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.
Topological frustration of artificial spin ice supplemental movies
(2015) Cumings, John; Marsh, Thomas; Drisko, Jasper
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.
Topological frustration of artificial spin ice
(Nature Publishing Group, 2017-01-13) Drisko, Jasper; Marsh, Thomas; Cumings, John
Frustrated systems, typically characterized by competing interactions that cannot all be simultaneously satisfied, display rich behaviours not found elsewhere in nature. Artificial spin ice takes a materials-by-design approach to studying frustration, where lithographically patterned bar magnets mimic the frustrated interactions in real materials but are also amenable to direct characterization. Here, we introduce controlled topological defects into square artificial spin ice lattices in the form of lattice edge dislocations and directly observe the resulting spin configurations. We find the presence of a topological defect produces extended frustration within the system caused by a domain wall with indeterminate configuration. Away from the dislocation, the magnets are locally unfrustrated, but frustration of the lattice persists due to its topology. Our results demonstrate the non-trivial nature of topological defects in a new context, with implications for many real systems in which a typical density of dislocations could fully frustrate a canonically unfrustrated system.
Strategies Based on Nitride Materials Chemistry to Stabilize Li Metal Anode
(John Wiley & Sons Ltd., 2017-03-03) Zhu, Yizhou; He, Xingfeng; Mo, Yifei
Lithium metal battery is a promising candidate for high-energy-density energy storage. Unfortunately, the strongly reducing nature of lithium metal has been an outstanding challenge causing poor stability and low coulombic efficiency in lithium batteries. For decades, there are significant research efforts to stabilize lithium metal anode. However, such efforts are greatly impeded by the lack of knowledge about lithium-stable materials chemistry. So far, only a few materials are known to be stable against Li metal. To resolve this outstanding challenge, lithium-stable materials have been uncovered out of chemistry across the periodic table using first-principles calculations based on large materials database. It is found that most oxides, sulfides, and halides, commonly studied as protection materials, are reduced by lithium metal due to the reduction of metal cations. It is discovered that nitride anion chemistry exhibits unique stability against Li metal, which is either thermodynamically intrinsic or a result of stable passivation. The results here establish essential guidelines for selecting, designing, and discovering materials for lithium metal protection, and propose multiple novel strategies of using nitride materials and high nitrogen doping to form stable solid-electrolyte-interphase for lithium metal anode, paving the way for high-energy rechargeable lithium batteries.
Statistical variances of diffusional properties from ab initio molecular dynamics simulations
(Nature Publishing Group, 2018-04-03) He, Xingfeng; Zhu, Yizhou; Epstein, Alexander; Mo, Yifei
Ab initio molecular dynamics (AIMD) simulation is widely employed in studying diffusion mechanisms and in quantifying diffusional properties of materials. However, AIMD simulations are often limited to a few hundred atoms and a short, sub-nanosecond physical timescale, which leads to models that include only a limited number of diffusion events. As a result, the diffusional properties obtained from AIMD simulations are often plagued by poor statistics. In this paper, we re-examine the process to estimate diffusivity and ionic conductivity from the AIMD simulations and establish the procedure to minimize the fitting errors. In addition, we propose methods for quantifying the statistical variance of the diffusivity and ionic conductivity from the number of diffusion events observed during the AIMD simulation. Since an adequate number of diffusion events must be sampled, AIMD simulations should be sufficiently long and can only be performed on materials with reasonably fast diffusion. We chart the ranges of materials and physical conditions that can be accessible by AIMD simulations in studying diffusional properties. Our work provides the foundation for quantifying the statistical confidence levels of diffusion results from AIMD simulations and for correctly employing this powerful technique.
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.
Single-digit-micrometer thickness wood speaker
(Springer Nature, 2019-11-08) Gan, Wentao; Chen, Chaoji; Kim, Hyun-Tae; Lin, Zhiwei; Dai, Jiaqi; Dong, Zhihua; Zhou, Zhan; Ping, Weiwei; He, Shuaiming; Xiao, Shaoliang; Yu, Miao; Hu, Liangbing
Thin films of several microns in thickness are ubiquitously used in packaging, electronics, and acoustic sensors. Here we demonstrate that natural wood can be directly converted into an ultrathin film with a record-small thickness of less than 10 μm through partial delignification followed by densification. Benefiting from this aligned and laminated structure, the ultrathin wood film exhibits excellent mechanical properties with a high tensile strength of 342 MPa and a Young’s modulus of 43.6 GPa, respectively. The material’s ultrathin thickness and exceptional mechanical strength enable excellent acoustic properties with a 1.83-times higher resonance frequency and a 1.25-times greater displacement amplitude than a commercial polypropylene diaphragm found in an audio speaker. As a proof-of-concept, we directly use the ultrathin wood film as a diaphragm in a real speaker that can output music. The ultrathin wood film with excellent mechanical property and acoustic performance is a promising candidate for next-generation acoustic speakers.
Unsupervised discovery of solid-state lithium ion conductors
(Springer Nature, 2019-11-20) Zhang, Ying; He, Xingfeng; Chen, Zhiqian; Bai, Qiang; Nolan, Adelaide M.; Roberts, Charles A.; Banerjee, Debasish; Matsunaga, Tomoya; Mo, Yifei; Ling, Chen
Although machine learning has gained great interest in the discovery of functional materials, the advancement of reliable models is impeded by the scarcity of available materials property data. Here we propose and demonstrate a distinctive approach for materials discovery using unsupervised learning, which does not require labeled data and thus alleviates the data scarcity challenge. Using solid-state Li-ion conductors as a model problem, unsupervised materials discovery utilizes a limited quantity of conductivity data to prioritize a candidate list from a wide range of Li-containing materials for further accurate screening. Our unsupervised learning scheme discovers 16 new fast Li-conductors with conductivities of 10−4–10−1 S cm−1 predicted in ab initio molecular dynamics simulations. These compounds have structures and chemistries distinct to known systems, demonstrating the capability of unsupervised learning for discovering materials over a wide materials space with limited property data.
Tuning the hysteresis of a metal-insulator transition via lattice compatibility
(Springer Nature, 2020-07-15) Liang, Y. G.; Lee, S.; Yu, H. S.; Zhang, H. R.; Liang, Y. J.; Zavalij, P. Y.; Chen, X.; James, R. D.; Bendersky, L. A.; Davydov, A. V.; Zhang, X. H.; Takeuchi, I.
Structural phase transitions serve as the basis for many functional applications including shape memory alloys (SMAs), switches based on metal-insulator transitions (MITs), etc. In such materials, lattice incompatibility between transformed and parent phases often results in a thermal hysteresis, which is intimately tied to degradation of reversibility of the transformation. The non-linear theory of martensite suggests that the hysteresis of a martensitic phase transformation is solely determined by the lattice constants, and the conditions proposed for geometrical compatibility have been successfully applied to minimizing the hysteresis in SMAs. Here, we apply the non-linear theory to a correlated oxide system (V1−xWxO2), and show that the hysteresis of the MIT in the system can be directly tuned by adjusting the lattice constants of the phases. The results underscore the profound influence structural compatibility has on intrinsic electronic properties, and indicate that the theory provides a universal guidance for optimizing phase transforming materials.
Plasmonic nanoarcs: a versatile platform with tunable localized surface plasmon resonances in octave intervals
(Optical Society of America Publishing, 2020-10-12) Zhang, Kunyi; Lawson, Andrew P.; Ellis, Chase T.; Davis, Matthew S.; Murphy, Thomas E.; Bechtel, Hans A.; Tischler, Joseph G.; Rabin, Oded
The tunability of the longitudinal localized surface plasmon resonances (LSPRs) of metallic nanoarcs is demonstrated with key relationships identified between geometric parameters of the arcs and their resonances in the infrared. The wavelength of the LSPRs is tuned by the mid-arc length of the nanoarc. The ratio between the attenuation of the fundamental and second order LSPRs is governed by the nanoarc central angle. Beneficial for plasmonic enhancement of harmonic generation, these two resonances can be tuned independently to obtain octave intervals through the design of a non-uniform arc-width profile. Because the character of the fundamental LSPR mode in nanoarcs combines an electric and a magnetic dipole, plasmonic nanoarcs with tunable resonances can serve as versatile building blocks for chiroptical and nonlinear optical devices.
Printable, high-performance solid-state electrolyte films
(AAAS, 2020-11-18) Ping, Weiwei; Wang, Chengwei; Wang, Ruiliu; Dong, Qi; Lin, Zhiwei; Brozena, Alexandra H.; Dai, Jiaqi; Luo, Jian; Hu, Liangbing
Current ceramic solid-state electrolyte (SSE) films have low ionic conductivities (10−8 to 10−5 S/cm ), attributed to the amorphous structure or volatile Li loss. Herein, we report a solution-based printing process followed by rapid (~3 s) high-temperature (~1500°C) reactive sintering for the fabrication of high-performance ceramic SSE films. The SSEs exhibit a dense, uniform structure and a superior ionic conductivity of up to 1 mS/cm. Furthermore, the fabrication time from precursor to final product is typically ~5 min, 10 to 100 times faster than conventional SSE syntheses. This printing and rapid sintering process also allows the layer-by-layer fabrication of multilayer structures without cross-contamination. As a proof of concept, we demonstrate a printed solid-state battery with conformal interfaces and excellent cycling stability. Our technique can be readily extended to other thin-film SSEs, which open previously unexplores opportunities in developing safe, high-performance solid-state batteries and other thin-film devices.
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.

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