Strategic Growth Area: Economical and Sustainable Materials (ESM)

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100163 - Materials Strategic Growth Area Research Workshop
(VT Continuing and Professional Education, 2016)
The Economical and Sustainable Materials Strategic Growth Area (Materials SGA) is committed to the development of cross-disciplinary teams that will tackle critical scientific materials challenges related to our pillars of interest: health, energy, environment, and resilient infrastructure. We view these challenges through an atoms/molecules-to-systems lens, so our research and education efforts will span the full scope and sequence of materials use from discovery and computational modeling to processing, manufacturing, and implementation. Our research pillars connect our mission with those of all the existing Destination Areas and Strategic Growth areas. In particular, Adaptive Brain and Behavior, Intelligent Infrastructure for Human Centered Communities, and Global Systems Science have been identified as natural partners.
3D Bioprinted Human Skeletal Muscle Constructs for Muscle Function Restoration
Kim, Ji Hyun; Seol, Young-Joon; Ko, In Kap; Kang, Hyun-Wook; Lee, Young Koo; Yoo, James J.; Atala, Anthony; Lee, Sang Jin (Springer Nature, 2018-08-17)
A bioengineered skeletal muscle tissue as an alternative for autologous tissue flaps, which mimics the structural and functional characteristics of the native tissue, is needed for reconstructive surgery. Rapid progress in the cell-based tissue engineering principle has enabled in vitro creation of cellularized muscle-like constructs; however, the current fabrication methods are still limited to build a three-dimensional (3D) muscle construct with a highly viable, organized cellular structure with the potential for a future human trial. Here, we applied 3D bioprinting strategy to fabricate an implantable, bioengineered skeletal muscle tissue composed of human primary muscle progenitor cells (hMPCs). The bioprinted skeletal muscle tissue showed a highly organized multi-layered muscle bundle made by viable, densely packed, and aligned myofiber-like structures. Our in vivo study presented that the bioprinted muscle constructs reached 82% of functional recovery in a rodent model of tibialis anterior (TA) muscle defect at 8 weeks of post-implantation. In addition, histological and immunohistological examinations indicated that the bioprinted muscle constructs were well integrated with host vascular and neural networks. We demonstrated the potential of the use of the 3D bioprinted skeletal muscle with a spatially organized structure that can reconstruct the extensive muscle defects.
3D printing of lignin: Challenges, opportunities and roads onward
Ebers, L. -S.; Arya, Aditi; Bowland, C. C.; Glasser, Wolfgang G.; Chmely, S. C.; Naskar, A. K.; Laborie, Marie-Pierre Genevieve (2021-06)
As the second most abundant biopolymer on earth, and as a resource recently becoming more available in separated and purified form on an industrial scale due to the development of new isolation technologies, lignin has a key role to play in transitioning our material industry towards sustainability. Additive manufacturing (AM), the most efficient-material processing technology to date, has likewise made great strides to promote sustainable industrial solutions to our needs in engineered products. Bringing lignin research to AM has prompted the emergence of the nascent "lignin 3D printing" field. This review presents the recent state of art of this promising field and highlights its challenges and opportunities. Following a review of the industrial availability, molecular attributes, and associated properties of technical lignins, we review R&D efforts at implementing lignin systems in extrusion-based and stereolithography (SLA) printing technologies. Doing so underlines the adage of lignin research that "all lignins are not created equal," and stresses the opportunity nested in this chemical diversity created mostly by differences in isolation conditions to molecularly select and tune the attributes of technical lignin systems towards desirable properties, be it by modification or polymer blending. Considering the AM design process in its entirety, we finally propose onward routes to bring the full potential to this emerging field. We hope that this review can help promote the unique value and overdue industrial role of lignin in sustainable engineered materials and products.
Additive manufacturing of complex micro-architected graphene aerogels
Hensleigh, Ryan M.; Cui, Huachen; Oakdale, James S.; Ye, Jianchao C.; Campbell, Patrick G.; Duoss, Eric B.; Spadaccini, Christopher M.; Zheng, Xiaoyu; Worsley, Marcus A. (Royal Society of Chemistry, 2018-08-13)
3D graphene foams exhibit immense degradation of mechanical properties. Micro-architecture can alleviate this problem, but no current technique meets the manufacturing requirements. Herein we developed a light-based 3D printing process to create hierarchical graphene structures with arbitrary complexity and order-of-magnitude finer features, showing enhanced mechanical properties at decreasing density.
Adsorbing/dissolving Lyoprotectant Matrix Technology for Non-cryogenic Storage of Archival Human Sera
Solivio, Morwena J.; Less, Rebekah; Rynes, Mathew L.; Kramer, Marcus; Aksan, Alptekin (Springer Nature, 2016-04-12)
Despite abundant research conducted on cancer biomarker discovery and validation, to date, less than two-dozen biomarkers have been approved by the FDA for clinical use. One main reason is attributed to inadvertent use of low quality biospecimens in biomarker research. Most proteinaceous biomarkers are extremely susceptible to pre-analytical factors such as collection, processing, and storage. For example, cryogenic storage imposes very harsh chemical, physical, and mechanical stresses on biospecimens, significantly compromising sample quality. In this communication, we report the development of an electrospun lyoprotectant matrix and isothermal vitrification methodology for non-cryogenic stabilization and storage of liquid biospecimens. The lyoprotectant matrix was mainly composed of trehalose and dextran (and various low concentration excipients targeting different mechanisms of damage), and it was engineered to minimize heterogeneity during vitrification. The technology was validated using five biomarkers; LDH, CRP, PSA, MMP-7, and C3a. Complete recovery of LDH, CRP, and PSA levels was achieved post-rehydration while more than 90% recovery was accomplished for MMP-7 and C3a, showing promise for isothermal vitrification as a safe, efficient, and low-cost alternative to cryogenic storage.
Adsorption of Xyloglucan onto Thin Films of Cellulose Nanocrystals and Amorphous Cellulose: Film Thickness Effects
Kittle, Joshua D.; Qian, Chen; Edgar, Emma; Roman, Maren; Esker, Alan R. (American Chemical Society, 2018-10-01)
Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential
Wang, Jun; Yu, Liang; Hu, Lin; Chen, Gang; Xin, Hongliang; Feng, Xiaofeng (Springer Nature, 2018-05-15)
Electrochemical reduction of N2 to NH3 provides an alternative to the Haber−Bosch process for sustainable, distributed production of NH3 when powered by renewable electricity. However, the development of such process has been impeded by the lack of efficient electrocatalysts for N2 reduction. Here we report efficient electroreduction of N2 to NH3 on palladium nanoparticles in phosphate buffer solution under ambient conditions, which exhibits high activity and selectivity with an NH3 yield rate of ~4.5 μg mg−1Pd h−1 and a Faradaic efficiency of 8.2% at 0.1 V vs. the reversible hydrogen electrode (corresponding to a low overpotential of 56 mV), outperforming other catalysts including gold and platinum. Density functional theory calculations suggest that the unique activity of palladium originates from its balanced hydrogen evolution activity and the Grotthuss-like hydride transfer mechanism on α-palladium hydride that lowers the free energy barrier of N2 hydrogenation to *N2H, the rate-limiting step for NH3 electrosynthesis.
Amphiphilic hydroxyalkyl cellulose derivatives for amorphous solid dispersion prepared by olefin cross-metathesis
Dong, Yifan; Mosquera-Giraldo, Laura I.; Troutman, Jacob; Skogstad, Brittny; Taylor, Lynne S.; Edgar, Kevin J. (Royal Society of Chemistry, 2016-07-07)
Olefin cross-metathesis (CM) has enabled design and synthesis of diverse, amphiphilic cellulose ether derivatives (e.g. of ethyl and methyl cellulose). In this paper, hydroxyalkyl cellulose was selected as a hydrophilic starting material, with the additional advantage that it has DS (OH) 3.0 that allows targeting of a full range of DS of selected functional groups. Hydroxypropyl cellulose (HPC) was first etherified with 5-bromopent-1-ene to attach olefin “handles” for metathesis, whereby control of molar ratios of sodium hydride and 5-bromopent-1-ene permits full DS control of appended olefin. These olefin-terminated HPC ethers then were subjected to CM with acrylic acid and different acrylates, followed by diimide hydrogenation to reduce the resulting α,β-unsaturation. NMR and FT-IR spectroscopies were useful tools for following reaction progress. One of the product carboxyl-functionalized HPC derivatives, designated HPC-Pen106-AA-H, showed high promise as a crystallization inhibitor of the antiviral drug telaprevir. Its nucleation-induction inhibitory ability was compared to those of commercial controls, HPC and HPMCAS. All three polymers were very effective for inhibiting telaprevir crystallization, increasing induction time up to 8-fold. HPC did not effectively prevent amorphous particle growth, whereas the carboxyl-containing HPC-Pen106-AA-H and HPMCAS were able to prevent formation of agglomerates of amorphous drugs.
Analysis of electricity consumption: a study in the wood products industry
Quesada, Henry Jose; Wiedenbeck, Janice K.; Bond, Brian H. (2016-10)
This paper evaluates the effect of industry segment, year, and US region on electricity consumption per employee, per dollar sales, and per square foot of plant area for wood products industries. Data was extracted from the Industrial Assessment Center (IAC) database and imported into MS Excel. The extracted dataset was examined for outliers and abnormalities with outliers outside the quantile range 0.5-99.5 dropped from the analysis. A logarithmic transformation was applied to eliminate the skewness of the original data distributions. Correlation measurements indicated a moderate association between the response variables; therefore, a multivariate analysis of variance test was performed to measure the impact of the three factors: industry type, year, and region, simultaneously on all response variables. The results indicated some effect associated with all three factors on the three measures of electricity consumption. Subsequently, univariate ANOVA tests were conducted to determine the levels of the factors that were different. Most levels of industry type were associated with significantly different energy consumption, an expected result since some of the industries are more energy intensive than others. The industries in Standard Industry Code (SIC) 2493 (reconstituted wood products) are the groups with the highest electricity consumption with means of 38,096.28 kWh/employee, 0.86 kWh/sales, and 154.14 kWh/plant area while industries grouped in SIC 2451 (mobile homes) have the smallest consumption with means of 6811.01 kWh/employee, 0.05 kWh/sales, and 9.45 kWh/plant area. Interestingly, differences in regional consumption were found to be linked to the proportion of industry types by region. Data analysis also indicated differences in electricity consumption per employee for the factor year, but for the other response variables, no differences were found. These main results indicate that industries in the wood products sector have different electricity consumption rates depending on the type of manufacturing processes they use. Therefore, industries in this sector can use these comparisons and metrics to benchmark their electricity consumption as well to understand better how electricity costs might vary depending on the region they are located.
Biodegradable Poly(Lactic Acid) Nanocomposites for Fused Deposition Modeling 3D Printing
Bardot, Madison; Schulz, Michael D. (MDPI, 2020-12-21)
3D printing by fused deposition modelling (FDM) enables rapid prototyping and fabrication of parts with complex geometries. Unfortunately, most materials suitable for FDM 3D printing are non-degradable, petroleum-based polymers. The current ecological crisis caused by plastic waste has produced great interest in biodegradable materials for many applications, including 3D printing. Poly(lactic acid) (PLA), in particular, has been extensively investigated for FDM applications. However, most biodegradable polymers, including PLA, have insufficient mechanical properties for many applications. One approach to overcoming this challenge is to introduce additives that enhance the mechanical properties of PLA while maintaining FDM 3D printability. This review focuses on PLA-based nanocomposites with cellulose, metal-based nanoparticles, continuous fibers, carbon-based nanoparticles, or other additives. These additives impact both the physical properties and printability of the resulting nanocomposites. We also detail the optimal conditions for using these materials in FDM 3D printing. These approaches demonstrate the promise of developing nanocomposites that are both biodegradable and mechanically robust.
Bioelectrochemical production of hydrogen in an innovative pressure-retarded osmosis/microbial electrolysis cell system: experiments and modeling
Yuan, Heyang; Lu, Yaobin; Abu-Reesh, Ibrahim M.; He, Zhen (Biomed Central, 2015-08-14)
Background While microbial electrolysis cells (MECs) can simultaneously produce bioelectrochemical hydrogen and treat wastewater, they consume considerable energy to overcome the unfavorable thermodynamics, which is not sustainable and economically feasible in practical applications. This study presents a proof-of-concept system in which hydrogen can be produced in an MEC powered by theoretically predicated energy from pressure-retarded osmosis (PRO). The system consists of a PRO unit that extracts high-quality water and generates electricity from water osmosis, and an MEC for organic removal and hydrogen production. The feasibility of the system was demonstrated using simulated PRO performance (in terms of energy production and effluent quality) and experimental MEC results (e.g., hydrogen production and organic removal). Results The PRO and MEC models were proven to be valid. The model predicted that the PRO unit could produce 485 mL of clean water and 579 J of energy with 600 mL of draw solution (0.8 M of NaCl). The amount of the predicated energy was applied to the MEC by a power supply, which drove the MEC to remove 93.7 % of the organic compounds and produce 32.8 mL of H2 experimentally. Increasing the PRO influent volume and draw concentration could produce more energy for the MEC operation, and correspondingly increase the MEC hydraulic retention time (HRT) and total hydrogen production. The models predicted that at an external voltage of 0.9 V, the MEC energy consumption reached the maximum PRO energy production. With a higher external voltage, the MEC energy consumption would exceed the PRO energy production, leading to negative effects on both organic removal and hydrogen production. Conclusions The PRO-MEC system holds great promise in addressing water-energy nexus through organic removal, hydrogen production, and water recovery: (1) the PRO unit can reduce the volume of wastewater and extract clean water; (2) the PRO effluents can be further treated by the MEC; and (3) the osmotic energy harvested from the PRO unit can be applied to the MEC for sustainable bioelectrochemical hydrogen production.
Biomass Valorization to Bioenergy: Assessment of Biomass Residues' Availability and Bioenergy Potential in Nigeria
Ezealigo, Uchechukwu Stella; Ezealigo, Blessing Nonye; Kemausuor, Francis; Achenie, Luke Ekem Kweku; Onwualu, Azikiwe Peter (MDPI, 2021-12)
The bioenergy sector in Nigeria currently lacks a proper assessment of resource availability. In this study, we investigated the bioenergy potential of agricultural residues and municipal solid and liquid waste using data from 2008 to 2018, and we applied a computational and analytical approach with mild assumptions. The technical potential for the production of cellulosic ethanol and biogas was estimated from the available biomass. It was discovered that higher energy was generated from biogas than cellulosic ethanol for the same type of residue. The available crop residue technical potential of 84 Mt yielded cellulosic ethanol and biogas of 14,766 ML/yr (8 Mtoe) and 15,014 Mm(3)/yr (13 Mtoe), respectively. Biogas has diverse applications ranging from heat to electric power generation and therefore holds great potential in solving the current electricity crisis in Nigeria. It will also position the nation towards achieving the 7th sustainable development goal (SDG 7) on clean and affordable energy.
Block copolymer derived uniform mesopores enable ultrafast electron and ion transport at highmass loadings
Liu, Tianyu; Zhou, Zhenping; Guo, Yichen; Guo, Dong; Liu, Guoliang (Nature Research, 2019)
High mass loading and fast charge transport are two crucial but often mutually exclusive characteristics of pseudocapacitors. On conventional carbon supports, high mass loadings inevitably lead to sluggish electron conduction and ion diffusion due to thick pseudocapacitive layers and clogged pores. Here we present a design principle of carbon supports, utilizing self-assembly and microphase-separation of block copolymers. We synthesize porous carbon fibers (PCFs) with uniform mesopores of 11.7 nm, which are partially filled with MnO2 of <2 nm in thickness. The uniform mesopores and ultrathin MnO2 enable fast electron/ion transport comparable to electrical-double-layer-capacitive carbons. At mass loadings approaching 7mg cm−2, the gravimetric and areal capacitances of MnO2 (~50% of total mass) reach 1148 F g−1 and 3141 mF cm−2, respectively. Our MnO2-coated PCFs outperform other MnO2-based electrodes at similar loadings, highlighting the great promise of block copolymers for designing PCF supports for electrochemical applications.
Boosting the Power-Generation Performance of Micro-Sized Al-H2O2 Fuel Cells by Using Silver Nanowires as the Cathode
Zhang, Heng; Yang, Yang; Liu, Tianyu; Chang, Honglong (MDPI, 2018-09-03)
Micro-sized fuel cells represent one of the pollution-free devices available to power portable electronics. However, the insufficient power output limits the possibility of micro-sized fuel cells competing with other power sources, including supercapacitors and lithium batteries. In this study, a novel aluminum-hydrogen peroxide fuel cell is fabricated using uniform silver nanowires with diameters of 0.25 µm as the catalyst at the cathode side. The Ag nanowire solution is prepared via a polyol method, and mixed uniformly with Nafion and ethanol to enhance the adhesion of Ag nanowires. We carry out electrochemical tests, including cyclic voltammetry, electrochemical impedance spectroscopy, and Tafel polarization, to characterize the performance of this catalyst in H₂O₂ reduction. The Ag nanowires exhibit a high effectiveness and durability while catalyzing the reduction of H₂O₂ with a low impedance. The micro-sized Al-H₂O₂ fuel cell equipped with Ag nanowires delivers a power density of 43 W·m⁻² under a low concentration of H₂O₂ (0.1 M), which is substantially higher than the previously reported devices.
Broadband/Wideband Magnetoelectric Response
Park, Chee-Sung; Priya, Shashank (Hindawi, 2012-04-08)
A broadband/wideband magnetoelectric (ME) composite offers new opportunities for sensing wide ranges of both DC and AC magnetic fields. The broadband/wideband behavior is characterized by flat ME response over a given AC frequency range and DC magnetic bias. The structure proposed in this study operates in the longitudinal-transversal (L-T) mode. In this paper, we provide information on (i) how to design broadband/wideband ME sensors and (ii) how to control the magnitude of ME response over a desired frequency and DC bias regime. A systematic study was conducted to identify the factors affecting the broadband/wideband behavior by developing experimental models and validating them against the predictions made through finite element modeling. A working prototype of the sensor with flat bands for both DC and AC magnetic field conditions was successfully obtained. These results are quite promising for practical applications such as current probe, low-frequency magnetic field sensing, and ME energy harvester.
Cascade degradation and upcycling of polystyrene waste to high-value chemicals
Xu, Zhen; Pan, Fuping; Sun, Mengqi; Xu, Jianjun; Munyaneza, Nuwayo Eric; Croft, Zacary L.; Cai, Gangshu; Liu, Guoliang (National Academy of Sciences, 2022-08-23)
Plastic waste represents one of the most urgent environmental challenges facing humankind. Upcycling has been proposed to solve the low profitability and high market sensitivity of known recycling methods. Existing upcycling methods operate under energy-intense conditions and use precious-metal catalysts, but produce low-value oligomers, monomers, and common aromatics. Herein, we report a tandem degradation-upcycling strategy to exploit high-value chemicals from polystyrene (PS) waste with high selectivity. We first degrade PS waste to aromatics using ultraviolet (UV) light and then valorize the intermediate to diphenylmethane. Low-cost AlCl3 catalyzes both the reactions of degradation and upcycling at ambient temperatures under atmospheric pressure. The degraded intermediates can advantageously serve as solvents for processing the solid plastic wastes, forming a self-sustainable circuitry. The low-value-input and high-value-output approach is thus substantially more sustainable and economically viable than conventional thermal processes, which operate at high-temperature, high-pressure conditions and use precious-metal catalysts, but produce low-value oligomers, monomers, and common aromatics. The cascade strategy is resilient to impurities from plastic waste streams and is generalizable to other high-value chemicals (e.g., benzophenone, 1,2-diphenylethane, and 4-phenyl-4-oxo butyric acid). The upcycling to diphenylmethane was tested at 1-kg laboratory scale and attested by industrial-scale techno-economic analysis, demonstrating sustainability and economic viability without government subsidies or tax credits.
The CEHMS Chronicle, April 2013
(Virginia Tech, 2013-04)
This is the quarterly newsletter for the Center for Energy Harvesting Materials and Systems.
The CEHMS Chronicle, April 2014
(Virginia Tech, 2014-04)
This is the quarterly newsletter for the Center for Energy Harvesting Materials and Systems.
The CEHMS Chronicle, August 2013
(Virginia Tech, 2013-08)
This is the quarterly newsletter for the Center for Energy Harvesting Materials and Systems.
The CEHMS Chronicle, February 2013
(Virginia Tech, 2013-02)
This is the quarterly newsletter for the Center for Energy Harvesting Materials and Systems.

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