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At least 37 records · Page 2

The anaerobic fungus Neocallimastix californiae shifts metabolism and produces melanin in response to lignin-derived aromatic compounds

Biological deconstruction of lignocellulose for sustainable chemical production offers an opportunity to harness evolutionarily specialized enzymes and organisms for industrial bioprocessing. While hydrolysis of cellulose and hemicellulose by CAZymes yields fermentable sugars, ligninolysis releases a heterogeneous mix of aromatic compounds that likely play a crucial role in shaping microbial communities and microbial metabolism. Here, we interrogated the metabolomic and transcriptomic response of a lignocellulolytic anaerobic fungus, Neocallimastix californiae, to a heterogeneous mixture of aromatic compounds derived from lignin. Through exposing the fungus to both a concentration it might experience in its native environment and an elevated concentration of alkaline lignin, we observe that N. californiae transforms vanillin and that supplying alkaline lignin at 0.125 g/L, alongside cellulose, enhances the growth and polysaccharide-degrading activity of N. californiae. Altogether, our results further suggest that vanillin consumption, increased polymer-degrading activity, increased metabolic activity, and transcriptomic remodeling of amino acid synthesis genes all coincide with increased melanin production by fungal cells. These observations challenge previous notions that aromatics from lignocellulose only inhibit the growth and polymer deconstruction capabilities of the biomass-degrading anaerobic fungi (Neocallimastigomycetes). This study demonstrates that anaerobic fungi have a complex relationship with aromatic chemicals derived from lignin and hemicellulose and shift their metabolism in response to the addition of lignocellulose-derived aromatics to their growth medium. Further, as no known pathways for the biochemical transformation of aromatics were detected in these organisms despite observed transcriptome remodeling in the presence of aromatics, we suggest they might encode novel biochemical routes for scavenging amino acid building blocks from aromatic monomers derived from hemicellulose side chains and lignin.

Anaerobic fungi↗

The Work of Mechanical Degradation in Elongating Polymer Melts

Molecular dynamics simulations are used to study the mechanical degradation of well-entangled polymer melts during uniaxial extensional flow. Simulations measure the transient rise in extensional stresses and relate them to the molecular alignment and scission of chain backbones. Intermolecular entanglements couple chain scission in space and time, making degradation sensitive to deformation history and strain rate in ways not displayed by dilute polymer solutions. The rate of chain scission is nonmonotonic and peaks at strains corresponding to the maximum extensibility of entanglement segments but prior to the full extension of chain backbones. We measure a specific work per scission event w* and decompose it into separate contributions associated with chain alignment, chemical bond breaking, and scission-induced plasticity. We find chain scission in melts requires activating plastic dissipation that is multiple orders of magnitude larger than the chemical work required to break a covalent backbone bond. Our findings underscore the critical need to consider bulk polymer mechanics and rheology in designing efficient mechanical degradation and mechanochemical processes.

36 MATERIALS SCIENCE↗

Constitutive Modeling of the Cross-Linked Polymers During the Trio-Aging Mechanism: Effects of Water, Oxygen, UV

Abstract The synergized effects of diverse environmental conditions such as humidity, temperature, UV, and oxygen, are considered through a generic model by combining the concepts of network alteration, hygrothermal, and Photo-thermo oxidation Models [1–4]. Hygrothermal and Photo-oxidation are considered dual aging mechanisms which are due to the synergized effects of moisture-oxygen, and UV-oxygen, respectively at elevated temperatures. Here Trio-aging is considered as the synergized effects of Hygrothermal, and Photo-oxidation which the main environmental elements involved in polymer degradation are oxygen, water, and UV radiation where each of which has a different micro-structural impact on the polymer matrix. While oxygen imposes chain scission and cross-link formation, water, and UV radiation mainly cause chain scission. Similar to our recent models, the dual network hypothesis of Topolosky is utilized and as a result, the strain energy of the polymer matrix is written in terms of two states namely unaged and infinity. The infinity state network, itself, is decomposed into three networks, namely brittle, flexible, and dead networks. While the brittle network models the cross-link formation as sub-structural phenomena, the flexible and dead networks are utilized to represent the cross-link reduction and chain scission. The contribution of these networks in the infinity state is based on the amount of relevant environmental elements. The model is developed for a domain with plenty of oxygen and holds true for a gradual aging process that happens in super-thin samples.

Bahrololoumi, Amir↗

Catalytic Degradation of Polyethylene Terephthalate Using a Phase‐Transitional Zirconium‐Based Metal–Organic Framework

Abstract Polyethylene terephthalate (PET) is utilized as one of the most popular consumer plastics worldwide, but difficulties associated with recycling PET have generated a severe environmental crisis with most PET ending its lifecycle in landfills. We report that zirconium‐based metal–organic framework (Zr‐MOF) UiO‐66 deconstructs waste PET into the building blocks terephthalic acid (TA) and mono‐methyl terephthalate (MMT) within 24 hours at 260 °C (total yield of 98 % under 1 atm H 2 and 81 % under 1 atm Ar). Extensive structural characterization studies reveal that during the degradation process, UiO‐66 undergoes an intriguing transformation into MIL‐140A, which is another Zr‐MOF that shows good catalytic activity toward PET degradation under similar reaction conditions. These results illustrate the diversity of applications for Zr‐MOFs and establish MOFs as a new class of polymer degradation catalysts with the potential to address long‐standing challenges associated with plastic waste.

Wu, Yufang↗

Catalytic Degradation of Polyethylene Terephthalate Using a Phase-Transitional Zirconium-Based Metal–Organic Framework

Polyethylene terephthalate (PET) is utilized as one of the most popular consumer plastics worldwide, but difficulties associated with recycling PET have generated a severe environmental crisis with most PET ending its lifecycle in landfills. We report that zirconium-based metal–organic framework (Zr-MOF) UiO-66 deconstructs waste PET into the building blocks terephthalic acid (TA) and mono-methyl terephthalate (MMT) within 24 hours at 260 °C (total yield of 98 % under 1 atm H 2 and 81 % under 1 atm Ar). Extensive structural characterization studies reveal that during the degradation process, UiO-66 undergoes an intriguing transformation into MIL-140A, which is another Zr-MOF that shows good catalytic activity toward PET degradation under similar reaction conditions. Here these results illustrate the diversity of applications for Zr-MOFs and establish MOFs as a new class of polymer degradation catalysts with the potential to address long-standing challenges associated with plastic waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer Retention Evaluation in a Heavy Oil Sand for a Polymer Flooding Application on Alaska’s North Slope

For a polymer flooding field trial in a heavy oil reservoir on Alaska’s North Slope, polymer retention is a key parameter. Because of the economic impact of retention, this parameter was extensively studied using field core material and conditions. Several important findings were noted. Polymer retention based on effluent viscosity measurements can be overestimated unless the correct (non-linear) relation between polymer concentration and viscosity is used. Polymer degradation (either mechanical or oxidative) can also lead viscosity-based measurements to overestimate retention. Inaccessible pore volume (IAPV) can be overestimated if insufficient brine is flushed through the sand between polymer banks. Around 100 pore volumes (PV) of brine may be needed to displace mobile polymer to approach a true residual resistance factor and properly measure IAPV. Even for a sand pack with kwsor = 20 mD, IAPV was zero for HPAM with molecular weight (Mw) of 18 million g/mol. Fine-grain particles (<20 μm) strongly impacted polymer retention values. Native NB#1 sand with a significant component of particles <20 μm exhibited 290 μg/g, while the same sand exhibited 28 μg/g after these small particles were removed. Polymer retention did not necessarily correlate with mineral composition. The NB#1, NB#3, and OA sands had similar elemental and clay compositions, but the NB#1 sand exhibited ~10 times higher retention than the NB#3 sand. Polymer retention did not necessarily correlate with permeability. NB#1 sand exhibited much higher retention than OA sand, even though NB#1 sand was twice as permeable as OA sand. No evidence of chromatographic separation of HPAM molecular weights was found in our experiments. Although retention tended to be greater without a residual oil saturation (than at Sor), the effect was not strong. Aging a core (with high oil saturation) at 60°C reduced HPAM retention by a factor of two. As expected, under similar conditions, polymer retention was greater for a higher Mw HPAM (18 million g/mol) than for a lower Mw HPAM (10-12 million g/mol). In many cases with high polymer retention values (e.g., 240 μg/g), polymer arrival at the end of the core was relatively quick, but achieving the injected concentration occurred gradually over many pore volumes. This effect was not due chromatographic separation of polymer molecular weights. Results from modeling of this behavior was consistent with concentrationdependent polymer retention. The form assumed for the retention function in a simulator can have an important impact on the timing and magnitude of the oil response from a polymer flood. Field-based observations can underestimate polymer retention, depending on when the tracer and polymer concentrations were measured and the assumptions made about reservoir heterogeneity.

Wang, Dongmei↗

Analytical Tools to Assess Polymer Biodegradation: A Critical Review and Recommendations

Many petroleum-derived plastic materials are highly recalcitrant and persistent in the environment, posing significant threats to human and ecological receptors due to their accumulation in ecosystems. In recent years, research efforts have focused on advancing biological methods for polymer degradation. Enzymatic depolymerization has emerged as particularly relevant for biobased plastic recycling, potentially scalable for industrial use. Biodegradation involves adsorption to the plastic solid surface, followed by an interfacial reaction, resulting in cleavage of bonds of polymer chains exposed on the surface. Here, widely varying substrate-specific kinetics are observed, with the polymer’s properties possessing a significant impact on the rate of this interfacial catalysis. Thus, there is a critical need for sensitive and accurate characterization of the material surface during and after interfacial depolymerization to fully understand the reaction mechanisms. Here, we provide a critical review of a range of techniques used in the analysis of material surfaces to characterize the chemical, topological, and morphological features relevant to the study of enzymatic biocatalysis, including microscopy techniques, spectroscopic techniques (e.g., X-ray diffraction analysis, Fourier transform infrared attenuated total reflectance spectroscopy, and mass spectrometry detection of analytes associated with degradation). Techniques for evaluation of surface energy and topology in their relevancy for sensitive detection of biological surface modifications are also discussed. In addition, this paper provides an overview of the strengths of these techniques and compares their performance in both sensitivity and throughput, including emerging techniques, which can be useful, particularly for the rapid analysis of the surface properties of polymeric materials in high-throughput screening of candidate biocatalysts. This research serves as a starting point in selecting and applying appropriate methodologies that provide direct evidence to the ongoing biotic degradation of polymeric materials.

Colachis, Matthew↗

Investigation of $\gamma$-irradiated polyvinylidene fluoride and its acute toxicity

Polyvinylidene fluoride (PVDF) is an industrial polymer with many applications. The EPR spectrum of polyvinylidene fluoride (PVDF) irradiated by γ-rays at low temperature (-196°C) provides evidence for the presence of radicals formed by loss of a fluorine atom from PVDF, and polyenyl radicals. Polyenyl radicals dominate in the polymer irradiated at room temperature. Peroxide radicals formed as a result of oxidation of primary free radicals by atmospheric oxygen are observed in the EPR spectrum of a polymer irradiated in air, or when air is introduced to a polymer irradiated in a vacuum. Carbonization and oxidation of γ-irradiated PVDF were observed in the XPS spectrum. A model for polymer degradation based on correlated G3(MP2) molecular orbital theory electronic structure calculations is described in this report. The presence of HF in the products and a low yield of products with the composition CxFyHz indicate the absence of noticeable thermal destruction of the main polymer chain upon heating to 220°C of both the initial and γ-irradiated PVDF. Although any HF released during the PVDF dehydrofluorination would be toxic, a study of the acute toxicity of γ-irradiated PVDF showed that the polymer does not exhibit toxicity after a single intragastric route of administration to mice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polymer-iron oxide hybrid films for controlling electrokinetic properties

Electrokinetic phenomena at polymer-water interfaces are central to technologies for water purification, ion separations, and energy conversion, yet the ability to systematically control polymer surface charge and associated electrokinetic processes remains limited. Here, we demonstrate a simple liquid-phase infiltration (LPI) method to synthesize polymer–metal oxide hybrid films with controllable interfacial properties. Hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) brushes grafted to silicon substrates were infiltrated with iron nitrate from ethanolic solution, followed by low-temperature thermal treatment to convert the infiltrated precursor into iron oxide. Spectroscopic ellipsometry, X-ray photoelectron spectroscopy, and thermogravimetric analysis confirmed oxide incorporation and hybrid film formation without polymer degradation. Electrokinetic measurements reveal that the hybrid films acquire the electrokinetic properties of the infiltrated oxide, with concentration-dependent streaming potentials and surface conductivities closely matching those of pure iron oxide films. These results establish metal oxide infiltration as a scalable and low-cost strategy for controlling interfacial charge in polymer surfaces. The approach introduces new materials and design parameters for tailoring ion selectivity, transport, and energy conversion, with broad implications for the development of advanced membranes, electrokinetic harvesting devices, and polymer-supported oxide electrodes.

36 MATERIALS SCIENCE↗

Weather aging effects on modified asphalt with rubber-polyethylene composites

Weather aging may cause more severe degradation on asphalt than thermal-oxidative aging due to the synergistic effect among oxygen, heat, ultraviolet (UV) radiation, and moisture. This study aimed to investigate weather aging effects and anti-aging mechanisms on asphalt modified with rubber-polyethylene (PE) composites. The modified binder blends and asphalt mixtures were subjected to outdoor weather aging. Dynamic shear rheometer (DSR), Fourier transform infrared spectroscopy (FTIR), Gel permeation chromatography (GPC), and optical microscopy tests were adopted to characterize the rheological properties, aging resistance, polymer degradation, and anti-aging mechanisms of modified binder blends, respectively. Mixture performance tests including Asphalt Pavement Analyzer (APA) and Ideal-CT tests were used to evaluate rutting and cracking resistance of asphalt mixtures. Results showed that weather aging can cause more severe aging to asphalt binders than pressure aging vessel (PAV) due to the severe degradation of PE particles. Rubber-PE composites alloyed with an extruder proved to stabilize PE particles in asphalt and significantly improve the aging resistance of modified binder blends. Furthermore, the enhanced aging resistance is attributed to the dispersion of PE particles and carbon black released by soluble rubbers.

Aging resistance↗

“Tailing” Phenomenon During Polymer Propagation at The Milne Point Polymer Flood

Chemical flooding simulators traditionally assume that polymer retention follows the Langmuir isotherm, while fractional-flow calculations assume concentration-independent retention. Both models predict a delay in propagation of the polymer front (in proportion to the retention value), followed by a rapid rise in produced polymer concentration to the injected level. In contrast, laboratory retention studies for the Milne Point polymer flood (North Slope of Alaska) consistently show virtually no delay in polymer propagation, a rapid rise in produced polymer to 70-90% of the injected concentration, followed by produced concentration gradually approaching the injected value over many pore volumes. From a practical viewpoint, this behavior means that retention causes no significant delay in propagation of the polymer bank (and therefore the oil bank), but the effective viscosity and displacement efficiency are less than originally planned. This paper explores why this polymer “tailing” phenomenon occurs. During core floods, effluent was analyzed for brine-tracer concentration, viscosity, total organic carbon, and total nitrogen. The latter three items allowed three independent measures of polymer concentration and polymer retention. Experiments were performed with Milne Point core material, oil, brine, and conditions. Mechanistic experiments were also performed with packs of glass beads with controlled levels of various minerals. In Milne Point cores, the presence of the tailing phenomenon was not sensitive to flow rate, polymer concentration, core heterogeneity, or whether the core was preserved, cleaned of oil, or cleaned and resaturated with oil, or cleaned, re-saturated and aged with oil. The three independent measures of polymer concentration confirmed that the tailing phenomenon was not an artifact associated with polymer degradation or detection interferences. Tailing was also observed during mechanistic floods using glassbead packs when sufficient levels of illite or kaolinite were present. This observation was consistent with high levels of illite noted in Milne Point cores. The tailing was not noted during mechanistic floods that contained beads with montmorillonite, chlorite, calcium carbonate, dolomite, siderite, pyrite, or calcium sulfate. A model is proposed to account for the tailing phenomenon. This work suggests that mineralogy analysis (especially for illite and kaolinite) may reveal whether tailing should be accounted for during simulations of polymer propagation/retention in a given field application.

Seright, Randy↗

Design, synthesis, and characterization of vinyl-addition polynorbornenes with tunable thermal properties

Unfunctionalized vinyl-addition polynorbornene (VAPNB) possesses many outstanding properties such as high thermal, chemical, and oxidative stability. These features make VAPNB a promising candidate for many engineering applications. However, VAPNB has a small service window between its glass transition temperature (T g ) and decomposition temperature (T d ), and it cannot be readily processed in a melt state. In this work, we demonstrate that the service window of VAPNBs can be tailored through the use of norbornene monomers bearing alkyl, aryl, and aryl ether substituents. The vinyl addition homopolymerization and copolymerization of these functionalized norbornyl-based monomers yielded VAPNBs with high T' g s (>150 °C) and large service windows (T d –T g > 100 °C), which are comparable to other commercial engineering thermoplastics. To further establish the feasibility of melt processing, a functionalized VAPNB material with T g = 209 °C and a service window of 170 °C was successfully extruded and molded into bars. Subsequent characterization of the bars by dynamic mechanical analysis (DMA), nuclear magnetic resonance spectroscopy (NMR), and gel permeation chromatography (GPC) revealed only minor signs of polymer degradation. Furthermore, these studies suggest that substituted VAPNBs could be developed into a new class of engineering thermoplastics that is compatible with workhorse melt processing techniques such as extrusion and injection molding, as well as emerging techniques such as extrusion-based 3D printing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding Recoverable vs Unrecoverable Voltage Losses and Long-Term Degradation Mechanisms in Anion Exchange Membrane Fuel Cells

Anion exchange membrane fuel cells (AEMFCs) have recently shown excellent progress in terms of their performance – e.g., achievable power and current density. However, very few AEMFCs have been demonstrated with the ability to operate for a long duration (>1000 h). In addition, it is unknown whether performance losses observed during operation are reversible, irreversible, or a combination of the two. In this study, a high-performance AEMFC operated continuously at 600 mA/cm 2 for 3600 h (150 days) at 80 °C with H 2 /O 2 reacting gases was demonstrated. Throughout testing, the electrochemical properties of the AEMFC were probed to provide information about performance degradation pathways and their degree of reversibility. It was found that a portion of the performance loss that occurs during AEMFC operation was due to suboptimal reaction conditions and can be recovered. At the end of the experiment, the cell was disassembled, and its structure and composition were evaluated at the nanoscale by aberration-corrected scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy. The structure and composition of the electrode were compared to cells at the beginning of their operational life. It was found that the primary mechanism for long-term AEMFC performance loss was catalyst agglomeration. During the operational time, there was no evidence of significant polymer degradation, likely due to the high hydration state of the cell. By documenting the long-term changes in high-performing AEMFCs, this work provides important information for the systematic design of cell components and demonstrates the importance of controlling cell operation, which can aid in the commercialization and widespread deployment of low-cost, long-life AEMFCs.

30 DIRECT ENERGY CONVERSION↗

In Situ EXAFS-Based Nanothermometry of Heterodimer Nanocrystals under Induction Heating

The ability to heat nanocrystalline materials through magnetic induction has been used in the fields of catalysis, biomedical sciences, and polymer degradation. However, the working temperature to which the inductively coupled material rises is still poorly understood. Herein, we use extended X-ray absorption fine structure spectroscopy in conjunction with thermal imaging to improve the understanding of heating in inductively coupled systems. After extraction of the Debye–Waller factor from the spectroscopy, we obtain the temperature of inductively heated nanocrystals from the correlated Debye model. We combine carbon-supported iron oxide nanocrystals as induction heating agents with platinum nanocrystals as thermal probes. By testing these nanocrystal species as both unattached nanocrystals and heterodimers, we report that nanostructured systems show a significant temperature difference of up to 73.60 °C when compared to their local support environment. Furthermore, this result has implications for inductively heated catalysis, magnetic hyperthermia for targeted cell death, and polymer synthesis.

09 BIOMASS FUELS↗

Biocomposite thermoplastic polyurethanes containing evolved bacterial spores as living fillers to facilitate polymer disintegration

The field of hybrid engineered living materials seeks to pair living organisms with synthetic materials to generate biocomposite materials with augmented function since living systems can provide highly-programmable and complex behavior. Engineered living materials have typically been fabricated using techniques in benign aqueous environments, limiting their application. In this work, biocomposite fabrication is demonstrated in which spores from polymer-degrading bacteria are incorporated into a thermoplastic polyurethane using high-temperature melt extrusion. Bacteria are engineered using adaptive laboratory evolution to improve their heat tolerance to ensure nearly complete cell survivability during manufacturing at 135 °C. Furthermore, the overall tensile properties of spore-filled thermoplastic polyurethanes are substantially improved, resulting in a significant improvement in toughness. The biocomposites facilitate disintegration in compost in the absence of a microbe-rich environment. Finally, embedded spores demonstrate a rationally programmed function, expressing green fluorescent protein. This research provides a scalable method to fabricate advanced biocomposite materials in industrially-compatible processes.

36 MATERIALS SCIENCE↗

The Bacteroidetes Aequorivita sp. and Kaistella jeonii Produce Promiscuous Esterases With PET-Hydrolyzing Activity

Certain members of the Actinobacteria and Proteobacteria are known to degrade polyethylene terephthalate (PET). Here, we describe the first functional PET-active enzymes from the Bacteroidetes phylum. Using a PETase-specific Hidden-Markov-Model- (HMM-) based search algorithm, we identified several PETase candidates from Flavobacteriaceae and Porphyromonadaceae. Among them, two promiscuous and cold-active esterases derived from Aequorivita sp. (PET27) and Kaistella jeonii (PET30) showed depolymerizing activity on polycaprolactone (PCL), amorphous PET foil and on the polyester polyurethane Impranil ® DLN. PET27 is a 37.8 kDa enzyme that released an average of 174.4 nmol terephthalic acid (TPA) after 120 h at 30°C from a 7 mg PET foil platelet in a 200 μl reaction volume, 38-times more than PET30 (37.4 kDa) released under the same conditions. The crystal structure of PET30 without its C-terminal Por-domain (PET30ΔPorC) was solved at 2.1 Å and displays high structural similarity to the Is PETase. PET30 shows a Phe-Met-Tyr substrate binding motif, which seems to be a unique feature, as Is PETase, LCC and PET2 all contain Tyr-Met-Trp binding residues, while PET27 possesses a Phe-Met-Trp motif that is identical to Cut190. Microscopic analyses showed that K. jeonii cells are indeed able to bind on and colonize PET surfaces after a few days of incubation. Homologs of PET27 and PET30 were detected in metagenomes, predominantly aquatic habitats, encompassing a wide range of different global climate zones and suggesting a hitherto unknown influence of this bacterial phylum on man-made polymer degradation.

59 BASIC BIOLOGICAL SCIENCES↗

Diffusion-limited hydrolysis in polymeric materials

Polymer degradation under aggressive environmental stressors often develops heterogeneities due to diffusion-limited reaction phenomena. This is well established for diffusion-limited oxidation (DLO), which is known to occur for most polymeric materials at elevated temperatures but has been less summarized for the conditions of diffusion-limited hydrolysis (DLH). Here, an overview of hydrolysis for several materials and a computational model, analogous to the underlying equations for DLO, able to define this diffusion-reaction system is presented. A systematic study of the influence of various parameters, such as water diffusivity, reaction rate and order, and a more in-depth focus on residual isocyanate hydrolysis in a polymeric methylene diphenyl diisocyanate (pMDI) based polyurethane (PU) foam is given. For this system, we present experimental data for model ‘input’ parameters and discuss predictions for different conditions. We conceptually compare the behavior of diffusion-limited oxidation to that of diffusion-limited hydrolysis (DLH). With the mathematical framework and key material properties presented herein, any DLH phenomena following Fickian diffusion behavior can be understood, modeled, and predicted.

36 MATERIALS SCIENCE↗

Opinion to address the personal protective equipment shortage in the global community during the COVID-19 outbreak

The current COVID-19 pandemic is stretching both the global supply for face masks and personal protective equipment (PPE). Production capacity is severely limited in many countries. This is a call for the R&D community, particularly to those in the polymer degradation and stability field. We have not only an opportunity but an obligation to engage and collaborate with virology and bio-medical experts. We require comparative R&D for extended, reuse and recyclability options. Additionally, there is urgent need for large scale institutional approaches and methods that can be quickly applied locally by non-experts with limited resources.

36 MATERIALS SCIENCE↗