Pristine Properties Research Articles

Sustainable multiphase jet polishing of additively manufactured heat pipes utilizing recycled glass chips

Each year, a huge amount of waste glass chips is produced by machining, which is not recycled and has been treated as waste, resulting in the wasting of resources. However, the pristine physical properties of these micro-sized chips show great potential to be recycled as abrasives in jet polishing. In this work, machined glass chips were recycled and directly used as the abrasives in multiphase jet (MPJ) and abrasive water jet (AWJ) polishing for aluminum heat pipes of additive manufacturing with complex structures. Polishing performance of the recycled abrasives from waste glass was compared with those of commercial quartz abrasives with mesh sizes of 600, 800, 1000, 1200, and 3000. The results show that the recycled abrasives of glass chips have comparable performance to the commercial abrasives with mesh size of 1000. Computational fluid dynamic simulations were conducted on the two jet polishing to elucidate the fundamental material removal mechanisms. It is found that a higher drag force in the AWJ polishing could lead to uniform material removal and induce four times higher for material removal rate (MRR). The cost of setup, water and energy consumptions of MPJ polishing are only one tenth those of AWJ polishing. Energy dispersive spectroscopy reveals that there is no element contamination on the polished surface. This work proposes a novel approach of MPJ polishing for components produced by additive manufacturing with complicated structures. These findings provide new insights for the recycling use of waste chips generated in manufacturing, and suggest new solutions for saving energy and resources, as well as for clean and green production.

Nanostructured Magnetite Coated with BiOI Semiconductor: Readiness Level in Advanced Solar Photocatalytic Applications for the Remediation of Phenolic Compounds in Wastewater from the Wine and Pisco Industry

Heterogeneous photocatalysis is an advanced, efficient oxidation process that uses solar energy to be sustainable and low-cost compared to conventional wastewater treatments. This study synthesized BiOI/Fe3O4 using the solvothermal technique, evaluating stoichiometric ratios of Bi/Fe (2:1, 3:1, 5:1, and 7:1) under simulated solar irradiation to optimize the degradation of caffeic acid, a pollutant found in wastewater from the wine and pisco industry. The nanomaterial with a 5:1 ratio (BF-5) was the most effective, achieving a degradation of 77.2% in 180 min. Characterization by X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM), Brunauer–Emmett–Teller (BET), Barrett–Joyner–Halenda (BJH), Fourier Transform Infrared Spectroscopy (FTIR), Diffuse Reflectance Spectroscopy (DRS), and Vibrating Sample Magnetometry (VSM) showed that BF-5 has a porous three-dimensional structure with BiOI nanosheets coating the Fe3O4 surface, while retaining the pristine BiOI properties. The magnetite provided magnetic properties that facilitated the recovery of the photocatalyst, reaching 89.4% recovery. These findings highlight the potential of BF-5 as an efficient and recoverable photocatalyst for industrial applications. The technical, economic, and environmental feasibility were also evaluated at the technological readiness level (TRL) to project solar photocatalysis in real applications.

Artifact-free sample preparation of metal thin films using Xe plasma-focused ion beam milling for atomic resolution and in situ biasing analyses

The focused ion beam (FIB) technique using Ga ion beams is generally employed for transmission electron microscopy (TEM) sampling owing to its location-specific beam controllability on materials. However, Ga ion beam bombardment-induced damage hinders reliable structural analysis. Furthermore, Ga ions implanted in the damaged surface layer substantially lower the chemical stability of the samples, such as metal thin films. Here, aiming for atomic-level interface structural analysis, we propose a useful approach for the TEM sample preparation of heteroepitaxial Ag/Cu metal films without physical damage or chemical instabilities using the Xe plasma FIB (PFIB) system. Xe plasma-assisted sampling ensured that the interface structure of the Ag/Cu metal film remained intact; in contrast, the sample prepared using the focused Ga ion beam was damaged by elemental mixing. Furthermore, the sample prepared by Xe plasma milling exhibited robust structural stability over time after exposure to air in contrast to the sample prepared by Ga-ion milling, which induced structural decomposition owing to oxidation. In addition to the static structural analysis, the Cu thin film sample prepared by Xe PFIB exclusively exhibited pristine structural properties under in situ electrical biasing experiments, thus confirming the feasibility of conducting a fundamental study of Cu electromigration without artifacts.

Yu-Shiba-Rusinov bands in a self-assembled kagome lattice of magnetic molecules

Kagome lattices constitute versatile platforms for studying paradigmatic correlated phases. While molecular self-assembly of kagome structures on metallic substrates is promising, it is challenging to realize pristine kagome properties because of hybridization with the bulk degrees of freedom and modified electron-electron interactions. We suggest that a superconducting substrate offers an compelling platform for realizing a magnetic kagome lattice. Exchange coupling induces kagome-derived bands at the interface, which are protected from the bulk by the superconducting energy gap. We realize a magnetic kagome lattice on a superconductor by depositing Fe-porphin-chloride molecules on Pb(111) and using temperature-activated de-chlorination and self-assembly. This allows us to control the formation of smaller kagome precursors and long-range ordered kagome islands. Using scanning tunneling microscopy and spectroscopy at 1.6 K, we identify Yu-Shiba-Rusinov states inside the superconducting energy gap and track their hybridization from the precursors to larger islands, where the kagome lattice induces extended YSR bands. These YSR-derived kagome bands inside the superconducting energy gap allow for long-range coupling and induced pairing correlations, motivating further studies to resolve possible spin-liquid or Kondo-lattice-type behavior.

Towards a zero-waste chemcycling of thermoset polymer composites: Catalyst assisted mild solvolysis for clean carbon fiber liberation and circular coating development

Thermoset materials and their reinforced composites are widely employed in the aircraft, wind energy and construction sectors. Their 3D-crosslinked network and their chemical and physical heterogeneity make them particularly difficult to be recycled. Nowadays, the management of composite scraps and end-of-life waste is still based on landfilling or incineration practices, which are clearly non-compliant with the principles of the circular economy. In this work, a catalysed solvolysis process in mild conditions (T = 180 °C, t = 1–3 h, catalyst 1–7 wt%) was applied for the chemical recycling (chemcycling) of anhydride-cured epoxy resins and their carbon fiber reinforced composites. The selection of the hydroxylated solvents followed thermodynamic considerations (Hansen solubility parameters) and green chemistry principles. The quality of the liberated fibers was studied through thermogravimetric analysis, scanning electron microscopy and single-fiber micromechanical testing, highlighting high surface purity and 100% retention of their pristine mechanical properties (Young's modulus, elongation at break and ultimate strength). The organic recyclates were characterized through gel permeation chromatography, Fourier-transform infrared spectroscopy and chemical titration, and directly reused as hydroxylated binders for the formulation and application of bicomponent polyurethane protective coatings. The resulting coatings were characterized by high chemical resistance (> 100 double rubs at methyl-ethyl ketone test), high surface scratch hardness (3H to 5H), good substrate adhesion (1.5–4 MPa), and excellent optical clarity and surface gloss. These results demonstrate the potential zero-waste reusability of all fractions derived from the chemical recycling of carbon fiber reinforced composites, in line with the principles of the circular economy.

In-depth analysis of γ-CuI as an HTM for perovskite solar cells: A comprehensive DFT study of structural, elastic, mechanical, charge density, and optoelectronic properties

Herein, we employed Density Functional Theory (DFT) to comprehensively investigate pristine γ-CuI properties under two computational schemes: Generalized Gradient Approximation (GGA) and GGA + Hubbard correction. Structural stability is rigorously assessed through ground state energy optimization, complemented by a meticulous examination of elastic constants to confirm mechanical stability. Later on, we analyzed the electronic properties, as well as the optical properties, incorporating parameters such as the extinction coefficient that was low and refractive index that was high in the IR and visible regions. Notably, γ-CuI exhibits low reflectivity and absorption in the critical regions of interest. Our findings demonstrate that γ-CuI can serve as a cost-effective Hole Transporting Material (HTM), effectively reducing optical losses in perovskite solar cells.

Hazard assessment of hexagonal boron nitride and hexagonal boron nitride reinforced thermoplastic polyurethane composites using human skin and lung cells

Hexagonal boron nitride (hBN) is an emerging two-dimensional material attracting considerable attention in the industrial sector given its innovative physicochemical properties. Potential risks are associated mainly with occupational exposure where inhalation and skin contact are the most relevant exposure routes for workers. Here we aimed at characterizing the effects induced by composites of thermoplastic polyurethane (TPU) and hBN, using immortalized HaCaT skin keratinocytes and BEAS-2B bronchial epithelial cells. The composite was abraded using a Taber® rotary abraser and abraded TPU and TPU-hBN were also subjected to photo-Fenton-mediated degradation mimicking potential weathering across the product life cycle. Cells were exposed to the materials for 24 h (acute exposure) or twice per week for 4 weeks (chronic exposure) and evaluated with respect to material internalization, cytotoxicity, and proinflammatory cytokine secretion. Additionally, comprehensive mass spectrometry-based proteomics and metabolomics (secretomics) analyses were performed. Overall, despite evidence of cellular uptake of the material, no significant cellular and/or protein expression profiles alterations were observed after acute or chronic exposure of HaCaT or BEAS-2B cells, identifying only few pro-inflammatory proteins. Similar results were obtained for the degraded materials. These results support the determination of hazard profiles associated with cutaneous and pulmonary hBN-reinforced polymer composites exposure.

A comparative adsorption study of activated carbon and Fe-modified activated carbon for trinitrotoluene removal

BackgroundActivated carbon (AC) is commonly used to remove many pollutants from water due to its appealing adsorption properties. However, the pristine surface properties of AC limit its ability to effectively remove 2,4,6-trinitrotoluene (TNT, a widely used explosive water contaminant). Modifying AC with Fe nanoparticles (NPs) can significantly improve the surface properties of the Fe/AC composite, thereby enhancing its adsorption capabilities. MethodCommercial charcoal-based AC was modified with Fe NPs via wet impregnation followed by a one-step carbothermal synthesis (labeled Fe-AC-800). A detailed characterization of Fe-AC-800 and its counterparts, pristine AC and thermally modified AC (AC-800, without Fe NPs doping) was performed using XRD, Raman Spectroscopy, SEM, EDS, BET, XPS, and FTIR. Then, the adsorption characteristics and performances of Fe-AC-800 were analyzed to determine its effectiveness in removing TNT and compared to AC and AC-800, considering the impact of in-situ Fe-modification and carbothermal treatment. Significant findingsFe-AC-800 displayed a higher adsorption capacity for TNT (387.74 mg/g) than the pristine AC (265.52 mg/g) but only slightly higher than AC-800 (339.64 mg/g). This was ascribed to the combined effect of the carbothermal treatment and Fe NPs doping, which constructed a richer porous structure that improved the Fe-AC-800 surface features and favored TNT removal. The optimal adsorption capacity of Fe-AC-800 was 464.13 mg/g under ambient conditions. TNT adsorption onto Fe-AC-800 and AC-800 conformed to only the Langmuir isotherm model, indicating uniform monolayer adsorption, whereas on the pristine AC, it satisfied both Langmuir and Freundlich isotherm models, respectively. The primary mechanism of TNT adsorption onto Fe-AC-800 was physical adsorption through pore filling, hydrogen bonding, and π-π EDA interactions, respectively.

Numerical simulation approach for consideration of ageing effects in PCB substrates by modifying viscoelastic materials properties

During operating time of electronic systems, the used materials in such devices are potentially subjected to ageing effects, which might limit the lifetime. Therefore, knowledge about the used materials and the way the materials are affected by ageing effects is of key importance to develop reliable products.In this study, a simulation approach is discussed that is able to consider ageing effects caused by oxidation at elevated temperature of a printed circuit board material, typically used for high frequency applications. The material was characterized for its thermomechanical properties with state-of-the-art techniques for different ageing durations. Ageing was accelerated by storing the samples in an oven at 175 °C for up to 1000 h.Within the simulation workflow, the thermomechanical properties of the different aged states are defined by modifying the pristine viscoelastic properties. Four exponential functions are derived modifying the initial modulus, the characteristic time constants, the shift function and the coefficient of thermal expansion, all in dependency of ageing time.To demonstrate the approach, the soldered interconnection lifetime of a theoretical chip-size-package on a printed circuit board is studied. State-of-the-art lifetime predictions of such interconnections only include thermomechanical ageing effects, for example by creep effects of the solder. By additionally considering the ageing of the printed circuit board, thermal ageing is combined with thermomechanical ageing.Results in the soldered interconnection are compared between either considering additional ageing effects of the printed circuit board or neglecting this behavior. Thus it is shown that thermal ageing plays a significant role in the development of accumulated creep strain which becomes increasingly important with increasing expected lifetime.

Graphene‐Based Lateral Heterojunctions for 2D Integrated Circuits

AbstractA method for patterning single‐layer graphene (SLG) and single‐layer oxidized graphene (SOG) within a continuous atomic layer to form lateral heterojunctions is presented. Raman spectroscopy is employed to investigate the evolution of defect‐related Raman peaks during excimer‐UV irradiation, facilitating the identification of structural changes and defect formation processes. Electrical transport measurements reveal that SOG‐patterned field‐effect transistors (FETs) exhibit varying characteristics depending on the degree of oxidation, thus offering the potential to tailor the electrical properties of graphene devices for specific requirements. Scanning Kelvin probe microscopy measurements reveal the surface potential and work function of the SOG regions compared with those of SLG. The effective functionality of the SOG pattern to operate as a resistor, allowing control of the electrical conductivity in the SOG‐patterned SLG channels, is demonstrated. This capability restricts the current flow while preserving the pristine electrical properties of the graphene channel. Moreover, the SOG pattern can serve as a potential barrier to constructing SLG‐SOG‐patterned integrated circuits, providing exciting opportunities for engineering advanced electronic components. This breakthrough in graphene devices simplifies the fabrication process of graphene‐based FETs and provides the foundation for developing atomically thin integrated circuits for a wide range of applications.

Ecotoxicity of tire wear particles to antioxidant enzyme system and metabolic functional activity of river biofilms: The strengthening role after incubation-aging in migrating water phases

Tire wear particles (TWPs) are commonly studied for their exudation toxicity, yet a critical knowledge gap exists regarding the source nature and migration of these particulate pollutants, hindering comprehensive environmental risk assessments. This study explores the pristine properties of three typical TWPs (rolling friction (R-TWPs), sliding friction (S-TWPs), and cryogenically milled tire treads (C-TWPs)) and their aging characteristics after incubation in runoff (primary aging) and sewage (further aging). Our investigation aims to unveil the intrinsic mechanisms of TWPs ecotoxicity towards freshwater biofilms. Results reveal that the generation modes significantly impact pristine physicochemical properties, including surface structure, particle size, and EPFR abundance. These factors, in turn, influence acute ecotoxicity, as evidenced by cell mortality, antioxidant enzyme activity responses, and metabolic changes in freshwater biofilms. The ecological toxicity ranking of pristine exposure groups is S-TWPs, R-TWPs, and C-TWPs, attributed to variations in surface properties and particle size. Following incubation and aging, especially in sewage, differences in physicochemical properties among TWPs types diminish. Alarmingly, ecotoxicity intensifies and becomes consistent across TWPs types, driven by the screening of small particles during water incubation aging and the formation of EPFRs on TWPs surfaces stimulated by photosensitive organic matter or groups. This study underscores the aquatic ecological risks associated with TWP surface properties, highlighting the significant influence of environmental aging conditions on these risks.

Effect of vitamin E–enhanced highly cross-linked polyethylene on wear rate and particle debris in anatomic total shoulder arthroplasty: a biomechanical comparison to ultrahigh-molecular-weight polyethylene

Particle-induced osteolysis resulting from polyethylene wear remains a source of implant failure in anatomic total shoulder designs. Modern polyethylene components are irradiated in an oxygen-free environment to induce cross-linking, but reducing the resulting free radicals with melting or heat annealing can compromise the component's mechanical properties. Vitamin E has been introduced as an adjuvant to thermal treatments. Anatomic shoulder arthroplasty models with a ceramic head component have demonstrated that vitamin E-enhanced polyethylene show improved wear compared with highly cross-linked polyethylene (HXLPE). This study aimed to assess the biomechanical wear properties and particle size characteristics of a novel vitamin E-enhanced highly cross-linked polyethylene (VEXPE) glenoid compared to a conventional ultrahigh-molecular-weight polyethylene (UHMWPE) glenoid against a cobalt chromium molybdenum (CoCrMo) head component. Biomechanical wear testing was performed to compare the VEXPE glenoid to UHMWPE glenoid with regard to pristine polyethylene wear and abrasive endurance against a polished CoCrMo alloy humeral head in an anatomic shoulder wear-simulation model. Cumulative mass loss (milligrams) was recorded, and wear rate calculated (milligrams per megacycle [Mc]). Under pristine wear conditions, particle analysis was performed, and functional biologic activity (FBA) was calculated to estimate particle debris osteolytic potential. In addition, 95% confidence intervals for all testing conditions were calculated. The average pristine wear rate was statistically significantly lower for the VEXPE glenoid compared with the HXLPE glenoid (0.81 ± 0.64 mg/Mc vs. 7.00 ± 0.45 mg/Mc) (P<.05). Under abrasive wear conditions, the VEXPE glenoid had a statistically significant lower average wear rate compared with the UHMWPE glenoid comparator device (18.93 ± 5.80 mg/Mc vs. 40.47 ± 2.63 mg/Mc) (P<.05). The VEXPE glenoid demonstrated a statistically significant improvement in FBA compared with the HXLPE glenoid (0.21 ± 0.21 vs. 1.54 ± 0.49 (P<.05). A newanatomic glenoid component with VEXPE demonstrated significantly improved pristine and abrasive wear properties with lower osteolytic particle debris potential compared with a conventional UHMWPE glenoid component. Vitamin E-enhanced polyethylene shows early promise in shoulder arthroplasty components. Long-term clinical and radiographic investigation needs to be performed to verify if these biomechanical wear properties translate to diminished long-term wear, osteolysis, and loosening.

Risk implications induced by behaviors of artificial and pavement-generated TWPs in river water: Role of particle-self properties and incubation aging

Here, we investigated the pristine properties of three typical tire wear particles (TWPs) and their aging properties after incubation in runoff (primary aging) and sewage (further aging), and captured the differences in the behavioral characteristics of nine TWPs in river water, with a view to paving the way for revealing the intrinsic mechanism of the hydroecological effects of TWPs. Our results highlight that the generation modes of three pristine tire wear particles (TWPs), stemming from typical tire and road wear processes—specifically, rolling friction (R-TWPs) and sliding friction (S-TWPs), alongside cryogenically milled tire treads (C-TWPs)—significantly impact their pristine physicochemical properties. This impact encompasses surface structure, particle size (D [4,3]: 8.5–121.3 μm), surface potential (−10.4 ∼ −1.8 mV), contact angle (95.2–129.8°), density (1.09–1.75 kg/m3), etc., consequently, these differences significantly influence their migration capability and sorption capacity during the incubation and aging in runoff and sewage. Interestingly, after incubation and aging in the migrating aqueous phase, particularly with additional aging in sewage, not only do distinctions in the aforementioned physicochemical properties (namely, particle size (5.6–6.6 μm), surface potential (−18.4 ∼ −18.1 mV), contact angle (124.5–125.4°), density (1.05–1.16 kg/m3)) among various types of TWPs diminish, but the environmental behaviors (encompassing, desorption capacity, aggregation kinetics, photochemical activity—formation of persistent free radicals, and exudation—derivative (6PPD-Quinone) of N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine: 6PPD) exhibited by this array of TWPs demonstrate a remarkable coherence within the downstream river water. Concerningly, the aforementioned features of aquatic system behaviors appear to be predisposed towards exacerbating the heightened toxicity of TWPs, for example, the leaching concentration of 6PPD-Q increased by two to three times after aging, aligning with established precedents regarding the toxicological causes associated with the quinone derivatives of antioxidants in rubber contaminants.

Experimental and computational meso-scale investigation on the deformation and failure behaviors of plain woven SiC/SiC with intrinsic and manufactured defect

For plain woven SiC/SiC composites used in aerospace thermal-structural applications, not only the pristine material properties but the open-hole performance are of critical concern for the components in service. This study investigated the influence of intrinsic pores induced during SiC matrix preparation and manufactured holes on the macro mechanical properties of plain woven SiC/SiC through experimental and numerical methods. Tensile tests at room temperature were conducted on SiC/SiC specimens with different hole apertures and configurations, and the digital image correlation (DIC) method was employed for full-field strain measurement. Moreover, micro-computed tomography (μ-CT) was utilized to characterize the internal microstructure, original defects, and failure fractures. Based on the reconstructed mesoscale model, the tensile strength and failure mechanisms of pristine and open-hole specimens were predicted and analyzed, with the models validated against the experimental results. The results showed that the inter-tow defects play an important role on the deformation and failure of pristine SiC/SiC specimens during tensile loading. The notch strength results indicated that SiC/SiC exhibits weak notch sensitivity, and the local mesoscopic deformation of the notch is affected by the combination of macroscopic stress gradients and mesoscopic structures. The mesoscale simulation results showed that the position of the hole has a significant impact on the strength of the single layer SiC/SiC composite. The more the notch invades the warp, the greater the decrease in load-bearing capacity, and the relative position of the weft mainly determines the crack propagation path. The failure mode in the simulation results is consistent with the experimental findings, indicating that the simulation model, which considers the weave architecture, can better explain the notch failure behavior of Ceramic Matrix Composites (CMCs).

Stripe-Like hBN Monolayer Template for Self-Assembly and Alignment of Pentacene Molecules.

Metallic surfaces with unidirectional anisotropy are often used to guide the self-assembly of organic molecules along a particular direction. Such supports thus offer an avenue for the fabrication of hybrid organic-metal interfaces with tailored morphology and precise elemental composition. Nonetheless, such control often comes at the expense of detrimental interfacial interactions that might quench the pristine properties of molecules. Here, hexagonal boron nitride grown on Ir(100) is introduced as a robust platform with several coexisting 1D stripe-like moiré superstructures that effectively guide unidirectional self-assemblies of pentacene molecules, concomitantly preserving their pristine electronic properties. In particular, highly-aligned longitudinal arrays of equally-oriented molecules are formed along two perpendicular directions, as demonstrated by comprehensive scanning tunneling microscopy and photoemission characterization performed at the local and non-local scale, respectively. The functionality of the template is demonstrated by photoemission tomography, a surface-averaging technique requiring a high degree of orientational order of the probed molecules. The successful identification of pentacene's pristine frontier orbitals underlines that the template induces excellent long-range molecular ordering via weak interactions, preventing charge transfer.

Optical patterning fullerene nanostructures with high purity and high surface quality

Nanoscale patterning of fullerene materials with peculiar intrinsic electronic and optical properties is of crucial importance for their widespread applications. However, it remains a daunting challenge for current methods that suffer from both complicated lithography procedures and additives of photopolymers or photochemicals detrimental to the pristine properties of fullerene. Here, we developed a contamination-free laser printing approach for in situ patterning of fullerene with nanoscale resolution and high purity. The optical trapping force within the tight focus provides a lithography-free means to form densely packed fullerene nanostructures with two-order-of-magnitude enhanced fluorescence emission and a surface roughness of 6 nm. In addition, versatile fullerene nano-patterns from dots to concentric rings can be realized by flexibly shaping the optical trapping force of higher-order Laguerre–Gaussian beams. These results open a new route to programmable and high-quality patterning of fullerene optoelectronic devices with complex nanostructures.

Additives enhancing supported amines performance in CO2 capture from air

AbstractThe utilization of supported amines as adsorbents in direct air capture (DAC) has been demonstrated to be a promising strategy for the reduction of CO2 emissions. To improve the performance of amine‐based adsorbents, the incorporation of additives has been widely adopted. In the present study, we conduct a comprehensive comparison of seven additives on tetraethylenepentamine‐impregnated mesoporous silica as a representative amine‐based adsorbent. The results indicate that minor molecular weight additives with hydroxyl groups show improved adsorption–desorption performance and increase oxidative stability. A proposed mechanism for these improvements is the combined physical and chemical promotion effects of hydroxyl groups. Through a comprehensive review of existing literature, it is found that the effects of additives on amine‐based adsorbents are dependent on factors, such as additive type, pristine adsorbent properties, incorporation method, and testing conditions. Based on these findings, it is recommended that future DAC systems prioritize the use of hydroxyl‐containing additives, whereas higher CO2 concentration and temperature capture may benefit from the incorporation of additives without hydroxyl groups. These conclusions are expected to contribute to the design of efficient adsorbents for CO2 capture.

Three-Dimensional Biomaterials with Spatiotemporal Control for Regenerative Tissue Engineering.

At Morehouse College, one of the nation's top liberal arts historically black colleges and universities (HBCU) for African American men, research experiences are used to enhance the liberal arts educational experience. Securing research funding to train HBCU students is highly competitive and challenging due to the review process that is typically vetted by scientists from research-intensive universities who may not be familiar with the HBCU enterprise that may be comprised of insolvent infrastructures. In this Account, the synthesis and preparation of synthetic polymeric biomaterials that are used to facilitate or support changes in biological processes, enhance mechanical properties, and foster tissue growth in three dimensions (3D) under disease conditions will be discussed. The use of biomaterials to help control biological processes in disease states is limited. Hence, the fabrication of 3D scaffolds with chemical variability to grow or repair damaged tissues by inhibiting molecular pathways shows promise by controlling the cellular response to recapitulate 3D tissues and organs. The Mendenhall laboratory at Morehouse College uses 3D biomaterials to solve biological problems by probing cellular mechanistic pathways using natural products and nanoparticles. Toward this end, we have fabricated and manufactured 3D biomaterial scaffolds using chemical strategies to mitigate biological processes to help restore pristine tissue properties. Hydrogels are 3D polymeric matrixes that swell in aqueous environments and support cell growth that later infuriates the 3D matrix to create new tissue(s). In contrast, electrospun fibers use high electric fields to create porous 3D polymeric structures that can be used to create 3D tissue molds.The synergistic use of 3D biomaterial templates that can inhibit cellular damage while providing a mechanically strong scaffold to support regenerative tissue growth is essential to creating the next generation of biomaterials. This approach will require foresight using tools from synthetic biology, molecular biology, autonomous processes, advanced biomanufacturing, and machine learning (ML). The use of several biomaterials has been explored by the Mendenhall laboratory to design, prepare, fabricate, characterize, and evaluate 3D electrospun fibers and hydrogels containing hybrid compositions of polylactic acid (PLA), poly(n-vinylcaprolactam) (PVCL), cellulose acetate (CA), and methacrylated hyaluronic acid (meHA). This work contributed to the newly fabricated PVCL-CA fibers with morphological changes and nanoscale fiber hydrophobic surface properties. While the use of electrospun fibers can create hierarchal scaffolds for bone tissue engineering, the use of injectable gels for nonporous tissues such as articular cartilage presents another compelling biomaterial challenge. Using graft polymerization, we prepared PVLC-graft-HA and studied the effect of lower critical solution temperatures (LCSTs), gelation temperatures, and mechanical properties using temperature-controlled rheology. Additionally, we reported that articular cartilage (chondrocyte) cells seeded in PVCL-g-HA gels and incubated at hypoxia 1% O2 produced a 10-fold increase in extracellular matrix proteins (collagen) after 10 days. This work supported exploring new approaches to protecting chondrocyte cells under hypoxia using a 3D scaffold technology.

Thermally Mendable Self-Healing Epoxy Coating for Corrosion Protection in Marine Environments

Polymeric coatings represent a well-established protection system that provides a barrier between a metallic substrate and the environment. The development of a smart organic coating for the protection of metallic structures in marine and offshore applications is a challenge. In the present study, we investigated the use of self-healing epoxy as an organic coating suitable for metallic substrates. The self-healing epoxy was obtained by mixing Diels-Alder (D-A) adducts with a commercial diglycidyl ether of bisphenol-A (DGEBA) monomer. The resin recovery feature was assessed through morphological observation, spectroscopic analysis, and mechanical and nanoindentation tests. Barrier properties and anti-corrosion performance were evaluated through electrochemical impedance spectroscopy (EIS). The film on a metallic substrate was scratched and subsequently repaired using proper thermal treatment. The morphological and structural analysis confirmed that the coating restored its pristine properties. In the EIS analysis, the repaired coating exhibited diffusive properties similar to the pristine material, with a diffusivity coefficient of 1.6 × 10-6 cm2/s (undamaged system 3.1 × 10-6 cm2/s), confirming the restoration of the polymeric structure. These results reveal that a good morphological and mechanical recovery was achieved, suggesting very promising applications in the field of corrosion-resistant protective coatings and adhesives.

Thermoplastic polyurethane film performance improvement by incorporation of furfuryl alcohol and polydimethylsiloxane

Thermoplastic polyurethanes (TPUs) films, widely used in industry and domestic, are required to have self/stimulate-healing ability and multifunction to achieve its recycling usage and adapt complex environment. Herein, the novel TPUs (PDMS/FA-PUDAs) were prepared by incorporation of biomass furfuryl alcohol (FA) and non-toxic polydimethylsiloxane (PDMS) through classic polymerization route accompanied by Diels-Alder (DA) reaction. This study investigated the combined effect of DA/rDA reaction and PDMS on improving TPU films' stimulate-healing, mechanical and anti-adhesion properties by adjusting PDMS additive amount. The experimental results demonstrated that 10 wt% PDMS and FA modified TPU film (10 % PDMS/FA-PUDA) still remained high stimulate-healing efficiency (73.48 %) after three times repair process, owing to the DA/rDA reaction was reversible between FA and bismaleimide (BMI). Besides, 10 % PDMS/FA-PUDA had superior pristine mechanical properties (Ts: 72.06 MPa, Eb: 162.45 %, Tt: 10.89 MJ/m3) because PDMS promoted the formation of microphase separation structure. Moreover, the film surface presented low surface free energy (16.79 mJ/m2) and satisfactory anti-adhesion behavior ascribed to the hydrophobicity of PDMS. This investigation might give a new perspective for designing multifunctional TPU using renewable and non-toxic materials.