanghanel, J Goff, N Hall, F. Marques dos Santos Vieira, I Dabo
The Dabo group focuses on understanding modern energy applications by expanding the capabilities of quantum-mechanical simulations for materials property optimization. By developing and utilizing techniques such as Monte Carlo sampling, phonon scattering, distortion symmetry groups and machine learning, we investigate novel materials for efficient semiconductor electrode in hydrogen production, improved pseudocapacitive materials, next-generation silicon metalattices for converting waste heat to energy and discover new minimum energy pathways for materials that have magnetic phase shifts and catalytic reactions.
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62-pm Understanding Ferroelectric Properties of BaTiO3 using ReaxFF Reactive Force Fields
D. Akbarian, D.E. Yilmaz, A.C. van Duin
Ferroelectric perovskites such as barium titanate (BaTiO3) have had numerous applications in nonvolatile memories, transducers, micro sensors and capacitors because of their unique properties such as spontaneous polarization, piezoelectric and pyroelectric effects, as well as large dielectric constants. In order to design and optimize these devices, it is essential to obtain detailed, atomistic-scale insight of the BaTiO3 ferroelectric perovskite. Currently, there are three approaches to model the ferroelectric behavior of BaTiO3: phenomenological, First-principles and Force field-based methods. Phenomenological models are not able to provide atomistic level description of the ferroelectric perovskites. First-principles methods such as the density functional theory (DFT) are considered as the most accurate models which derive the electronic structures of ferroelectric materials based on the laws of quantum mechanics. However, because of heavy computational costs these methods can be only viable for relatively small systems and short time scales. Moreover, since the DFT models are mainly limited to zero kelvin, most of ferroelectric properties of the perovskite materials such as hysteresis loop, sequential phase transitions and domain wall motions cannot be investigated using the first-principles methods.
Although, First-principles methods such as the density functional theory (DFT) provides accurate description of the material but mainly limited to zero kelvin, most of ferroelectric properties of the perovskite materials such as hysteresis loop, sequential phase transitions and domain wall motions cannot be investigated using the first-principles methods. ReaxFF reactive force fields first developed for hydrocarbons and later ported to different systems such as ceramics, metals and their oxides and provided precise results for those systems. We developed the first reactive force field for BaTiO systems which captures both chemical and electro-mechanical properties of the material. We performed molecular dynamics simulations to investigate the phase transition sequence, ferroelectric and thermal hysteresis loops for the BaTiO3 crystal structure. Furthermore, we investigated the effects of oxygen vacancies, sample thickness and surface chemistry on the material polarization.
63-pm µ-pro: Phase-Field-Based Package for Modeling and Simulating Materials Microstructure and Properties
X. Cheng, T. Yang, B. Wang, J. Wang, Y. Ji, R. Wang, L.-Q. Chen
µ-pro is a commercialized microstructure-property modeling package, containing a series of phase-field models implemented with modern fortran and MPI. It excels in dealing with numerous types of problems, ranging from grain growth, precipitation, and martensitic transformation in alloys, to domain structure evolution in ferroelectric, magnetic, and ferroelastic systems. µ-pro has a Penn State academic counterpart called MesoExplorer.
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64-pm Understanding, Prediction, and Design of Materials -- Guided by Multiscale/Mesoscale Computation X. Cheng, T. Yang, Y. Ji, Z. Liu, B. Wang, Y. Shi, R. Wang, C. Dai, Y. Tan, J. Zorn, D. Fontino, F. Xue, J. Wang, Y. Wang, L.-Q. Chen
Chen’s group focus on modeling the thermodynamics and kinetics of materials processes and multiscale microstructure evolution. They study both bulk and thin film materials using the phase-field method as well as multi-scale approaches combining first-principles calculations, phase-field method, micromechanics, electrostatics, and micromagnetics. They use mesoscale computer simulations to understand, predict, and design materials and their properties through extensive collaborations with experimentalists around the world, industry, and national labs.
65-pm ReaxFF : A Predictive Tool for Low Cost Carbon Fiber S. Rajabpour, Zan Gao, Q. Mao, M. Khajeh Talkhoncheh, B. Damirci, M. Kowalik, X. Li, A.C.T. van Duin
The automotive industry is looking for alternative high strength, lightweight materials in vehicle designs in order to decrease emission by reducing vehicle weight. Carbon fiber reinforced polymer (CFRP) composites are a promising alternative due to high strength-to-weight ratio. However, to overcome the high cost of carbon fibers (CFs), alternative precursors are required to replace polyacrylonitrile (PAN), the most widely used CFs precursor. Investigating graphene (2D carbon allotrope) inclusion into PAN matrix precursor provides insights whether adding graphene to lower cost precursors such as polyethylene (PE) and Nylon can improve their performance. Our ReaxFF molecular dynamics simulations alongside with scanning electron microscopy (SEM) and X-ray nanotomography inspection revealed that the small amount of added graphene could effectively enhance the microstructure of the PAN/graphene CFs. Compared to the PAN control sample, PAN/graphene-0.075 CF demonstrated a ~225% increase in tensile strength and ~184% increase in Young’s modulus. In addition, our simulation suggested that carbonization temperature has a significant role in CFs performance, and we can achieve a more robust CFs by increasing the carbonization temperature.
66-pm Electrochemical Double Layer and Size Effects on Platinum Nanoparticle Dissolution Using COMB3 and Continuum Electrolyte Models
J. Goff, S. Sinnott, I. Dabo
Platinum and platinum group alloys are commonly used as hydrogen fuel cell catalysts. Nanoparticle-based catalytic electrodes used in fuel cell devices suffer from degradation loss of catalytic activity over cycling; this is partially attributed to platinum corrosion. Some kinetic models of these systems utilize approximations such as the Kelvin equation to get an average thermodynamic driving force for dissolution in vacuum. To improve models that use average chemical potentials in vacuum, we aim to account for effects of the electrochemical double layer and explicit treatment of edges and facets in the early stages of dissolution. We apply semi-local density functional calculations with implicit solvation techniques to model dissolution as a function of applied voltage, nanoparticle shape, and size. These calculations have shown that the dissolution is sensitive to voltage and may not follow simple trends in platinum ion coordination on a nanoparticle. In conjunction with these calculations, reactive molecular dynamics potentials were used to simulate nanoparticles as a function of shape and size. Results from the molecular dynamics simulations indicate that the thermodynamic driving forces for dissolution are highly site-dependent and show regimes where more simple approximations are valid.
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67-pm Sustainable and Functional Protein Fibers and Films
H. Jung, C. Skidmore, S. Sayin, Y. Kikuchi, H. Zhu, Be. Allen, M. Demirel
Production of repetitive polypeptides that comprise one or more tandem copies of a single unit with distinct amorphous and ordered regions have been an interest for the last couple of decades. Their molecular structure provides a rich architecture that can micro-phase-separate to form periodic nanostructures (e.g., lamellar and cylindrical repeating phases) with enhanced physicochemical properties via directed or natural evolution that often exceed those of conventional synthetic polymers. In this talk, we review programmable design, structure, and properties of functional fibers and films from squid-inspired tandem repeat proteins, with applications in advanced textiles.
68-pm Intra-operative Composite Tissue Bioprinting for Craniomaxillofacial Reconstruction
K.K. Moncal, H. Gudapati, K.P. Godzik, D.N. Heo, E. Rizk, D. Ravnic, H.B. Wee, D.F. Pepley, V. Ozbolat, G. Lewis, J. Z. Moore, R. Driskell, I.T. Ozbolat
Craniomaxillofacial (CMF) malfunctions affect 7% of newborn children and as many as 3 million adults each year in the United States because of congenital disorders and traumatic injuries. Current approaches in repairing CMF defects possess several limitations and the reconstruction of CMF defects seamlessly is highly challenging, as precise layer-by-layer stacking of multiple tissue compartments is not trivial. Such compartmentalization necessitates the precision and effective use of stem cells and differentiation factors and differentiating stem cells into multiple lineages is crucial in order to recapitulate the native tissue anatomy. With the advances in three-dimensional (3D) bioprinting, reconstruction of composite tissues in situ for CMF repair has recently become feasible as 3D bioprinting enables complex tissue heterogeneity in an anatomically accurate and cosmetically appealing manner. In particular, intra-operative bioprinting – the robot-assisted deposition of various biological materials directly into the defect site(s) - can be utilized to reconstruct various anatomically-correct tissue types such as bone and skin in surgical settings. This technology aims to reduce the manual interventions, eliminate issues such as swelling and change in morphology during the construct fabrication by immediately delivering constructs to defect side for accurate personalized reconstructions. This study is the first attempt toward the reconstructing both soft and hard tissues together through intra-operative bioprinting using advanced robotics technology in the surgical setting, which has not been previously demonstrated. Here, we investigated the efficacy of the modality for the reconstruction of bone and skin tissue constituting the CMF tissue of the 12 weeks-old male inbred rats by employing extrusion- and droplet-based bioprinting techniques. Direct printing of osteoconductive bone bio-ink and fibroblasts-laden skin bio-ink provided immediate treatment and delivery of bone and skin regenerating constructs into the defect site(s) and promoted advance surgical robotic integration toward clinical studies for long-term bone and skin repair. Ultimately, this work will open up a new research fields in intra-operative composite tissue printing of bone and skin tissue constructs to reduce bone and skin graft shortages and implantation needs.
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69-pm In vitro Efficacy in Treating Metastatic Triple Negative Breast Cancer in Bone via a Targeted Calcium Phosphosilicate Nanoparticle (CPSNPs) Encapsulating Modified 5-Fluro-Uracil
C. Gigliotti, B. Adair, J. Snyder, N. Gigliotti, W. Loc, J-K Liu, J.H. Adair, A. Mastro
Targeted delivery of chemotherapeutics encapsulated in our CPSNPs have potential to treat human cancers such as metastatic breast cancer in bone which has no accepted protocol for treatment. The hypothesis for the current study was that nanoparticles encapsulating chemotherapeutics with surface bioconjugation of an anti-sense target molecule on the nanoparticles would promote cell death in the breast cancer without infiltrating the bone cells. The target molecule, a-CD71, for receptors associated with the triple negative human breast cancer cell membrane, MDA-MB-231, was combined with encapsulated Rhodamine WT (Red) fluorophore and a novel chemotherapeutic, phosphorylated 5-Fluoro-Uracil (FdUMP), in CPSNPs for fluorescent microscopy evaluation, DAPI staining, and MTS bioassays. The metastatic breast cancer cells in bone cell cultures within 48 hours after introduction of the CPSNP formulations at 400nM FdUMP demonstrated a fascinating range of behavior captured in fluorescent photomicrographs. There was widespread evidence that the red fluorescing a-CD71-FdUMP-RhWT-CPSNPs associated with breast cancer cell membranes and, where red blossoming occurred, the small (20nm) CPSNPs dissolved and RhWT and FdUMP infiltrated the breast cancer cell cytosol. The onset of apoptosis was indicated by unraveling of many cell membranes of the breast cancer that decomposed into smaller spherical bodies, the so-called blebs associated with apoptosis. DAPI staining of the viable nucleic acid material in the cell nuclei indicated that only bone cells maintained robust viability relative to the apoptotic breast cancer cells up to 96 hours after introduction of the nanomedical formulation. In contrast, 200uM free FdUMP was required to achieve similar effects validating the utility of the targeting of the nanoparticle formulations. MTS assays were more ambiguous in the metastatic cell cultures. Detailed approaches and experimental results to separate the effect of the mixed cell cultures on the measurements of mitochondrial activity provided by the MTS assay will be presented.
70-pm Acoustic Characterization of Polymeric Membrane and Coatings Provides Environmental Impacts on Mechanical Properties
B.D. Vogt
Environmental or operational conditions can compromise the performance of polymer membranes and coatings through plasticization or adhesion loss. Understanding the mechanical properties of the membranes and coatings under these conditions can be challenging to measure. For example, the performance of membranes for the separation of biologically derived chemicals from fermentation is commonly limited by fouling caused by byproduct components. The complexity of such systems with both biological products and additives lead to a plethora of potential interactions and equilibration can be long to limit the ability of using bulk samples to assess their influence. Here, we examine how a common polyol antifoam agent (Antifoam 204) unexpectedly and dramatically swells and plasticizes a high performing biobutanol membrane copolymer of hydroxyhexafluoroisopropyl and n-butyl substituted norbornene using acoustic measurements based on the piezoelectric oscillation of quartz. When equilibrated against 1 wt %(aq) butanol, the solvent in the copolymer increases from < 10 vol% without the antifoam to >40 vol% at 1 ppm antifoam and >80 vol% at 100 ppm antifoam. The effect of the antifoam on the properties of the copolymer is much more significant than that of butanol concentration. Even with 4 wt % butanol (greater than typically viable for biobutanol), the copolymer swells < 25 vol% without the antifoam. The rheological properties of the copolymer are also
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influenced with a phase angle of <15º (viscoelastic solid) with nearly GPa modulus when swollen with aqueous butanol solution, while the phase angle increases to >50º (viscoelastic liquid) with MPa modulus with the addition of ppm of antifoam at 37 ºC despite the glass transition temperature of the copolymer exceeding 350 ºC. Additionally, we show how this same technique can be used to show signatures of solvent induced adhesive failure through the changes in the energy dissipation for a similar polymer when exposed to basic conditions. These results demonstrate the striking effect of solution additives on the properties of advanced polymers for membranes and illustrate the importance of considering the potential interactions of all components with a membrane beyond those of interest for the separation.
71-pm Aspiration-assisted Bioprinting
B. Ayan, I.T. Ozbolat
In contrast to traditional two-dimensional (2D) cell culture, three-dimensional (3D) tissue spheroids offer many advantages, such as the ability of cells to secrete their own extracellular matrix (ECM) and increasing effective communication between cells in a particular tissue microenvironment. Recently, one of the primary focus of bioprinting research has been the development of various methods to automate the manufacturing process of functional 3D tissue constructs for large scale tissue biofabrication. In order to bioprint tissue spheroids, we have investigated a new process, which enables precise positioning of tissue spheroids onto a fibrin scaffold. We have developed an aspiration-assisted bioprinter (ABB), where a pipette, mounted on the arm, picks the spheroids via the aspiration pressure and place them one by one onto fibrin. Each spheroid is visually inspected before printing onto desired location. The inspection process reduces the chances of contamination and ensures that only the spheroids of desired size and shape are used to construct the tissue. Automatic and semi-automatic control modes implement a rapid process cycle with a variable level of control and process automation. By monitoring spheroids and reducing the handling time we maximize the cell proliferation of the final biostructure. This printing technique has the ability to monitor and maintain required back pressure while capturing and placing the spheroids during their placement. This novel bioprinting technique can be used for many organ-on-a-chip platforms for drug screening.
72-pm Adaptive Thermal Composites
H. Jung, C. Skidmore, S. Sayin, Y. Kikuchi, H. Zhu, B. Allen, M. Demirel
Recent advances in synthetic biology and two-dimensional (2D) layered materials combined with parallel improvements demonstrated that more complex composites materials with properties engineered precisely to optimize performance could be achieved. We created functional programmable materials with user defined physical properties from composites of 2D-layered materials and polymeric proteins [1]. Our approach is based on directed evolution of polymeric proteins to screen molecular morphology of adaptive materials [2]. These proteins have several advantages as adaptive materials [3]: (i) their chain length, sequence, and stereochemistry can be easily controlled, (ii) their molecular structure and morphology is well-defined, (iii) they provide a variety of functional chemistries for conjugation to 2D materials, and (iv) they can be designed to exhibit a variety of physical properties. The variability of the amino-acid sequences in the polymeric proteins, which will dictate the degree of crystallinity and alignment of the protein layers, are used to control the interactions at the 2D material/protein interface, ultimately dictating the
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functional physical properties (e.g., Phononic, electronic or photonic) of novel materials and devices. References: [1] Demirel et al., Advanced Functional Materials 28 (27), 1704990, 2017; [2] Tomko et al., Nature nanotechnology 13 (10), 959, 2018; [3] Jung et al., Proceedings of the National Academy of Sciences 113 (23), 6478-6483, 2016.
73-pm 2DLM: The Center for 2-Dimensional and Layered Materials
M. Terrones, J. Robinson
The Center for 2-Dimensional and Layered Materials conducts leading international and multidisciplinary research on 2D layered materials aiming at finding new phenomena and applications, that could be transformed into high impact products. The center offers a unique, vertically integrated research education to graduate and undergraduate students, with extremely valuable components including state-of-the-art infrastructure, and research environment.
The facilities that are offered in the center include furnaces and deposition tools that are used to produce the 2D materials, specialized analytical instruments to examine and probe the films, and computational resources that help to model the formation and structure. An example project in the center is the growth of crystalline large area WS2 directly on SiO2/Si substrates.
2DLM organizes a workshop called “Graphene and Beyond” that has been held every May since 2011. This workshop receives abstracts and presentations from all over the world, and it is expected to form ties to the Graphene Flagship organization in the EU in 2019. Consider joining 2DLM for Graphene and Beyond in 2019.
74-pm Plasmonic Metalattices P. Moradifar, L. Kang, P. Mahale, Y. Liu, N. N. Nova, A. Glaid, T. E. Mallouk, J. Badding, D. Werner, N. Alem
Various noble metals (gold and silver) based nanostructures have been extensively studied for their well-known plasmonic responses. However, there are strong motivations in exploring new plasmonic structures that exhibit lower losses and more functionally diverse properties. Metamaterials have been proposed because of their highly tunable optical properties through engineering the internal structures that may not exist in nature.
Metalattices as a subgroup of metamaterials, are nanostructured 3D ordered hybrid materials on the range of sub 100 nm (sub wave-length scale). A metalattice structure is comprised of dielectric silica nanospheres and meta-atoms linked through thin interconnected channels named meta-bonds. A void-free infiltration of these 3D ordered frameworks with semiconducting materials and/or metals can provide a versatile and tunable platform as integrated plasmonic interconnects for large optical confinement and long propagation distance applications. Recently, chemical fluid deposition from supercritical carbon dioxide, has been shown as a robust and cost-effective approach to achieve void-free infiltration of such hybrid systems.
Monochromated electron-energy loss spectroscopy (EELS) in conjunction with aberration corrected scanning transmission electron microscopy (STEM) and x-ray energy dispersive spectroscopy (XEDS) was used to undertake a detailed study of nanoscale optical response variations in metalattices. This has been done by indirect mapping of the spatial variation of electromagnetic hotspots associated with the localized surface plasmon (LSP) resonances at the nanoscale level on Ag
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metalattices metalattices as a novel plasmonic structure for a wide spectral range across visible and UV regime followed with detailed analysis of LSP resonances features. In addition, Si-Ge core-shell metalattices with etched cavities are studied to explore the effect of periodic cavities on optical response variations in this structure. This work will also combine CST calculations to further elaborate the experimental EELS measurements.
75-pm Liquid-Liquid Phase Separation in Nanoscale Particles
M.A. Freedman
The phase and morphology of aerosol particles impacts their optical properties, reactive chemistry, water uptake behavior, and fate. My research group has focused on studies of aerosol particles of atmospheric relevance that undergo liquid-liquid phase separation due to salting out of the organic component. We discovered that phase separation is inhibited in particles less than approximately 50 nm because particles of this size cannot overcome the activation energy needed to form a new phase. In this poster, I will share our newest results in this area. Namely, 1) we have extended our initial systems to ones that better mimic atmospheric particles, containing several to hundreds of organic compounds mixed with ammonium sulphate. We show that the size dependence of morphology is observed for all systems, though more complex phase separated morphologies are observed as well. 2) We have developed a chamber to flash freeze particles as a function of relative humidity to determine the water content of the particles at the point of phase separation. 3) We have explored the role of viscosity in the phase separation behaviour of these systems. Implications of our results for atmospheric chemistry and climate will be discussed.
76-pm Two-Dimensional Material Synthesis via Chemical Vapor Deposition (CVD), Chemical Vapor Transport (CVT) and Physical Vapor Transport (PVT) Processes
J. Kronz, B.Huet, R. Lavelle, J. Fox, R. Cavalero, T. Mirabito, M.Pagan, N. Christie, D. Snyder
Two-dimensional (2D) materials are of interest for the next generation of nanoelectronics offering unique electronic and mechanical properties in materials confined to the atomic plane. 2D materials of current interest include graphene, various transition metal dichalcogenides, and hexagonal boron nitride (hBN). Graphene and MoS2 have attractive properties for electronic devices that have been heavily studied lately, but both have shown superior electronic properties when integrated in a van der Waals (vdW) heterostructure with hBN as the substrate. The atomically smooth surface and the insulating nature of hBN reduces electron scattering and improves the electrical transport properties in the 2D material on top. CVD growth of MoS2 on hBN has also demonstrated a more oriented growth mechanism leading to better single crystal formation. This suggests that using hBN as a substrate for 2D materials would enable higher quality growth and subsequently better electronic performance due to these van der Waal’s and insulating properties.
One of the most common methods to fabricate these structures is through the use of exfoliation. While this method is useful for small scale testing, it lacks scalability and structure control. Chemical vapor deposition (CVD) involves the use of chemically reactive precursors and generally allows for large area growths in addition to crystal structure and thickness control. Chemical vapor transport (CVT) involves the use of a transport agent (typically a halogen) to allow transport of difficult to volatize species. In our lab CVT is used to grow various bulk crystals, typically for subsequent exfoliation. Physical vapor transport (PVT) processes
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typically thermally volatize precursors which are then transported either by diffusion or convection to a substrate crystal.
In this poster we present results for the synthesis of a range of two-dimensional materials including graphene, hBN, MoS2, WS2, ZrS2, ZrSe2, and Sn(S,Se)2 using these three processes.
77-pm Abnormal Interlayer Coupling in Janus MoSSe/MoS2 Heterostructures K. Zhang, Y. Guo, H. Wang, A.A. Puretzky, D. Geohegan, J. Kong, X. Qian and S. Huang
Janus transition metal dichalcogenides (TMDs) possess additional degree of freedom compared to their mother TMDs. MoSSe, as an example, has one layer of S atoms replaced by Se atoms. The unique crystal structure has broken out-of-plane mirror symmetry in the monolayer and leads to an out-of-plane dipole moment that can be added up by increasing the number of layers. As the first successfully synthesized Janus monolayer, MoSSe has motivated a series of theoretical work on the lattice dynamics and electronic properties of Janus multilayers and heterostructures with other two-dimensional materials. Janus MoSSe is predicted and proven experimentally to possess out-of-plane dipole moment, large in-plane and out-of-plane piezoelectricity, and strong second harmonic generation, which are essential to optoelectronic applications based on interfacial properties. In this work, we studied the fundamental phonon properties and interlayer coupling of the monolayer Janus MoSSe and MoSSe/MoS2 HSs. Interlayer shear and breathing modes of high-symmetry 2H (AB) and 3R (AA) heterostackings are probed by low-frequency (LF) Raman spectroscopy. Both shear and breathing of MoSSe/MoS2 HSs show noticeable variations in frequencies for different stacking patterns. Unintuitively, interlayer coupling in the HSs is significantly enhanced compared to their pure MoS2 counterparts as a result of the strain effect introduced during synthesis. Further, changes in the high-frequency modes of the HSs are consistent with variations in the LF modes, serving as strong evidence for the abnormally enhanced interlayer coupling. These spectroscopic features are signatures of stacking configurations, interlayer coupling in heterostructures, and degree of conversion in the fabrication process from TMDs to Janus TMDs.
78-pm Surface-Initiated Ring-Opening Metathesis Polymerization as a Route to Versatile and Complex Nanocomposite Materials
J. LaNasa, R.J. Hickey
Polymer grafted nanoparticles have been targeted as an effective method for creating well-dispersed polymer nanocomposite materials. The bonding of organic and inorganic components at their interface helps to deter phase separation of otherwise incompatible components can drastically increase the dispersion, particle loading, and nanoscale properties of these materials in matrix or matrix free cases. Surface initiated polymerization is one of several popular strategies for combining the two components into a single building block. Many of the well utilized surface-initiated polymerization (SI-P) techniques afford styrenic or methacrylate-based polymer grafts, while the possibility of grafting semi-crystalline and complex chain architectures are very much being developed in today’s nanocomposite field.
Ring-opening methathesis polymerization (ROMP) has for decades been known as an effective way to polymerize cyclic olefins. This class of polymers are exciting due to their customizable monomers and post polymerization modifications. The surface initiated of this polymerization (SI-ROMP) has been underutilized by comparison to other SI-P techniques but presents a route to affording polymer
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grafted nanoparticles that drastically differ in their architectural, thermal, and modification properties to that of traditional polymer grafted particles.
The work presented in this poster implements SI-ROMP as a synthetic technique for grafting polymer chains of controllable molecular weights from the surface of silica nanoparticles of tunable size. We demonstrate the versatility of the SI-ROMP technique through the grafting of semi-crystalline (polyethylene) and bottlebrush (poly(ethylene oxide)) chains. Furthermore, we incorporate SI-ROMP synthesized 1,4 poly(butadiene) grafted particles into free radical polymerization of styrene and investigate the impact of embedding grafted particles in organization and performance of high impact polystyrene nanocomposite materials.
79-pm Seeded Growth of Metal Nitrides on Noble Metal Nanoparticles to Form Complex Nanoscale Heterostructures
R.W. Lord, C.F. Holder, J.L. Fenton, R.E. Schaak
Hybrid nanostructures represent an emerging class of colloidal nanoparticles which incorporate the direct solid-state interfacing of multiple disparate chemical species within a single particle framework. The solid-state interface gives rise to synergistic electronic, magnetic, and catalytic properties beyond those of the individual components. Despite the diverse library of hybrid nanostructures reported, chemical and synthetic considerations have restricted the materials landscape. Among the material classes largely missing from colloidal heterostructures, transition metal nitrides represent an interesting class of materials for electro-optic, energy harvesting and storage, and catalysis. Historically, the lack of reactive nitrogen precursors accessible at temperatures amendable to solution processing, has limited transition metal nitride nanostructures to a few systems. Cu3N and Cu3PdN represent two materials which are both accessible through colloidal methodologies and are synthetically interesting for their applications towards catalysis and energy storage. This work demonstrates the synthesis of metal nitride containing heterostructures through seeded growth of Cu3N and Cu3PdN on noble metal seeds, Au and Pt. Utilizing Pt-Cu3PdN as a model system, it is shown that the seeded growth of Cu3PdN undergoes a step-wise growth pathway with a final product morphology dependent on starting seed morphology. Utilizing these insights, higher order heterostructures were synthesized including three distinct material components.
80-pm Shear Flow-induced Nucleation of Poly(ether ether ketone)
J. Seo, A. M. Gohn, R.P. Schaake, A.M. Rhoades, R. H. Colby
Polymer nucleation is a chain-ordering process that is the first step to crystallization. When a polymer melt is subjected to intense shear flow before nucleation, the flow can stretch the longest chains, lowering their entropy and accelerating nucleation. In this study, the flow-induced nucleation of commercial poly(ether ether ketone) is investigated by means of rheology and differential scanning calorimetry to elucidate the role of well-defined shearing parameters; shear rate (γ ̇) and shearing time (ts). Moreover, the combination effects of γ ̇ and ts on the acceleration are monitored in terms of specific work (𝑊 = ∫ �̇�𝜎'(
) 𝑑𝑡). The specific work is proven to be the main variable controlling flow-induced nucleation kinetics. From the results, a flow-induced nucleation model is suggested based on the entropy reduction model of Flory and the nucleation model of Hoffman and Lauritzen. Finally, the flow-induced crystal orientation and morphology are observed using small angle X-ray scattering and atomic force microscopy.
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81-pm
Crosslinked Polymer-Graphene Composite Membranes for High-Performance Dewatering of Bio-energy Relevant Aqueous Streams
O. Agboola M. Lu, M. Hu
We prepared, and tested, novel water-transporting membranes based on sulfonated polybenzimidazole (s-PBI)-additive-filler composite coatings supported on porous ceramic tubes. These membranes are of interest because they can be used to dewater aqueous solutions of acetic acid. Large amounts of acetic acid are used by the chemical, pharmaceutical, medical and food industries. Aqueous acetic acid is also a byproduct of producing aspirin and biofuel; therefore, further separation is needed to reduce environmental pollution and recover the acid. Traditional distillation columns can be used for this purpose, but these are economically expensive and relatively ineffective, because acetic acid and water have similar volatilities. Distillation systems also require large inputs of energy. Pervaporation is potentially a more useful separation method that involves the partial vaporization of a solution, followed by vapor transport through a membrane. We studied multiple feed concentrations and temperatures for dewatering aqueous acetic acid by pervaporation and evaluated the results of our experiments with respect to flux and the separation factor. We found that higher temperatures increased flux and reduced the separation factor, and that lower temperatures reduced flux but allowed a higher separation factor. Thermal treatment, sulfonation, fillers, and cross-linker additives in composite membranes have been investigated and have strong effects on pervaporation performance. We performed numerous characterizations (FTIR, TGA, NMR, in situ-Raman Spectroscopy, QCM, HPLC, and contact angle) to exemplify the physiochemical transformations of the polymer coating and its additives upon thermal and chemical modifications. Our membrane achieved a flux of 0.396 L/hr/m2 (LMH) and a separation factor of 24.3 when dewatering a feed mixture of acetic acid and water (30/70 wt%) at 80°C. A ceramic support is vital because it increases the lifetime of polymer membranes and can be scaled up for industry needs.
82-pm “Structural Instability” Induced High-performance NiFe Layered Double Hydroxides as Oxygen Evolution Reaction Catalysts for pH-near-neutral Borate Electrolyte
Y. Dong, S. Komarneni
It is urgent to develop cost-effective and highly efficient oxygen evolution reaction (OER) catalysts for the water splitting processes in neutral or near-neutral pH. Compared to alkaline or acidic conditions, pH-neutral or pH-near-neutral conditions are expected to be less corrosive and safer. In addition, electrolytes from natural sources such as sea water could be used directly. Here, we discovered for the first time that the anion-exchange properties of Ni-Fe layered double hydroxides (NiFe LDHs) can be exploited to make them excellent OER catalysts through intercalation of large organic anions for pH-near-neutral borate electrolyte (K-Bi, pH=9.2). In this work, NiFe LDHs intercalated with different dicarboxylate anions were synthesized and were studied as OER catalysts in the K-Bi electrolyte (pH=9.2). Sebacate anion intercalated NiFe LDH (NiFe LDH Seb) and suberate anion intercalated NiFe LDH (NiFe LDH Sub) were found to be excellent OER catalysts which outperformed RuO2 in the K-Bi electrolyte (pH=9.2). The NiFe LDH Seb needed an overpotential of 376mV and NiFe LDH Sub needed an overpotential of 387mV to reach a current density of 1 mA/cm2 which are the lowest among all the reported earth-abundant OER catalysts and lower than that of RuO2 powder (393mV). For the first time, earth-abundant OER catalysts outperformed precious RuO2 in the pH-near-neutral borate electrolyte. Moreover, these materials also showed great stability for at least 24 hours. Besides, all the NiFe LDHs intercalated with dicarboxylate anions showed good OER performances in K-Bi (pH=9.2). The good OER performances of the
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dicarboxylate anions intercalated NiFe LDHs can be attributed to the “structural instability” induced by in-situ anion exchange process during the OER in which borate anions can enter the interlayers of LDH and facilitate the activation of more Ni. This study shows that the “structural instability” caused by pillaring of transition metal LDHs with large organic anions could be a promising way to make novel highly-efficient OER catalysts for the pH-near-neutral K-Bi electrolyte.
83-pm Atomic Layer Deposition of and on Transition Metal Dichalcogenides
T. N. Walter, A. J. Mughal, O. Cook, K. A. Cooley, S. Lee, X. Zhang, M. Chubarov, J.M. Redwing, T.N. Jackson, S. E. Mohney
Atomic layer deposition (ALD) offers a low-temperature route to preparing transition metal dichalcogenide (TMD) layers. In this presentation, we describe the preparation of molybdenum disulfide and hafnium disulfide by plasma atomic layer deposition. To prepare molybdenum disulfide, we used the co-reactants bis (tert-butylimido)-bis (dimethylamido) molybdenum and a hydrogen disulfide–argon plasma. Few-layer films were controllably prepared, as confirmed by transmission electron microscopy, atomic force microscopy, and x-ray photoelectron spectroscopy. Resonance Raman spectroscopy allowed us to draw conclusions about the relative crystalline perfection of films on various substrates (sapphire, gallium nitride and the thermal oxide on silicon). Likewise, we explored the growth of hafnium disulfide with tetrakis (dimethylamido) hafnium; however, films could only be prepared by using a hydrogen disulfide–argon plasma. The process for hafnium disulfide was also less reproducible than the process for molybdenum disulfide due to the strong tendency for hafnium disulfide to oxidize.
The second theme of this presentation is the deposition of ZnO films on the basal plane of TMDs by ALD. Inducing nucleation on the inherently passivated surfaces of 2D materials can be challenging for ALD; however, this situation also presents an opportunity for selective growth by ALD. Here, the growth of ZnO is performed on the TMDs MoS2 and WSe2 using thermal ALD, thermal ALD with UV-O3 surface pre-treatment, and plasma enhanced ALD (PEALD). Depositions were performed on few-layer exfoliated flakes and coalesced single-layer films (with scattered 2- or 3-layer islands) grown by gas source chemical vapor deposition (CVD). Characterization by atomic force microscopy (AFM), Raman spectroscopy, photoluminescence (PL) spectroscopy, and X-ray photoelectron spectroscopy (XPS) gave insight into the ZnO films grown and the effect of different growth methods on the underlying TMD. For both MoS2 and WSe2, thermal ALD of ZnO using diethyl zinc (DEZ) and water at 125 °C resulted in a long nucleation delay on the TMD surfaces, showing selectivity against ZnO growth on TMDs compared to the surrounding SiO2/Si substrate. However, nucleation did occur at defects and caused surface roughness to increase. UV-O3 pre-treatment before thermal ALD yielded different results on MoS2 compared to WSe2. UV-O3 functionalizes MoS2 for nucleation and subsequent growth of ZnO without destroying the underlying MoS2; however, UV-O3 fully oxidized regions of the WSe2 surface and promoted nucleation. PEALD using diethyl zinc and N2O on both TMDs resulted in a conformal and smooth film, but it oxidized the top layer of both TMDs.
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84-pm Nano- and Micro-structure Engineering of Superalloy and Ceramic Composites by Field Assisted Sintering
J. Dai, C.I. Lin, J. Singh, N. Yamamoto
Unlike conventional sintering methods such as pressureless sintering and hot-pressing, field assisted sintering technology (FAST) combines pressure with direct or pulsed current, creating rapid Joule heating within the graphite die and conductive powders. The resulting rapid volumetric heating offers benefits including high heating rates, short sintering cycles, localized heating and thus enhanced control over the microstructure of the sintered product. As a result, FAST can be used to sinter a wide variety of materials, including metals, inter-metallics, ultra-high-temperature ceramics, and may also be used to join dissimilar or functional graded materials. This collaborative work explores the engineering of two material systems using FAST: strengthening of nickel (Ni)-based superalloys with carbide additions and fabrication of hierarchical- structured boron carbide composites.
First, we study the micro-structure engineering of the Ni-based superalloy CM247LC for high-temperature aerospace turbine applications. In order to increase the thrust-to-weight ratio in turbine engines, thermal or mechanical properties of the disk and blade materials must improve. By engineering the phases between grains in polycrystalline Ni-superalloys, it is possible to control grain growth as well as strengthening mechanisms, thus modifying the material strength. In this work, between 0 and 5 vol.% of hafnium carbide (HfC) micro-powder is mixed with CM247LC powder using two methods: acoustic mixing and ball milling. Both mixing methods result in a HfC grain boundary phase with no pullout. The HfC phase pins the grain boundaries, slowing diffusion between CM247LC particles and allowing porosity to migrate out of the material, resulting in higher relative densities. The addition of HfC leads to material hardness and elastic modulus consistent with those predicted using the rule of mixtures, suggesting that a CM247LC-HfC composite was successfully formed using FAST without detriment to material properties.
Second, we study the sintering behavior and mechanical properties of boron carbide (B4C) composites with hierarchical micro-structure. With a unique combination of properties including high hardness, low density, and thermal stability, B4C is suitable for applications such as protective armor, high-temperature thermal electric converter, etc. However, its applications are limited by its intrinsic brittleness. To toughen B4C, we designed hierarchical micro-structures consisting of micron and nano-sized B4C grains, ‘soft’ carbon, and titanium diboride (TiB2) reinforcement phases, to utilize toughening mechanisms at multiple size-scales. The introduction of these micro-structure features was attempted through the co-sintering of B4C micro-powder, carbon-rich B4C nano-powder, and in-situ reactively formed TiB2 using FAST. The fabricated B4C composites were inspected using SEM/TEM and evaluated for their hardness and indentation fracture toughness. The addition of carbon-rich B4C nano-particles resulted in a marginal increase in fracture toughness due to crack deflection and bridging of graphite platelets formed during sintering, but the addition led to degradation in hardness due to the low hardness of graphite. For samples with both nano-powder addition and in-situ formation of TiB2, the high hardness of B4C was retained while fracture toughness enhancement from ~3.0 to 4.7 MPa·m1/2 was achieved.
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85-pm Atomic Layer Deposition of Metals and Metal Nitrides
B. Liu, B. Rainer
We recently developed a number of new plasma ALD processes on KJ Lesker Cluster ALD LX150, including TiN, Pt, SiO2, GaN, etc. It is a big challenge to grow TiN with low O concentration due to the high reactivity of Ti. Factors like tool design and gas purification are all needed to address the issue. Significant progress has been made by working with KJ Lesker. Results of TiN process and film characterization and tool upgrade are going to be presented in this poster. Results of Pt and SiO2 will also be included.
86-pm Early Age Microstructural Differences of Tricalcium Aluminate and Gypsum Pastes from Hydration in Microgravity
P.J. Collins, R.N. Grugel, A. Radlińska
It is envisioned that humans will embark on space exploration missions for extended periods of time. This articulates the need of resilient habitats that would protect humans and equipment from radiation and harsh extraterrestrial environments. A cement-like binder from in-situ materials is one of the most viable options for the shelters, however, the material’s behavior under reduced gravity has not been explored yet. In Earth-based concrete construction, a flash set is a highly undesirable event as it results in a loss of workability and a rapid hardening of the concrete, making it unusable. To help mitigate flash set, gypsum, a sulphate bearing phase is added to OPC in small amounts. The reason for gypsum leading to a delay in set time is still debated. To investigate cement solidification in space and shed some light on the flash set phenomenon, samples were sent to the International Space Station to be mixed by astronauts and solidify without gravities effects. A set of the tricalcium aluminate and gypsum samples were analyzed at various times in the first 24 hours of hydration. At around three hours of hydration, substantial microstructural differences are present due to minimized fluid convection and a diffusion-controlled hydration process. At these early ages, concentrations of reaction products are seen on and around the decomposing gypsum. Dissolution of gypsum on the ground is typically a layer by layer process leading to a rather smooth looking surface. In microgravity, the gypsum becomes heavily striated showing signs of preferential dissolution. Studying this system in microgravity is a first step towards resilient habitats for extended human space exploration missions and results in a better understanding of the reaction on Earth.
87-pm New Frontiers for Cold Sintering: Instrumentation to Functional Materials
R.D. Floyd, S.M. Lowum, J.P. Maria
Reduced sintering temperatures is a topic of growing interest due to the need for materials integration, microstructure control, and fabrication of dense monoliths from temperature-sensitive materials. A technique termed cold sintering has allowed for densification of materials at temperatures 300°C or below via the addition of a secondary mass transport phase and moderate pressures. A custom-designed press, named the Sinterometer, was built in order to monitor in situ compaction of the cold sintering process and has led to a wealth of knowledge about densification rates and mechanisms that were unobtainable using previous equipment. Specifically, long-term experiments have shown that the aqueous solutions of acids, bases, or salts primarily used for mass transport phases may be inherently limiting the number of materials that can be densified at such low temperatures. New, non-aqueous transport phases inspired by flux crystal growth have recently been applied to cold sintering and have proven advantageous in densifying materials that had proven resistant to cold sintering before, such as Bi2O3, NaxK1-xNbO3, and BaFe12O19. Typically, molten fluxes are used well above the low temperature range of cold sintering, however adding a small percentage of water to many fluxes has shown to suppress the melting point such that they
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can be used below 300°C. Experimentation has been conducted to investigate the mechanisms of densification involved in cold sintering using non-aqueous transport phases as well as the dependence on process variables such as pressure, temperature, and transport phase quantity. Additionally, work has been done to expand cold sintering to functional materials with useful properties. Magnetic properties of BaFe12O19 and dielectric properties of Li2MoO4- BaFe12O19
composites, a material system difficult to fabricate at high temperatures, will be demonstrated.
88-pm Characterization of Atypical Martensite Behavior in NiTiNb Alloys
R. W. LaSalle, Dr. R.F. Hamilton
Adding niobium to nickel-titanium alloys produces a class of NiTiNb shape memory alloys (SMAs) that exhibit underlying martensitic phase transformation (MT) occurring in temperature ranges such that the shape memory behavior is compatible with temperatures typically experienced in the human body. The result is a compliant martensitic structure that enables the SMA to be deployed in a heavily deformed state which can be leveraged to keep vessels open at a constant force or provide clamping/morphing functionality. Utilizing deformation processing to tailor the oriented Nb morphology (i.e. discontinuous fiber size and spacing) allows for tuning the underlying MT and customizing the shape memory behavior for deployable biomedical structures. This work investigates the impact of differential Nb microconstituent morphologies, in different wrought forms that have experience different extents of deformation during processing, on stabilizing the otherwise unstable atypical martensitic structures. Post processing heat treatments are employed in order to relieve microstructure constraints associated with the oriented Nb microconstituent phase. We contrast the thermal recovery of thermal-induced martensite (TIM) behavior without external load with the recovery of stress-induced martensite (SIM) produced by increasing levels of pre-strain. The stress-strain-temperature responses of heat-treated alloys exhibit TIM, SIM, and locked martensite. The results support that martensite becomes stable due to interactions with the Nb fiber-like reinforcements. There are two interesting factors when studying this locked martensite; a sufficient amount of pre-deformation must be applied to lock the martensite, and the relatively high recovery temperature range is only observed once upon the first heating of the material and unobserved upon the following temperature scans, leading to the idea that the locked martensite is unstable. The pairing of pre-straining of various geometries of NiTiNb and DSC has shown evidence of locked martensite that is formed by way of a non-repeatable elevated reverse transformation peak upon the initial heating of the material.
89-pm Production of Graphene and Conductive Carbon Black Analogue Using Advanced Microwave Plasma Technology
R.R Kumal, A.Gharpure, A Mantri, K.Zeller, G. Skoptsov, R.V. Wal
The advanced plasma technology practically and cost-effectively converts natural gas to value-added chemicals and premium carbon materials such as graphene and conductive carbon black analogues (CCBA) with no CO2 emissions and low capital and infrastructure expenditures. A microwave driven plasma drives hydrocarbon decomposition – producing a variety of carbon nanostructures without the use of catalyst. With lower-energy requirements than conventional thermal plasmas, reactions in microwave plasmas are driven by electron kinetics rather than thermodynamics, and their non-equilibrium energy distribution opens reaction pathways that are unavailable with conventional chemical or thermal plasma processes. The form and purity of carbon material can be controlled by optimizing the several interrelated parameters that include methane to hydrogen
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ratio in the feed stream and reactor conditions such as input energy and formation temperature. Primary products include nanographene comprised of 2-6 sheets per stack with lateral dimensions between 100 and 500 nm, and graphitic carbon particles with structure analogous to conductive carbon blacks Analytical techniques including high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), Raman spectroscopy and electrical conductivity measurements are utilized to study the form and quality of these valued carbon materials. Optical spectra are collected and analyzed to determine the formation temperature of these carbons using blackbody radiation and C2* Swan band emission. The electrical conductivity of the as-produced CCBA material is higher than that of commercially available conductive carbon blacks. These results highlight the importance of advanced plasma technology for the economic utilization of natural gas by producing premium carbon materials.
90-pm Advanced Additive Manufacturing of Metals for Emerging Energy Applications
T.A. Palmer
The Additive Manufacturing (AM) of metallic systems represents both great promise for the larger scale implementation of AM and challenges in producing structurally sound components with consistent material properties. The characteristic layer-by-layer deposition of the AM process produces complex processing conditions that can lead to unique microstructures and properties. In addition, it provides the opportunity to much more easily integrate different materials into complex geometries. Significant work is being undertaken globally on improving the process understanding as well as characterizing material properties in AM fabricated monolithic and functionally graded metallic components. Much of this work involves alloy systems of use in high temperature and corrosive environments of interest to a wide range of energy applications. Alloy systems currently being pursued include a range of austenitic, duplex, and precipitation hardened (PH) grade stainless steels as well as nickel base alloys. However, the traditional process-structure-property relationships developed for thermomechanical processing of these alloys are not applicable to the rapid heating, solidification, and cooling conditions prevalent in AM or the ease with which these conditions can be varied with changing processing parameters. The future promise of AM processing of metallic systems of interest to the energy industry will depend on the development of new alloy systems and improved understanding and control of the processing conditions and process-structure-property relationships.
91-pm Solid Sorbent Development for CO2 Capture
X.X. Wang, R. Zhang, S.M. Liu, C.S. Song
The rapid increase in the atmospheric CO2 concentration has aroused a significant concern on the global climate change. Carbon capture, utilization and sequestration (CCUS) is considered as one of key options for mitigating CO2 emissions. Although amine scrubbing has been commercially used for separation of CO2 in industry, it is still challenging to apply it for CO2 capture from flue gas because its regeneration is very energy intensive and costly due to the high heat capacity of aqueous solution. Therefore, developing cost-effective and energy-more-efficient approaches for CO2 capture has attracted great attention worldwide. In our laboratory, we have developed a series of solid amine sorbents called “molecular basket” sorbents (MBS) through near past two decades, which have demonstrated high capacity, high selectivity, good regenerability and stability with lowered energy consumption and material cost for CO2 capture
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covering wide CO2 concentrations (ppm to 100%). Characterization techniques improves the fundamental understanding of the MBS materials and CO2 capture process, thus benefits the development of new MBS sorbents with improved CO2 sorption capacity and sorption/desorption kinetics. The results are highly promising for further development of sorbent-based CO2 capture technologies.
92-pm Low-Temperature Sputtered Gallium Nitride (GaN)
J. Nordlander, K. Ferri, R. Collazo, Z. Sitar, J.-P. Maria
GaN is a desirable wide bandgap semiconductor for applications as blue and UV emitters as well as high temperature, high power, and high frequency electronic devices. In order to overcome the low reactivity of gallium with nitrogen at low temperatures, thin film GaN deposition techniques such as Metal Organic Chemical Vapor Deposition often use high pressure growth at temperatures in excess of 1000 °C. While higher temperatures allow for high crystal quality thin film GaN with favorable morphology, this presents challenges to abrupt junction formation due to fast diffusion rates that cause dopant migration during deposition. It is thus advantageous to find avenues to lower the deposition temperature for GaN to a region where controlled doping can occur. While doing so, it is imperative to maintain epitaxy and growth morphology for device fabrication. In this presentation, we demonstrate that reactive High-Power Impulse Magnetron Sputtering (HiPIMS) is an effective low temperature alternative for depositing high quality, epitaxial GaN thin films. In contrast to conventional direct current (DC) or radio frequency (RF) sputtering, pulsed DC provides the needed kinetic energy and ionization fraction to establish a sufficiently reactive environment to promote full nitridation. This can be challenging with many other Ga sources. More specifically, the low duty cycle regime of pulsed DC known as HiPIMS provides access to kW/cm2 peak power densities without target degradation and thus dramatically increased gallium reactivity. In addition, adding an opposite polarity voltage pulse between the target bombarding events, known as a kick pulses, further allows one to tailor both the adatom landing energy on the substrate surface, and mitigate target poisoning. This unique capability set enables us to prepare high crystal quality epitaxial GaN thin films with smooth surface morphologies characterized by c/2 steps and terraces at temperatures below 500 °C. The presentation will focus on the relationships between sputtering parameters including voltage, kick pulse, pulse length, and duty cycle, on GaN thin film crystal quality, surface morphology, and growth rate. Preliminary transport properties will be reported.
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93-pm Center for Self-Assembled Organic Electronics E.Gomez, J. Asbury, S. Milner, G. Galli, Z. Bao, A. Salleo, B.Ganapthysubramanian, M.Toney, I. McCulloch
Organic semiconductors have the potential to enable a variety of applications, including light-emitting diodes, bioelectronics, flexible electronics, and printable solar cells. Key to these devices is control of the active layer morphology. Thus, the recently founded Center for Self-Assembled Organic Electronics (SOE) is focused on developing strategies to control microstructure and electronic properties of this emerging class of electronic materials. Despite tremendous advances in controlling self-assembly of organic molecules in the literature, the impact on high-performance organic electronic materials has been limited. The challenge lies in the stiff conformations and complex phase behavior of conjugated molecules and polymers, including liquid crystalline interactions and phases that complicate the control of domain sizes and interface structures. As such, there is a tremendous opportunity to design materials that exploit these factors to control self-assembly in the active layer of devices. Our recent advances in theoretical descriptions of interaction parameters, chain conformations and liquid crystallinity of stiff molecules uniquely position us to develop new ways to control the microstructure. We aim to systematically control donor-acceptor interfaces of organic photovoltaic (OPV) materials composed of high-performance polymers and state of the art non-fullerene acceptors. Multi-scale tight-binding models that are coupled to universal descriptions of stiff polymers at interfaces will build predictive design rules about how molecular structure influences self-assembly and guide further development of high performance OPV devices.
94-pm Strategies for the manipulation of the Transport Properties of Ion Exchange Membranes
C. Capparelli, M. A. Hickner
Although polymeric materials are inherently ionic insulators, ion-containing polymers have been fabricated in which ionic groups are integrated to the polymer network, enabling ionic-conducting properties. These type of materials allowed for the development of ion exchange membranes, which consist of a polymer backbone with tethered ionic groups that serve as carriers for ions in separation processes, such as electrodialysis for water desalination, diffusion dialysis for wastewater treatment, and fuel cells for energy storage and conversion. These devices are key components in solving some of the challenges of the 21st century, such as renewable energy and water technologies.
The performance of ion exchange membranes is usually determined by two transport properties: conductivity and permselectivity. The conductivity of an ion exchange membrane is the rate of transport of ions through the membrane, while permselectivity is a measure of the selectivity of the membrane. These transport properties are determined by both the polymeric backbone material and the quantity and nature of the ionic groups. For this reason, conductivity and permselectivity are generally fixed quantities for a specific chemical composition. This research project focuses on developing strategies towards manipulating the transport properties of ion exchange membranes of a fixed chemical composition, which would give the membranes more diverse capabilities compared to the current technologies. Additionally, understanding the fundamentals behind the transport properties is key to designing next generation materials that would meet the needs of these ever-evolving devices.
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95-pm Oligomeric Ruthenium Dye for the Improved Efficiency of Water-Splitting Dye-Sensitized Solar Cells
C. Gray, T. E. Mallouk
Water-splitting dye-sensitized photoelectrochemical cells (WS-DSPECs) utilize high surface area semiconductor electrodes sensitized with a molecular light absorber and catalyst in order to drive photoelectrochemical water oxidation. Electron transfer occurs from the photoexcited dye to the electrode material while holes are laterally transferred across the surface until reaching a water oxidation catalyst. We have synthesized a novel oligomeric ruthenium bipyridine dye that is attached to the electrode through phosphonate groups. The oligomer was designed to mitigate desorption of the dye and increases lateral hole transport. These two effects are demonstrated by electrochemical hole diffusion studies. All of these studies are compared to electrodes sensitized by the traditionally-used molecular ruthenium bipyridine complex, which is essentially a monomeric analogue of the oligomer dye.
96-pm New Polymer-Based Materials for Triboelectric Energy Conversion and Harvesting J. Dhanani, X. Zhao, Z. Ounaies, O. Rashwan
There is an ever-increasing demand for portable electronic devices arising from the advent of wearable electronics, implantable devices and the Internet of Things (IOT). Traditional sources of power for these devices are facing limitations, such as size, weight and frequency constraints. These challenges demand alternative sources of power generation. Triboelectricity is a promising and developing technology that appears to enable an adaptable and passive power source. Triboelectric nanogenerators (TENGs) are competitors to existing technologies such as piezoelectric generators, electromagnetic generators, and electrostatic generators owing to their simplicity, flexibility and ability to harvest small magnitudes of stray mechanical energy, such as human motion or tidal waves. TENGs, functioning on the basic fundamentals of triboelectrification and electrostatic induction, operate in four principal modes: contact/separation, lateral sliding, single electrode, and freestanding. Ongoing research efforts focus on maximizing the electrical output of the TENG; since the output is primarily based on the materials employed in the TENG, there have been several attempts to optimize these materials by means of judicious selection of the right pair of materials, addition of fillers, surface texturing, etc. Polymers serve as the predominant choice for triboelectric materials owing to their superior dielectric properties, lightweight and flexibility. In our current research, our objective is to investigate the effect of material properties, such as the dielectric permittivity, in addition to geometric considerations, such as surface texturing, on the electrical output of a TENG. This objective is being carried out through an integrated experimental and computational approach.
We focus on the contact separation mode, which is comprised of two parallel triboelectric materials that undergo oscillating contact. In order to produce this motion, we have designed and fabricated a crank-slider mechanism, where one plate is stationary while the other one undergoes linear motion (slider) as a result of rotary motion generated by an electric motor (crank). The non-contacting surfaces of the two plates are electroded to harness and measure the electrical signals. Electrical signals in the form of voltage and current are measured across a series of external loads using electrometers and picoammeters. The triboelectric materials currently in consideration include Polydimethylsiloxane (PDMS), Polytetrafluoroethene (PTFE) along with Lead zirconate titanate (PZT) as a filler. On the computational front, COMSOL Multiphysics is used where the
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electrostatics, deformed geometry and electrical circuit modules are being coupled to generate results that can be compared to experiments. A successful representation of the TENG will include material properties, such as dielectric constant and surface charge density and surface textures being depicted through 3D geometries. Tuning of these parameters and different geometries will allow for the prediction of electrical output for varied cases of material combinations and surface treatments, further assisting with validation of experiments and eventually the design of an optimized TENG.
97-pm Synthesis of ZnSe Mn2+ Doped Nanoparticles for Tuning Charge Carrier Lifetimes
K.M. Schlegel, J. Asbury
Colloidal semiconductors nanoparticles have been the focus of much research due to their uniquely tunable electronic properties. However, surface traps result in short carrier diffusion lengths and poor charge extraction efficiencies. Traditionally, the passivation of surface traps has been approached by modifying core-shell architectures. Our research focuses on establishing the role of Mn2+ doping as an alternate method to prolong charge carrier lifetimes. Herein we report the synthesis and characterization by transmission electron microscopy, electron paramagnetic resonance spectroscopy, absorbance spectroscopy, transient absorption spectroscopy, steady state and time resolved photoluminescence spectroscopy of ZnSe Mn2+ doped nanoparticles. This work presented will serve as a foundation for future studies addressing electron transfer to acceptor molecules and catalyst design.
98-pm Achromatic Metalenses with Inversely Designed Random-Shaped Meta-Atoms
X. Zhang, H. Huang, X. Guo, X. Ni
Metalenses, which can focus light like conventional bulky lenses, attracted enormous research interest recently. They are ultrathin, planar, and lightweight, making them easy to be integrated, and therefore have the great potential to replace or complement their conventional bulk counterparts. However, since the metalenses are based on diffractive optics, one of the critical drawbacks is their chromatic aberration. Recently, several studies showed that it is possible to compensate the chromatic aberration using a large set of building blocks – meta-atoms with engineered dispersion, either for circularly polarized or linearly polarized light. However, the designs are all based on regular shapes and are limited by human cognitive capabilities, resulting in a small coverage of the whole physically possible design space. To address this challenge, we developed a method to inversely design the random-shaped meta-atoms to fulfill the phase and phase dispersion requirements for creating achromatic metalenses. The random shapes introduce no bias in selection and increases the variety of the designs. Global optimization method was used to find the best shapes. This efficient optimization-based inverse design saves a lot of time since there is no need to generate the total unit cell library. Different constrains on the shape generation can be applied selectively in order to achieve desired properties such as polarization independence and nanofabrication compatibility. In contrast to the current reported works based on rigorously designed elements to compensate the chromatic aberration, this new kind of achromatic metalenses which are consisting of inversely designed random-shaped elements can cover much larger physically possible design space and achieve better performance. This technique provides an automated and time-saving way to generate the optimum design for achromatic lenses in any desired wavelength ranges. We believe this is the first step to inversely design achromatic metalenses at the device level.
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99-pm Optics Device Fabrication in the Nanofab
C. Eichfeld
The Penn State Nanofabrication Laboratory is fabricating an increasing number of optics devices using their nanofabrication toolset. This poster will highlight the current devices and propose possible new directions. In conjunction with Dr. Randal McEntaffer the Nanofab is considering the formation of an optics center covering a wide range and interest in optics. The objective is to promote and leverage the expertise of the faculty and Nanofab capabilities in the optics arena by promoting interactions of faculty across various colleges and departments. Inquiries may be directed to Dr. Randy McEntaffer and or Dr. Chad Eichfeld.
100-pm Advanced Electroactive Materials and Devices
Q. M. Zhang, Xin Chen, T. Zhang, H. Xi, Q. Zhang, X. Jian, Q. Yang
We present in this poster several recent advances in the Laboratory for Electroactive Materials and Devices in developing multifunctional polymer and nanocomposites and their energy conversion, energy storage, and biomedical sensing devices: (i) The giant electrocaloric effect (ECE), i.e., large temperature and entropy changes induced electrically in ferroelectric materials and advanced EC cooling devices. (ii) Unconventional high temperature polymer nanocomposites for energy storage with high dielectric breakdown and charge/discharge efficiency over broad temperature. (iii) Ultra-high sensitivity piezo-magnetic sensor array systems for biomedical imaging.
101-pm Synthesis of 2D Semiconductors for Sensing and Electronics
R. Torsi, A. Kozhakhmetov, B. Jariwala, N. Simonson, R. Zhao, J. Robinson
The family of 2D atomically thin crystals has been steadily expanding ever since the isolation of graphene in 2004. Within this family, 2D semiconductors have received particular attention due to the wide variety of band gaps that span from far infrared and ultraviolet and relatively high carrier mobilities. More excitingly, 2D semiconductors have displayed electronic properties tunability via substrate engineering, layer number modulation, strain, and doping. This property manipulation exhibited in these systems, make 2D semiconductors an intriguing platform for sensing and electronics application. The J.A. Robinson Research Group at Penn State has been at the forefront of 2D semiconductors research focusing on the synthesis of transition metal dichalcogenides (TMDs) such as MoS2, WSe2, and MoTe2 via chemical vapor deposition (CVD). By careful control of critical CVD process parameters such as reactor pressure, growth temperature, and carrier gas flow we were able to achieve the growth of vertically aligned MoS2 nanoflowers on a variety of substrates. The large number of active edge sites present in the nanoflower microstructure vastly improve the hydrogen evolution reactions (HERs) capabilities of the material for future sustainable energy applications. We have also investigated the copper diffusion barrier qualities of Nb-incorporated MoS2 grown via MOCVD at back end of line (BEOL) compatible temperatures for next-generation interconnect technology. By introducing NbCl5 powder into the growth chamber a NbOx layer forms on the substrate before MoS2 nucleation which enhances MoS2 grain size and vastly improves its copper diffusion blocking performance even at low barrier thicknesses (~2.8nm). Furthermore, we have demonstrated the scalable Re- doping of WSe2 via a novel synthesis process that employs Re2 (CO)10 as the metal organic dopant source. By careful manipulation of Re2 (CO)10 flow during WSe2 MOCVD growth, the dopant concentrations can be tuned down to the <0.1% range which is unprecedented in the field of TMD doping. Remarkably, this doping control was also observed at low growth temperatures (450°C) which opens opportunities for application of the 2D
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film in BEOL structures. Lastly, via the addition of sulfur flow in the MOCVD synthesis of MoTe2, the synthesis of the less stable semiconducting 2H-phase was achieved. Although the more stable metallic 1T’ phase was still present in the film, this novel synthesis technique has the potential of unlocking the potential for MoTe2 utilization in low energy consumption phase change memory technology.
102-pm Functional Electroceramics
S Troiler-McKinstry, K. Coleman, D. Wang, C. Cheng, L. Jacques, N. Bishop, T. Liu, J.I. Yang, W. Zhu, S. Shetty, B. Akgun, S. Gupta, M. Hahn, T. Peters, P. Tipsawat, S. Aman, D. Hama, S.W. Ko, D. Koh, V. Kovocova, B. Jones, M. Ritter, B. Gibble, D. Moses, K. Sterling
The Trolier-McKinstry group primarily focuses on the development of dielectric and piezoelectric thin films and composites. Advancement of novel processing techniques and the integration of new materials into smart devices may have significant impact in energy harvesters, ultrasonic transducers, sensors, actuators, and for probing the fundamental mechanisms that control the magnitude of the achievable property limits. Lead zirconate titanate (PZT) has been industrialized in an array of applications due to its high piezoelectric coefficients, good coupling, and reasonable temperature stability. A broad array of devices using PZT films has been made on Si, glass, metal foil, and polymer substrates; the group is also exploring fabrication of lead-free piezoelectrics such as bismuth ferrite and sodium potassium niobate. Conventional sintering of piezoelectric thin films requires high temperatures; however, novel fabrication techniques like cold sintering permits lower processing temperatures. Additional work on piezoelectric reliability has investigated how the functionality and properties of the thin films change under varying mechanical, chemical, and thermal environments with a wide range of electrical loads.
103-pm Epitaxial Growth and Morphology Change of Organic Single-crystalline Heterojunctions on Graphene
Z. Guo, A.L. Briseno, S.C.B. Mannsfeld, A. Baca, E.D. Gomez
We report on the epitaxial growth of single crystalline p-n junctions on a graphene substrate using two organic small molecules: Zinc phthalocyanine (ZnPc) as a donor-type material (p-type), and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) as an acceptor-type material (n-type). The morphology of a p-n junction was demonstrated to vary upon deposition sequence, as an epitaxial PTCDA layer grown on top of ZnPc exhibits nanopillar structure, while a ZnPc layer grown on PTCDA shows a bulk, island-like structure. The epitaxy mechanism follows “point-on-line” rule where organic crystalline layers grow on top of each other by sensing and registering the spacings and periodicities of the lattice plane it grows on, which leads to different molecular packing motifs and resultant different morphologies. Preliminary Grazing incidence wide angle X-ray scattering (GIWAX) and high resolution TEM studies showed both types of p-n junctions are highly orientated and molecules have preferred face-on packing motif. Together with the conducting AFM results which showed diode characteristics of p-n junctions under the dark environment, it is believed graphene-templated p-n junctions can be suitable for use in the organic photovoltaics (OPV). From this study, we can better understand the packing/orientation of molecules in vertical aligned nanostructures and how the geometrical arrangement, and resultant different morphology, will affect the electronic properties and photovoltaic device design.
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104-pm 3D Printing of PDMS Microfluidic Device by Nanoclay-reinforced Pluronic F-127 as Sacrificial Material
K. Zhou, B. Ayan, I.T. Ozbolat
3D printing technology enables the fabrication of complex microfluidic devices and is receiving increasing attention in biochemical and clinical applications. 3D printing of a mold following by dissolution of the sacrificial ink is an attractive approach that allows for rapid prototyping, low cost, possibility of complex channel architectures and simplicity of manufacture.
In this work, Pluronic-nanoclay composite ink has been used as a sacrificial gel in order to create 3D microfluidic channels in PDMS devices. 0, 4, 8, 12 and 16 w/v% nanoclay were added into 30 w/v% Pluronic F-127 aqueous solution respectively to obtain printing inks. The effect of nanoclay on inks rheology and printability has been researched. Then, 30 w/v% Pluronic F-127 aqueous solution with 12 w/v% nanoclay (called P30-N12 ink) was used as printing ink to fabricate complex microfluidic device.
Our study demonstrated that Pluronic-nanoclay composite ink possessed a shear-thinning behavior and the gel strength and the yielding properties were significantly influenced by the concentration of nanaclay. The ink has better printability with an increase of nanoclay concentration. P30-N12 and P30-N16 inks can be good candidates to maintain good printability and shape fidelity in 3D printing of overhanging or unsupported structures. The obtained PDMS microfluidic device exhibits uniform diameter and approximately circular in cross-section.
Overall, we here present an approach in fabrication of PDMS devices with 3D complex fluid channels, which may have great potential in a myriad of applications from cancer treatments to infectious disease diagnostics to artificial organs.
105-pm Scale-up of Moringa-coated Filters for Water Treatment by Varying Packing Fractions of Sustainable Materials
D. Velegol
This poster will show the scale-up of a moringa-coated sand filter using a mixture of sand sizes appropriate in the developing world. The hypothesis is that we can mix sustainable materials of different sizes (e.g. sand, silt and crushed glass), to decrease the porosity of the filter and therefore increase pathogen capture. These seeds of the Moringa oleifera tree contain an antimicrobial cationic protein (MOCP) that will preferentially adhere to negatively charged sand (or any negatively charged surface), reversing the charge of the sand from negative (same as microorganisms) to positive. The resulting functionalized sand material, or f-sand, attracts and removes microbes from water. Our lab has recently shown that f-sand filters made from 106 micron glass beads remove >99.99999% of E. coli (8-log) and >99.9999% of the MS2 virus (7log). However, this sand size is small and readily available where this technology is needed most. Models and experiments confirm that increasing the size of the sand results in less removal. This work shows that sufficient removal can indeed be obtained using a mixture of 106 micron sand and both crushed glass and sieved sand based.
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106-pm Development of Clay-based Mixture Design for 3D Printing of Tiny Homes
A. Al-Qenaee, A. Memari, J. Duarte, S. Nazarian, A. Radlinska, M. Hojati
3D printing of cementitious material can provide an affordable, sustainable and optimized approach and opportunity for construction of homes in a short period of time, without compromising quality, craftsmanship, or customization. 3D printing of concrete structures results in higher precision, safer working conditions, faster construction speed, and lower costs of construction (avoiding the costs associated with formwork and labor). While most of the current R&D efforts in this field are focused on cement based concrete printing, this research has focused on design and development of a sustainable clay-based mixture design that mainly includes clay, sand, straw, lime, and water. This allows truly affordable home construction system for underprivileged areas and societies. The goal of the project is to design a mixture that will be printable for a tiny house construction. The specific objective of the current project is to demonstrate printability of such a mixture design. This presentation will provide a review of the current state of the art in clay-based traditional construction such as cob and adobe homes, and then transitioning to 3D printing construction. The presentation will describe typical mixture designs for such construction and describe the challenges in going from lab scale research to actual tiny home and small home construction. In particular, because of the low tensile capacity of clay-based mixture even with straw reinforcement, the presentation will illustrate how curves shapes can reduce the tensile stresses and how gravity loads can be resisted through compressive stresses. Typical conceptual designs based on domed shape homes will be presented.
107-pm Cross-Species Inspired Patterned Slippery Surfaces for Fog Harvesting L. Wang, J. Wang, R. Wang, T.-S. Wong
Developing a technology that could efficiently harvest fresh water from fog is essential to alleviate the global water crisis, especially in the coastal and arid regions. In nature, Namib Desert beetles have developed hydrophobic/hydrophilic patterned surfaces to capture fog efficiently as drinking water to thrive in the desert. A variety of methods have been proposed to fabricate such wettability patterned materials. However, these surfaces are still plagued with problems in rapidly shedding off the collected water. Nepenthes pitcher plant, on the other hand, has evolved micro-structured surface which becomes super-slippery when infused with a liquid lubricant within their porous structures. Recent studies have shown that synthetic slippery surfaces are advantages over other conventional surfaces in droplet shedding. In this study, we present a cross-species inspired design approach by incorporating both of the tactics used by desert beetle and pitcher plant to fabricate a hybrid patterned slippery surface. We have shown that the cross-species inspired surface outperforms the conventional fog harvesting surfaces significantly.
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108-pm Non-symmetric Pinning of Topological Defects in a Living Nematic N. F.Morales, A. Sokolov, M.M. Genkin, I.S. Aranson
A realization of active nematics has been conceived by combining swimming bacteria and a lyo-tropic liquid crystal. The complex dynamics of such active material arises from the non-trivial in-terplay between hydrodynamic flows and elastic forces: while bacteria are guided by the local di-rector field, the local alignment of the liquid crystal is disturbed by the swimming bacteria. At high bacterial concentration, the domination of bacterial activity leads to creation of motile topo-logical defects, which alter bacterial distribution. Here, we experimentally explore the possibility of controlling and pinning of emerged topological defects by artificially created microstructures. The microstructures were printed using a state-of-art multiphoton 3D lithography system and mimicked the shape of defects cores. While -1/2 defects may be easily pinned to the created pattern, +1/2 defects remain motile. Due to an attraction between opposite defects, positive defects remain in the vicinity of pined negative defects, significantly diminishing their diffusivity.
109-pm Ultra-Low Power Biomimetic Sensors
Das Research Group at Penn State Authors: A. Dodda, S. Das, A. Sebastian, A. Oberoi, D.S. Schulman, D.E. Buzzell, S. Abstract
With the steady decline in complexity, energy, and size scaling in the industry of electronic device manufacturing, there has been a need for device innovation at the fundamental level. Materials innovation when applied with effective and smart strategies can help overcome these scaling barriers. Nature, for instance, has evolved through such rigorous evolutional upgrades and downgrades and the time-tested strategies from nature can help solve complicated problems. Our research focuses on building sensors on 2D materials that mimic certain aspects from nature making the electronics smarter and more energy efficient. In order to better understand the low-power, probabilistic method of biological sensing, we build sensors using the bottom-up approach i.e. starting from understanding how a neuron fires when it senses a change in its environment. Human brain comprising of billions of these neurons consumes extremely low power and yet is able to perform extremely complex computational tasks. Vision sensing capabilities using photodetectors on 2D materials like MoS2 capable of capturing the visible spectrum while operating with ultra-low power (sub-threshold regime of operation) has been achieved. Barn owls, which can detect auditory cues for navigation, even in complete darkness have been explored through a split-gate device structure. Locusts, known for navigating in swarms without collision are being explored where the collision detection is done by a single neuron. Nature has also evolved in order to be able to detect signals even in noisy environments. Noise is often considered as a detriment in information transmission. However, biological and physical experiments in nature have shown that noise can help to enhance the signal, with the phenomenon termed as stochastic resonance. Enhancing a signal with the help of noise can prove to be beneficial as it could help us implement sensors and detect signals in the presence of noise, which could not otherwise be detected. Probabilistic computing, another feature used by neurons for learning and firing, helps decrease the number of hidden layers in the hardware-run neural network to compute low-error outputs. Mimicking the neuronal methodologies onto two dimensional electronic devices can help make on-chip, real-time learning, possible. Inspired by neurobiological architecture evolved through the course of lifetimes, nature can help make better and smarter sensors that can work in an ultra-low power regime making electronic devices that can evolve with changing environments.
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110-pm Fabrication of a Vascularized Tumor Microenvironment for Immunotherapy
M. Dey, E. Karhan, C. Tastan, D. Unutmaz, I.T. Ozbolat
Despite the plethora of research and advances in treatment, cancer remains one of the leading causes of mortality worldwide. Immunotherapy for cancer treatment is an emerging field of research but lacks a proper understanding of cancer-immune cell interaction which is vital to tumor progression. To better understand the underlying mechanisms a three-dimensional (3D) organoid based vascularized breast tumor microenvironment has been fabricated using a highly metastatic breast cancer cell line, MDA-MB-231. This 3D tumor model recapitulates the dynamic immune-cancer microenvironment which traditional two-dimensional cell culture models or even animal models cannot. As tumor angiogenesis is a definitive hallmark of cancer, pre-vascularized micro-tumors encapsulated in fibrin hydrogel exhibited not only robust vascular network formation around the growing tumor but also enabled contiguous internal vascularization of the tumor itself, mimicking native physiology. Tumor spheroids exhibited extensive capillary sprouting in fibrin which anastomose to form a well-connected capillary network. The presence of a hollow lumen as well as intravasation of cancer cells in these capillaries was confirmed by 3D surface rendered images from two-photon microscopy. Additionally, a novel method was developed using primary human T cells engineered with T cell receptors (TCRs) that can recognize bacterial metabolites in the context of MR1 molecule expressed on the surface of cancer cells, therefore bypassing MHC and antigen requirements. These engineered TCR+ T cells effectively eradicated the 3D-fabricated tumor mass over three days of culture. Thus, this system creates a platform for studying immune-cancer cell interactions, as well as for anti-cancer drug screening therapies for breast cancer in future.
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