Materials Science & Engineering Research Works

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Simplified Reflection Fabry-Perot Method for Determination of Electro-Optic Coefficients of Poled Polymer Thin Films
(MDPI, 2011-08-18) Park, Dong Hun; Luo, Jingdong; Jen, Alex K.-Y.; Herman, Warren N.
We report a simplified reflection mode Fabry-Perot interferometry method for determination of electro-optic (EO) coefficients of poled polymer thin films. Rather than fitting the detailed shape of the Fabry-Perot resonance curve, our simplification involves a technique to experimentally determine the voltage-induced shift in the angular position of the resonance minimum. Rigorous analysis based on optical properties of individual layers of the multilayer structure is not necessary in the data analysis. Although angle scans are involved, the experimental setup does not require a θ-2θ rotation stage and the simplified analysis is an advantage for polymer synthetic efforts requiring quick and reliable screening of new materials. Numerical and experimental results show that our proposed method can determine EO coefficients to within an error of ∼8% if poled values for the refractive indices are used.
Decomposition Mechanisms and Kinetics of Novel Energetic Molecules BNFF-1 and ANFF-1: Quantum-Chemical Modeling
(MDPI, 2013-07-18) Tsyshevsky, Roman V.; Kuklja, Maija M.
Decomposition mechanisms, activation barriers, Arrhenius parameters, and reaction kinetics of the novel explosive compounds, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1), and 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) were explored by means of density functional theory with a range of functionals combined with variational transition state theory. BNFF-1 and ANFF-1 were recently suggested to be good candidates for insensitive high energy density materials. Our modeling reveals that the decomposition initiation in both BNFF-1 and ANFF-1 molecules is triggered by ring cleavage reactions while the further process is defined by a competition between two major pathways, the fast C-NO2 homolysis and slow nitro-nitrite isomerization releasing NO. We discuss insights on design of new energetic materials with targeted properties gained from our modeling.
Topography of Photochemical Initiation in Molecular Materials
(MDPI, 2013-11-15) Aluker, Edward D.; Krechetov, Alexander G.; Mitrofanov, Anatoly Y.; Zverev, Anton S.; Kuklja, Maija M.
We propose a fluctuation model of the photochemical initiation of an explosive chain reaction in energetic materials. In accordance with the developed model, density fluctuations of photo-excited molecules serve as reaction nucleation sites due to the stochastic character of interactions between photons and energetic molecules. A further development of the reaction is determined by a competition of two processes. The first process is growth in size of the isolated reaction cell, leading to a micro-explosion and release of the material from the cell towards the sample surface. The second process is the overlap of reaction cells due to an increase in their size, leading to the formation of a continuous reaction zone and culminating in a macro-explosion, i.e., explosion of the entire area, covering a large part of the volume of the sample. Within the proposed analytical model, we derived expressions of the explosion probability and the duration of the induction period as a function of the initiation energy (exposure). An experimental verification of the model was performed by exploring the initiation of pentaerythritol tetranitrate (PETN) with the first harmonic of YAG: Nd laser excitation (1,064 nm, 10 ns), which has confirmed the adequacy of the model. This validation allowed us to make a few quantitative assessments and predictions. For example, there must be a few dozen optically excited molecules produced by the initial fluctuations for the explosive decomposition reaction to occur and the life-time of an isolated cell before the micro-explosion must be of the order of microseconds.
Directed Kinetic Self-Assembly of Mounds on Patterned GaAs (001): Tunable Arrangement, Pattern Amplification and Self-Limiting Growth
(MDPI, 2014-05-12) Lin, Chuan-Fu; Kan, Hung-Chih; Kanakaraju, Subramaniam; Richardson, Christopher; Phaneuf, Raymond
We present results demonstrating directed self-assembly of nanometer-scale mounds during molecular beam epitaxial growth on patterned GaAs (001) surfaces. The mound arrangement is tunable via the growth temperature, with an inverse spacing or spatial frequency which can exceed that of the features of the template. We find that the range of film thickness over which particular mound arrangements persist is finite, due to an evolution of the shape of the mounds which causes their growth to self-limit. A difference in the film thickness at which mounds at different sites self-limit provides a means by which different arrangements can be produced.
3-(4-Amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole
(MDPI, 2014-05-22) Pagoria, Philip; Zhang, Maoxi; Racoveanu, Ana; DeHope, Alan; Tsyshevsky, Roman V.; Kuklja, Maija M.
The title compound 3-(4-amino-1,2,5-oxadiazol-3-yl)-4-(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (ANFF-1) was synthesized by: (1) by reaction of 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BNFF-1) with gaseous ammonia in toluene and (2) by partial oxidation of 3,4-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole (BAFF-1) with 35% H2O2 in concentrated H2SO4.
Effect of Extended Extinction from Gold Nanopillar Arrays on the Absorbance Spectrum of a Bulk Heterojunction Organic Solar Cell
(MDPI, 2015-02-18) Tsai, Shu-Ju; Ballarotto, Mihaela; Kan, Hung-Chih; Phaneuf, Raymond J.
We report on the effects of enhanced absorption/scattering from arrays of Au nanopillars of varied size and spacing on the spectral response of a P3HT:PCBM bulk heterojunction solar cell. Nanopillar array-patterned devices do show increased optical extinction within a narrow range of wavelengths compared to control samples without such arrays. The measured external quantum efficiency and calculated absorbance, however, both show a decrease near the corresponding wavelengths. Numerical simulations indicate that for relatively narrow nanopillars, the increased optical extinction is dominated by absorption within the nanopillars, rather than scattering, and is likely dissipated by Joule heating.
Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials
(MDPI, 2016-02-19) Tsyshevsky, Roman V.; Sharia, Onise; Kuklja, Maija M.
This review presents a concept, which assumes that thermal decomposition processes play a major role in defining the sensitivity of organic energetic materials to detonation initiation. As a science and engineering community we are still far away from having a comprehensive molecular detonation initiation theory in a widely agreed upon form. However, recent advances in experimental and theoretical methods allow for a constructive and rigorous approach to design and test the theory or at least some of its fundamental building blocks. In this review, we analyzed a set of select experimental and theoretical articles, which were augmented by our own first principles modeling and simulations, to reveal new trends in energetic materials and to refine known existing correlations between their structures, properties, and functions. Our consideration is intentionally limited to the processes of thermally stimulated chemical reactions at the earliest stage of decomposition of molecules and materials containing defects.
Photochemistry of the α-Al2O3-PETN Interface
(MDPI, 2016-02-29) Tsyshevsky, Roman V.; Zverev, Anton; Mitrofanov, Anatoly; Rashkeev, Sergey N.; Kuklja, Maija M.
Optical absorption measurements are combined with electronic structure calculations to explore photochemistry of an α-Al2O3-PETN interface formed by a nitroester (pentaerythritol tetranitrate, PETN, C5H8N4O12) and a wide band gap aluminum oxide (α-Al2O3) substrate. The first principles modeling is used to deconstruct and interpret the α-Al2O3-PETN absorption spectrum that has distinct peaks attributed to surface F0-centers and surface—PETN transitions. We predict the low energy α-Al2O3 F0-center—PETN transition, producing the excited triplet state, and α-Al2O3 F0-center—PETN charge transfer, generating the PETN anion radical. This implies that irradiation by commonly used lasers can easily initiate photodecomposition of both excited and charged PETN at the interface. The feasible mechanism of the photodecomposition is proposed.
A Review of Metastable Beta Titanium Alloys
(MDPI, 2018-06-30) Kolli, R. Prakash; Devaraj, Arun
In this article, we provide a broad and extensive review of beta titanium alloys. Beta titanium alloys are an important class of alloys that have found use in demanding applications such as aircraft structures and engines, and orthopedic and orthodontic implants. Their high strength, good corrosion resistance, excellent biocompatibility, and ease of fabrication provide significant advantages compared to other high performance alloys. The body-centered cubic (bcc) β-phase is metastable at temperatures below the beta transus temperature, providing these alloys with a wide range of microstructures and mechanical properties through processing and heat treatment. One attribute important for biomedical applications is the ability to adjust the modulus of elasticity through alloying and altering phase volume fractions. Furthermore, since these alloys are metastable, they experience stress-induced transformations in response to deformation. The attributes of these alloys make them the subject of many recent studies. In addition, researchers are pursuing development of new metastable and near-beta Ti alloys for advanced applications. In this article, we review several important topics of these alloys including phase stability, development history, thermo-mechanical processing and heat treatment, and stress-induced transformations. In addition, we address recent developments in new alloys, phase stability, superelasticity, and additive manufacturing.
Effect of Irradiation and Detection of Long-Lived Polyenyl Radicals in Highly Crystalline Ultra-High Molar Mass Polyethylene (UHMMPE) Fibers
(MDPI, 2019-05-27) Forster, Amanda L.; Tsinas, Zois; Al-Sheikhly, Mohamad
To improve properties such as thermal conductivity, low temperature thermal strain, and creep resistance of ultra-high molar mass polyethylene (UHMMPE) fibers, several researchers have previously undertaken efforts to crosslink these fibers using radiation. Ionizing radiation is commonly used to crosslink bulk UHMMPE in other applications, such as artificial joints. However, UHMMPE fibers differ from bulk UHMMPE in that they have a higher crystallinity (approximately 85% to 90%) and are very highly oriented during manufacturing in which the fibers are stretched 50 to 100 times their original length. Thus, the amorphous fraction of the UHMMPE fibers is also highly ordered. Several experiments were conducted to crosslink the UHMMPE fibers using both low dose rate (gamma) and high dose rate (electron beam) irradiation, all in the absence of oxygen. In all cases, the tensile strength of the fiber was greatly reduced by the irradiation. The oxidation index was also measured for the irradiated samples, and oxidation was not found to play a major role in the reduction of tensile strength in the fibers after irradiation. While this work did not achieve the desired result of improving the mechanical properties of the UHMMPE fiber, a significant result was found. The electron paramagnetic resonance (EPR) spectrum of the UHMMPE fibers was measured shortly after irradiation, and a mixture of allyl and alkyl radicals were detected. The irradiated samples were stored in dark ambient conditions for at least six years, then reexamined using EPR for free radical characterization. Surprisingly, the gamma-irradiated samples showed clear evidence of long-lived polyenyl radicals present in the material. Free radicals are very reactive species that will typically migrate to the surface of the crystalline domain and decay in a relatively short time through various reactions in the amorphous regions. It is hypothesized herein that due to the high crystallinity and large anisotropy of the highly drawn UHMMPE fiber, the polyenyl radicals were trapped in the crystal phase and were unable to migrate and decay. An experiment was performed to test this hypothesis, by which samples of the irradiated fibers were heated to temperatures above first the alpha relaxation and then melting point of polyethylene, and EPR measurements were taken. Results showed that the polyenyl radical signal persisted below the Tm, but was rapidly eliminated upon melting of the crystals. These experiments support the hypothesis that the long-lived polyenyl radicals are trapped in the crystalline region of the polyethylene fibers.
Cellulose Nanocomposites of Cellulose Nanofibers and Molecular Coils
(MDPI, 2021-07-30) Henderson, Doug; Zhang, Xin; Mao, Yimin; Hu, Liangbing; Briber, Robert M.; Wang, Howard
All-cellulose nanocomposites have been produced from cellulose nanofiber (CNF) suspensions and molecular coil solutions. Morphology and small-angle neutron scattering studies show the exfoliation and dispersion of CNFs in aqueous suspensions. Cellulose solutions in mixtures of ionic liquid and organic solvents were homogeneously mixed with CNF suspensions and subsequently dried to yield cellulose composites comprising CNF and amorphous cellulose over the entire composition range. Tensile tests show that stiffness and strength quantities of cellulose nanocomposites are the highest value at ca. 20% amorphous cellulose, while their fracture strain and toughness are the lowest. The inclusion of amorphous cellulose in cellulose nanocomposites alters their water uptake capacity, as measured in the ratio of the absorbed water to the cellulose mass, reducing from 37 for the neat CNF to less than 1 for a composite containing 35% or more amorphous cellulose. This study offers new insights into the design and production of all-cellulose nanocomposites.
On the Mechanism of Electron Beam Radiation-Induced Modification of Poly(lactic acid) for Applications in Biodegradable Food Packaging
(MDPI, 2022-02-10) Grosvenor, Eleanor C.; Hughes, Justin C.; Stanfield, Cade W.; Blanchard, Robert L.; Fox, Andrea C.; Mihok, Olivia L.; Lee, Kristen; Brodsky, Jonathan R.; Hoy, Ann; Uniyal, Ananya; Whitaker, Sydney M.; Acha, Chris; Gibson, Kalina; Ding, Lilly; Lewis, Catherine A.; González López, Lorelis; Wentz, Charlotte M.; Sita, Lawrence R.; Al-Sheikhly, Mohamad
Poly(lactic acid) (PLA) is a biodegradable polymer used for food packaging. The effects of electron beam radiation on the chemical and physical properties of amorphous PLA were studied. In this study, amorphous, racemic PLA was irradiated at doses of 5, 10, 15, and 20 kGy in the absence of oxygen. Utilizing electron paramagnetic resonance spectrometry, it was found that alkoxyl radicals are initially formed as a result of C-O-C bond scissions on the backbone of the PLA. The dominant radiation mechanism was determined to be H-abstraction by alkoxyl radicals to form C-centered radicals. The C-centered radicals undergo a subsequent peroxidation reaction with oxygen. The gel permeation chromatography (GPC) results indicate reduction in polymer molecular mass. The differential scanning calorimetry and X-ray diffraction results showed a subtle increase in crystallinity of the irradiated PLA. Water vapor transmission rates were unaffected by irradiation. In conclusion, these results support that irradiated PLA is a suitable material for applications in irradiation of food packaging, including food sterilization and biodegradation.
Challenges of Overcoming Defects in Wide Bandgap Semiconductor Power Electronics
(MDPI, 2021-12-22) Setera, Brett; Christou, Aristos
The role of crystal defects in wide bandgap semiconductors and dielectrics under extreme environments (high temperature, high electric and magnetic fields, intense radiation, and mechanical stresses) found in power electronics is reviewed. Understanding defects requires real-time in situ material characterization during material synthesis and when the material is subjected to extreme environmental stress. Wide bandgap semiconductor devices are reviewed from the point of view of the role of defects and their impact on performance. It is shown that the reduction of defects represents a fundamental breakthrough that will enable wide bandgap (WBG) semiconductors to reach full potential. The main emphasis of the present review is to understand defect dynamics in WBG semiconductor bulk and at interfaces during the material synthesis and when subjected to extreme environments. High-brightness X-rays from synchrotron sources and advanced electron microscopy techniques are used for atomic-level material probing to understand and optimize the genesis and movement of crystal defects during material synthesis and extreme environmental stress. Strongly linked multi-scale modeling provides a deeper understanding of defect formation and defect dynamics in extreme environments.
Nanoscale Bending Dynamics in Mixed-Chain Lipid Membranes
(MDPI, 2023-01-09) Kelley, Elizabeth G.; Frewein, Moritz P. K.; Czakkel, Orsolya; Nagao, Michihiro
Lipids that have two tails of different lengths are found throughout biomembranes in nature, yet the effects of this asymmetry on the membrane properties are not well understood, especially when it comes to the membrane dynamics. Here we study the nanoscale bending fluctuations in model mixed-chain 14:0–18:0 PC (MSPC) and 18:0–14:0 PC (SMPC) lipid bilayers using neutron spin echo (NSE) spectroscopy. We find that despite the partial interdigitation that is known to persist in the fluid phase of these membranes, the collective fluctuations are enhanced on timescales of tens of nanoseconds, and the chain-asymmetric lipid bilayers are softer than an analogous chain-symmetric lipid bilayer with the same average number of carbons in the acyl tails, di-16:0 PC (DPPC). Quantitative comparison of the NSE results suggests that the enhanced bending fluctuations at the nanosecond timescales are consistent with experimental and computational studies that showed the compressibility moduli of chain-asymmetric lipid membranes are 20% to 40% lower than chain-symmetric lipid membranes. These studies add to growing evidence that the partial interdigitation in mixed-chain lipid membranes is highly dynamic in the fluid phase and impacts membrane dynamic processes from the molecular to mesoscopic length scales without significantly changing the bilayer thickness or area per lipid.
Direct and Rapid High-Temperature Upcycling of Degraded Graphite
(Wiley, 2023-06-27) Li, Tangyuan; Tao, Lei; Xu, Lin; Meng, Taotao; Clifford, Bryson Callie; Li, Shuke; Zhao, Xinpeng; Rao, Jiancun; Lin, Feng; Hu, Liangbing
Recycling the degraded graphite is becoming increasingly important, which can helped conserve natural resources, reduce waste, and provide economic and environmental benefits. However, current regeneration methods usually suffer from the use of harmful chemicals, high energy and time consumption, and poor scalability. Herein, we report a continuously high-temperature heating (≈2000 K) process to directly and rapidly upcycle degraded graphite containing impurities. A sloped carbon heater is designed to provide the continuous heating source, which enables robust control over the temperature profile, eliminating thermal barrier for heat transfer compared to conventional furnace heating. The upcycling process can be completed within 0.1 s when the degraded graphite rolls down the sloped heater, allowing us to produce the upcycled graphite on a large scale. High-temperature heating removes impurities and enhances the graphitization degree and (002) interlayer spacing, making the upcycled graphite more suitable for lithium intercalation and deintercalation. The assembled upcycled graphite||Li cell displays a high reversible capacity of ≈320 mAh g−1 at 1 C with a capacity retention of 96% after 500 cycles, comparable to current state-of-the-art recycled graphite. The method is a chemical-free, rapid, and scalable way to upcycle degraded graphite, and is adaptable to recycle other electrode materials.
Frustration in Super-Ionic Conductors Unraveled by the Density of Atomistic States
(Wiley, 2023-02-07) Wang, Shuo; Liu, Yunsheng; Mo, Yifei
The frustration in super-ionic conductors enables their exceptionally high ionic conductivities, which are desired for many technological applications including batteries and fuel cells. A key challenge in the study of frustration is the difficulties in analyzing a large number of disordered atomistic configurations. Using lithium super-ionic conductors as model systems, we propose and demonstrate the density of atomistic states (DOAS) analytics to quantitatively characterize the onset and degree of disordering, reveal the energetics of local disorder, and elucidate how the frustration enhances diffusion through the broadening and overlapping of the energy levels of atomistic states. Furthermore, material design strategies aided by the DOAS are devised and demonstrated for new super-ionic conductors. The DOAS is generally applicable analytics for unraveling fundamental mechanisms in complex atomistic systems and guiding material design.
Nanocellulose-Carboxymethylcellulose Electrolyte for Stable, High-Rate Zinc-Ion Batteries
(Wiley, 2023-04-02) Xu, Lin; Meng, Taotao; Zheng, Xueying; Li, Tangyuan; Brozena, Alexandra H.; Mao, Yimin; Zhang, Qian; Clifford, Bryson Callie; Rao, Jiancun; Hu, Liangbing
Aqueous Zn ion batteries (ZIBs) are one of the most promising battery chemistries for grid-scale renewable energy storage. However, their application is limited by issues such as Zn dendrite formation and undesirable side reactions that can occur in the presence of excess free water molecules and ions. In this study, a nanocellulose-carboxymethylcellulose (CMC) hydrogel electrolyte is demonstrated that features stable cycling performance and high Zn2+ conductivity (26 mS cm−1), which is attributed to the material's strong mechanical strength (≈70 MPa) and water-bonding ability. With this electrolyte, the Zn-metal anode shows exceptional cycling stability at an ultra-high rate, with the ability to sustain a current density as high as 80 mA cm−2 for more than 3500 cycles and a cumulative capacity of 17.6 Ah cm−2 (40 mA cm−2). Additionally, side reactions, such as hydrogen evolution and surface passivation, are substantially reduced due to the strong water-bonding capacity of the CMC. Full Zn||MnO2 batteries fabricated with this electrolyte demonstrate excellent high-rate performance and long-term cycling stability (>500 cycles at 8C). These results suggest the cellulose-CMC electrolyte as a promising low-cost, easy-to-fabricate, and sustainable aqueous-based electrolyte for ZIBs with excellent electrochemical performance that can help pave the way toward grid-scale energy storage for renewable energy sources.
A semi-supervised deep-learning approach for automatic crystal structure classification
(Wiley, 2022) Lolla, Satvik; Liang, Haotang; Kusne, A. Gilad; Takeuchi, Ichiro; Ratcliff, William
The structural solution problem can be a daunting and time-consuming task. Especially in the presence of impurity phases, current methods, such as indexing, become more unstable. In this work, the novel approach of semi-supervised learning is applied towards the problem of identifying the Bravais lattice and the space group of inorganic crystals. The reported semi-supervised generative deep-learning model can train on both labeled data, i.e. diffraction patterns with the associated crystal structure, and unlabeled data, i.e. diffraction patterns that lack this information. This approach allows the models to take advantage of the troves of unlabeled data that current supervised learning approaches cannot, which should result in models that can more accurately generalize to real data. In this work, powder diffraction patterns are classified into all 14 Bravais lattices and 144 space groups (the number is limited due to sparse coverage in crystal structure databases), which covers more crystal classes than other studies. The reported models also outperform current deep-learning approaches for both space group and Bravais lattice classification using fewer training data.
Tuning the temperature range of superelastic Ni-Ti alloys for elastocaloric cooling via thermal processing
(Institute of Physics, 2023-04-28) Yamazaki, Takahiro; Montagnoli, Andre L.; Young, Marcus L.; Takeuchi, Ichiro
Caloric cooling enlisting solid-state refrigerants is potentially a promising eco-friendly alternative to conventional cooling based on vapor compression. The most common refrigerant materials for elastocaloric cooling to date are Ni-Ti based superelastic shape memory alloys. Here, we have explored tuning the operation temperature range of Ni50.8Ti49.2 for elastocaloric cooling. In particular, we have studied the effect of thermal treatments (a.k.a. aging) on the transformation temperature, superelasticity, and elastocaloric effects of Ni50.8Ti49.2 shape memory alloy tubes. The isothermal compressive test revealed that the residual strain of thermally-treated Ni-Ti tubes at room temperature approaches zero as aging time is increased. Short-time aging treatment at 400 ◦C resulted in good superelasticity and elastocaloric cooling performance with a large tunable austenite finish (Af) temperature range of 24.7 ◦C, as determined from the Af temperature of the samples that were aged 5–120 min. The main reason of the property change is the formation of a different amount of Ni4Ti3 precipitates in the NiTi matrix. Our findings show that it is possible to tailor the Af temperature range for development of cascade elastocaloric cooling systems by thermally treating a starting single composition Ni-Ti alloy.
Remote Chemical Sensing by SERS with Self-Assembly Plasmonic Nanoparticle Arrays on a Fiber
(Frontiers Media, 2022-01-25) Zhang, Xin; Zhang, Kunyi; von Bredow, Hasso; Metting, Christopher; Atanasoff, George; Briber, Robert M.; Rabin, Oded
An optical fiber was modified at the tip with a self-assembled plasmonic metamaterial that acts as a miniature surface-enhanced Raman spectroscopy (SERS) substrate. This optical fiber-based device co-localizes the laser probe signal and the chemical analyte at a distance remote from the spectrometer, and returns the scattered light signal to the spectrometer for analysis. Remote SERS chemical detection is possible in liquids and in dried samples. Under laboratory conditions, the analyte SERS signal can be separated from the background signal of the fiber itself and the solvent. An enhancement factor greater than 35,000 is achieved with a monolayer of the SERS marker 4-aminothiophenol.

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