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72 records · Page 4

Sandwich-Structured Photothermal Wood for Durable Moisture Harvesting and Pumping

Moisture capture coupled with photothermal regeneration provides an alternative and sustainable way to acquire fresh water. Composite moisture absorbents based on hygroscopic salts are environmentally friendly, economically feasible, and of high efficiency but suffer from the unavoidable desiccant leakage during absorption and evaporation-induced salt accumulation on material surfaces during desorption. Additionally, in this study, we develop a superhydrophobic–hydrophilic–hydrophobic photothermal wood embedded with CaCl 2 to promote the durability of the absorbents. The sandwich structure serves as a liquid/vapor gate allowing vapor transport but forbidding liquid permeation, enabling the condensation and evaporation within the wood. Beyond moisture harvesting, the sandwich-structured photothermal wood exhibits potential in indoor dehumidification by pumping the moisture through an absorption–desorption cycle.

36 MATERIALS SCIENCE↗

Microfluidic film evaporation with femtosecond laser-patterned surface

Systems, apparatuses, and methods for microfluidic fluid evaporation using femtosecond laser-patterned surfaces are disclosed. A microfluidic device may comprise a femtosecond laser-patterned substrate having at least one input path and at least one output path. The femtosecond laser-patterned substrate may comprise both superhydrophobic and superhydrophilic sections. Fluid deposited at an input path may be wicked to an output path due to the surface pattern. A heating device may be provided to heat the fluid to evaporate volatiles therefrom. Vacuums and gas streams may be used to aid in volatile removal. Gas streams may add gas to the microfluidic device to react with the fluid.

Pearson, Connor Daniel↗

Superhydrophobic Phosphonium Modified Robust 3D Covalent Organic Framework for Preferential Trapping of Charge Dispersed Oxoanionic Pollutants

Abstract Charge dispersed and less hydrophilic anionic pollutants are often difficult to be preferentially captured by common cationic framework materials. A gamma radiation modification approach is employed to anchor a superhydrophobic phosphonium‐containing coating on a robust crystalline 3D covalent organic framework (COF). By regulating the surface hydrophobicity, the prepared 3DCOF‐ g ‐VBPPh 3 Cl is endowed with a strong affinity for charge dispersed and less hydrophilic oxoanions, such as MnO 4 − , TcO 4 − and ReO 4 − , to surmount the Hofmeister bias, which much favors remediation of oxoanionic pollutants in complex aqueous systems. Batch and column experiments with 3DCOF‐g‐VBPPh 3 Cl in both tap water and simulated groundwater are performed, and rapid sequestration is achieved with removal efficacy up to 99.995%, record‐high distribution coefficient of 1.0 × 10 8 mL g −1 , and desirable priority over competing anions such as Cl − , SO 4 2− , HCO 3 − , and NO 3 − , confirming promise for remediation of charge dispersed anionic pollutants. Theoretical calculations reveal a mechanism of preferential capture based on electrostatic and dispersion interaction between charge dispersed anions and 3DCOF‐g‐VBPPh 3 Cl that effectively competes with solvation of the aqueous anions.

Wang, Yue↗

Corrosion Behavior of Hydrophobic Coatings in Aqueous CO2 Environments

Internal corrosion is caused by gas impurities such as CO2, moisture, and H2S, leading to material degradation. To combat this, the National Energy Technology Laboratory (NETL) developed a novel hydrophobic coating to reduce surface hydrophobicity and enhance the corrosion resistance of steel. NETL’s approach uses multi-layer hydrophobic coatings, a novel and promising coating that could potentially revolutionize the industry's approach to internal corrosion mitigation. This work aims to investigate the corrosion performance of the hydrophobic coating and determine the water uptake. Electrochemical corrosion experiments were carried out on bare X65 carbon steel without and with coating in 3.5 wt.% NaCl saturated with CO2 at 20 °C to follow the water uptake as a function of exposure time. Linear polarization resistance (LPR) was used to determine the corrosion rate for carbon steel immersed in a NaCl electrolyte saturated with CO2. Electrochemical impedance spectroscopy (EIS) of uncoated and coated bare carbon steel was investigated. The analyses of impedance models and water uptake behaviors of hydrophobic coatings were studied for 200 hours during the corrosion process. The water uptake was estimated using the Brasher and Kingsbury relation. The results showed that the superhydrophobic coating that was developed used innovative nano-based materials to act as protection layers on the surface of metallic parts against mechanical aggressors, corrosion, and fouling agents.

corrosion behavior↗

Resource Recovery and Environmental Protection in Wyoming’s Greater Green River Basin Using Selective Nanostructured Membranes (Final Report)

Produced water (PW) represents a sizable waste stream that is co-generated with oil and natural gas production. In 2021 Wyoming ranked 8th and 9th, respectively in domestic oil and natural gas production. In 2017 Wyoming ranked as the 4th highest generator of PW in the U.S, accounting for 7% of the total volume generated. In the context of being the 3rd most arid state in the U.S., the value of water reuse becomes obvious. PW reuse, and resource recovery, in any form requires some level of treatment to remove particulates, residual (free, dispersed) hydrocarbons, organics, and salts. The level of treatment depends on the requirements of the reuse, or resource recovery, application. PW management systems in Wyoming employ in order of volume of PW managed the following management strategies: reinjection for enhanced oil recovery, surface discharge, deep well injection, evaporation ponds (impoundments), and commercial management/treatment. Complicating treatment efforts are the relatively high concentrations of organics (natural and synthetic), dispersed/free hydrocarbons, benzene-toluene-ethylbenzene, and xylenes (BTEX) compounds, biologicals, salts, and minerals. Hydrocarbons (dispersed/dissolved crude oils) and BTEX compounds, as well as synthetic organics, present economic and environmental concerns. The former represents lost revenue, while the latter results in negative environmental impacts like emissions from surface impoundments. The overall objective of this proposal was to synthesize superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes for selectively concentrating and then separating BTEX compounds and oil and grease (O&G) from PW originating from the Greater Green River Basin (GGRB) in Wyoming. Three specific research aims were pursued to accomplish this overall objective. This final report details the development of the superhydrophobic and superhydrophilic membranes, as well as the design of the membrane module prototypes specifically. The technoeconomic assessment is separately reported in another document. 1. Aim #1 – Material optimization and performance evaluation of superhydrophilic/oleophobic and superhydrophobic/oleophilic membranes made by electrospinning/spraying. 2. Aim #2 – Design and construction of cross-flow membrane modules for selectively concentrating and then separating BTEX/oil from GGRB produced water. 3. Aim #3 – Techno-economic assessment of BTEX/oil recovery, and clean water production, using superhydrophilic/oleophobic and superhydrophobic/oleophilic membrane separation for GGRB PW. Superhydrophobic membranes were synthesized by electrospinning poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofibers onto polyester (PET) substrates and electrospraying nano-carbon black/PVDF-HFP onto the nanofibrous layer. These membranes were characterized by high (>8000 liters per square meter per hour per bar (LMH/bar)) permeance values for pure hydrocarbon phases and a high hydrocarbon selectivity (>96%) when treating GGRB PW. All results were obtained when operating the membrane in a crossflow configuration representative of actual field operating conditions. Solvent/oil properties, specifically viscosity and total surface energy/tension, affected permeance across the membrane, which resulted in light mineral oil (394 LMH/bar) and o-xylene (1834 LMH/bar) being characterized by lower permeance values in the pure phase tests. Mixed phase fluxes between 40 to 80 LMH were obtained for the PW when operating the membrane at a feed pressure of 0.3 bar. Flux decreased as the mixed phase concentration in the feed decreased pointing to the importance of maximizing the collision efficiency between the emulsion and the membrane surface and maximizing the emulsion concentration in the feed and the turbulence within the feed channel. These tests demonstrated that the superhydrophobic membranes developed here are a viable hydrocarbon recovery method for GGRB PWs and should be pursued for testing in pilot-scale trials. Superhydrophilic membranes were successfully synthesized via electrospinning/spraying using polyacrylonitrile (PAN) nanofibers as a base nanofibrous matrix. Integration of polyaniline (PANI) into the nanofibrous matrix produced a superior membrane, for water filtration applications, relative to PAN alone and reduced graphene oxide (RGO) when integrated into the nanofibrous matrix. This conclusion was based on the PANI-PAN resistance to flux loss (fouling) when treating model solvent/oil solutions representative of GGRB PWs and field collected PW from the GGRB. The synthesized PAN membranes outperformed a commercially available PAN membrane designed for oil/water separation. This finding indicates that the surface chemical and physical characteristics of the electrospun membranes presents improved properties for filtration of challenging waters like GGRB PWs. The electrospun membranes therefore show promise overall as a substitute for conventionally polymerized membranes in PW treatment applications. The PANI-PAN membrane specifically presents superior performance characteristics for concentration O&G prior to treatment by the hydrocarbon recovery membrane and producing high-quality filtrate for reuse and/or additional treatment (desalination).

02 PETROLEUM↗

Durable polymer-aerogel based superhydrophobic coatings: a composite material

Provided are polymer-aerogel composite coatings, devices and articles including polymer-aerogel composite coatings, and methods for preparing the polymer-aerogel composite. The exemplary article can include a surface, wherein the surface includes at least one region and a polymer-aerogel composite coating disposed over the at least one region, wherein the polymer-aerogel composite coating has a water contact angle of at least about 140° and a contact angle hysteresis of less than about 1°. The polymer-aerogel composite coating can include a polymer and an ultra high water content catalyzed polysilicate aerogel, the polysilicate aerogel including a three dimensional network of silica particles having surface functional groups derivatized with a silylating agent and a plurality of pores.

Kissel, David J.↗

The Unrealized Potential of Superhydrophobic Substrates in Advanced Life Support Systems

Nearly all water processing equipment aboard spacecraft is to a large extent controlled by capillary forces arising from substrate wetting conditions. Superhydrophobic wetting conditions provide an essentially passive means to keep water away from certain substrates providing a level of no-moving-parts phase separation and control. This work presents a host of non-wetting aqueous microgravity capillary fluidics phenomena arising from interactions with easily fabricated superhydrophobic substrates. The value of such phenomena for potential life support applications aboard spacecraft is clear, especially for substrate properties that are thermally robust, corrosion resistant, and self-cleaning for both long- and short term applications. Large length scale low-g demonstrations of the phenomena are provided in HD video format for the extensive drop tower tests conducted. The broader crosscutting impacts to numerous fluids processing operations for life support are discussed. Current practical applications addressed in light of superhydrophobicity include urine-processing, water recovery, fire safety, and others.

Superhydrophoic↗

Fluorine-Free Superhydrophobic Coatings: Rapid Fabrication and Highly Efficient Oil/Water Separation

In this work, a rapid method is demonstrated to obtain a fluorine-free superhydrophobic/superoleophilic coating by a simple two-step method: dip-coating and oven curing. The chemical structure of the coating is based on the crosslinking reaction of an alkyl methacrylate, a dimethacrylate (crosslinker) and a silane (adhesive), using AIBN as initiator, toluene as solvent, and silica nanoparticles to enhance surface roughness. Chemorheology results show that the coating is fully cured even in 20 min at 100 °C, exhibiting a water contact angle (CA) of 162 ± 2°, sliding angle (SA) of 4 ± 1°, nanometrical structures throughout the surface, and excellent adhesion properties for the mesh screen. The coating exhibits outstanding oil/water separation efficiency (96–99%) for seven different types of oil (gasoline, diesel, petroleum ether, hexane, toluene, chloroform, and dichloromethane), and in addition presents high recyclability. Based on nonisothermal TGA, the activation energy of degradation, calculated using the Kissinger and Ozawa models, is 113.5 and 114 kJ mol -1 , respectively. Finally, the coating is thermally aged at 150 °C: the CA exhibits a smooth decrease up to 129 ± 1° at 120 min, and FTIR analysis shows structural changes possibly related to the generation of thermal oxidation products.

36 MATERIALS SCIENCE↗

Superhydrophobic coated micro-porous carbon foam membrane and method for solar-thermal driven desalination

A solar membrane distillation apparatus includes a housing comprising a light transmitting wall. A solar distillation membrane is positioned in the housing to receive solar radiation transmitted through the light transmitting wall. The solar distillation membrane includes a porous graphitic foam and a coating of a hydrophobic composition on the surface and pores of the graphitic foam. A water chamber within the housing is provided for retaining water adjacent to the solar distillation membrane. A vapor chamber is provided for collecting water vapor distilling through the solar distillation membrane. A condenser is provided for condensing distilled water vapor from the vapor chamber into liquid water. A separation membrane and a method of solar distillation are also disclosed.

Jang, Gyoung Gug↗

A Water-Resistant Hydrogen-Bonded Organic Framework for Ethane/Ethylene Separation in Humid Environments

The separation of ethane (C 2 H 6 ) and ethylene (C 2 H 4 ) represents a crucial process for the production of polymer-grade C 2 H 4 , and adsorptive separation holds enormous promise for this industrially important but challenging task. Furthermore we report a new hydrogen-bonded organic frameworks (HIAM-102) with suitable channel and superhydrophobicity for preferential adsorption of C 2 H 6 over C 2 H 4 . HIAM-102 shows a C 2 H 6 /C 2 H 4 IAST selectivity of 1.9 and C 2 H 6 uptake of 48.25 cm 3 /g at 1 bar and 298 K. Benefitted from the hydrophobic pore surface, it can well-separate C 2 H 6 and C 2 H 4 under highly humid conditions as confirmed by experimental column breakthrough measurements. Computational calculations provide additional support for the experimental observations that the nonpolar channel of HIAM-102 interact favorably with C 2 H 6 over C 2 H 4 .

36 MATERIALS SCIENCE↗

3D Printed Parahydrophobic Surfaces as Multireaction Platforms

We report Parahydrophobic surfaces (PHSs) composed of arrays of cubic μ-pillars with a double scale of roughness and variable wettability were systematically obtained in one step and a widely accessible stereolithographic Formlabs 3D printer. The wettability control was achieved by combining the geometrical parameters (H = height and P = pitch) and the surface modification with fluoroalkyl silane compounds. Homogeneous distribution of F and Si atoms onto the pillars was observed by XPS and SEM-EDAX. A nano-roughness on the heads of the pillars was achieved without any post-treatment. The smallest P values lead to surfaces with static contact angles (CAs) >150° regardless of the H utilized. Interestingly, the relationship 0.6 ≤ H/P ≤ 2.6 obtained here was in good agreement with the H/P values reported for nano- and submicron pillars. Furthermore, experimental CAs, advancing and receding CAs, were consistent with the theoretical prediction from the Cassie–Baxter model. Structures covered with perfluorodecyltriethoxysilane with high H and short P lead to PHSs. Conversely, structures covered with perfluorodecyltrimethoxysilane exhibited a superhydrophobic behavior. Finally, several aqueous reactions, such as precipitation, coordination complex, and nanoparticle synthesis, were carried out by placing the reactive agents as microdroplets on the parahydrophobic pillars, demonstrating the potential application as chemical multi-reaction array platforms for a large variety of relevant fields in microdroplet manipulation, microfluidics systems, and health monitoring, among others.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design and synthesis of biobased superhydrophobic biochar catalyst derived from Citrus sinensis for biodiesel production using inedible oil feedstocks

In an one-pot in situ trans/esterification of low-grade feedstocks, the simultaneous presence of triglycerides (TAGs) and free fatty acids (FFAs) presents a dual catalytic challenge. While TAGs undergo transesterification to form biodiesel and glycerol, FFAs present in the feedstocks are esterified simultaneously, producing water as a by-product. This water can deactivate acid catalysts by interacting with their active sites, reducing catalytic efficiency and reusability. To overcome this, we developed a hydrophobic sulfonic acid-functionalized biochar catalyst derived from Citrus sinensis (orange peel) via sulfonation with H 2 SO 4 and subsequent silylation using hexamethyldisilazane (HMDS). The optimized catalyst exhibited a high surface area (355.09 m 2 g −1 ), sulfur content (5.33 wt%), and strong hydrophobicity (water contact angle: 154°). Compared to non-hydrophobic analogs, it showed enhanced activity and reusability (up to 10 cycles). Using response surface methodology with central composite design, a biodiesel yield of 99.1 ± 0.4% was achieved under optimal conditions. Life cycle assessment was performed to evaluate the environmental impacts of biodiesel production utilising the synthesized catalyst, considering 1000 kg of biodiesel produced as 1 functional unit. In conclusion, the recorded results showed the cumulative abiotic depletion of fossil resources over the entire biodiesel production process as 87 243.423 MJ and global warming potential as 4103.494 kg CO 2 equivalent.

Biochar↗

3D-Printed Repeating Re-Entrant Topography to Achieve On-Demand Wettability and Separation

While it is difficult and expensive to fabricate a complicated surface structure via conventional techniques, three-dimensional (3D) printing serves as a time-efficient and cost-efficient alternative. In the current study, a novel repeating re-entrant topography is fabricated by two-photon polymerization 3D printing. The experimental results show that the repeating re-entrant surface enhances the desired on-demand surface wettability. Furthermore, the 3D-printed membranes with the repeating re-entrant structures enable the efficient on-demand separation of liquid mixtures with high flux, which is critical for the wastewater treatment in the chemical industry.

36 MATERIALS SCIENCE↗

Tunable 1D and 2D Polyacrylonitrile Nanosheet Superstructures

Carbon superstructures are widely applied in energy and environment-related areas. Among them, the flower-like polyacrylonitrile (PAN)-derived carbon materials have shown great promise due to their high surface area, large pore volume, and improved mass transport. In this work, we report a versatile and straightforward method for synthesizing one-dimensional (1D) nanostructured fibers and two-dimensional (2D) nanostructured thin films based on flower-like PAN chemistry by taking advantage of the nucleation and growth behavior of PAN. The resulting nanofibers and thin films exhibited distinct morphologies with intersecting PAN nanosheets, which formed through rapid nucleation on existing PAN. We further constructed a variety of hierarchical PAN superstructures based on different templates, solvents, and concentrations. These PAN nanosheet superstructures can be readily converted to carbon superstructures. As a demonstration, the nanostructured thin film exhibited a contact angle of ~180° after surface modification with fluoroalkyl monolayers, which is attributed to high surface roughness enabled by the nanosheet assemblies. In conclusion, this study offers a strategy for the synthesis of nanostructured carbon materials for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Scale up, Field testing, and Optimization of Nontoxic, Durable, Economical Coatings for Control of Biofouling and Corrosion (Abstract Only)

The objective of this project is the technical maturation and demonstration of a durable, economical, and nontoxic coating, Superhydrophobic Lubricant Infused Composite (SLIC), that will prevent fouling organisms from growing on marine and hydrokinetic (MHK) structures and prevent invasive mussels from growing on hydropower structures. SLIC technology was developed and patented by PNNL. It combines multiple antifouling mechanisms to provide excellent antifouling performance, durability, and low hydrodynamic drag without using toxic materials. Advanced proof-of-concept testing and demonstrations completed during a Phase 1 TCF project attracted industry interest and partnerships for this Phase 2 effort focused on maturation of a commercial product. Specific tasks and tests will shift the development emphasis to optimizing formulations, validating antifouling performance to address specific application needs, explore compatibility with other paint systems, develop a product with useful shelf life (in can), and determine curing times and effective applications methodology. Phase 2 efforts will focus upon technology transfer and commercialization of the technology with the industrial team. Industrial partners now include a coatings development specialist (Lorama), hydrophobic material manufacturer and paint developer (Dry Surface Technologies), nontoxic biodegradable lubricants manufacturer (BioBlend), and aquatic applications specialists (Prometheus Innovations, River Connectivity Systems). Engagement with the MHK device developers, the PNNL Marine and Coastal Research Laboratory (MCRL) test site in Sequim WA, Bureau of Reclamation, and Taylor Shellfish throughout the project will provide topical expertise and field test sites that will deliver crucial real-world performance data. Through this Phase 2 effort, SLIC will transition from a Technical Readiness Level (TRL) 5 to TRL 6 and long-term performance data will be acquired through demonstrations. The field test data will allow optimization of SLIC formulation to enhance performance (e.g., durability) and packaging, which are key de-risking activities for technology transfer and ultimately to the production of a viable commercial product.

13 HYDRO ENERGY↗

Improving Marine Energy Production Through Commercialization of a Low Cost, Drag-Reducing Slippery Coating (CRADA 679 Abstract)

Marine energy capture systems offer great promise for providing clean energy, but they operate in a challenging and dynamic environment and must be optimized to the highest extent possible. Computational studies predict that drag reduction on marine energy and blue economy systems will result in meaningful improvements in energy efficiency. Based on extensive coating experience, PNNL is proposing to bring to market a new drag-reducing coating called Superhydrophobic Lubricant-Infused Drag-Efficient Coating – SLIDE-Coat. PNNL has a deep knowledge base regarding this class of slippery coatings, and we have a group of enthusiastic industry partners who have committed to partnering, conducting field testing, and providing well over 50% cost share. In addition to validating the technology, the team will create a commercialization roadmap to ensure the commercial success of the technology after the government-sponsored two-year program is complete. The main technical goal is to design, manufacture, and experimentally validate a new coating that can reduce hydrodynamic skin friction drag by 20%. The main commercialization goal is to develop a roadmap that identifies activities needed to complete SLIDE-Coat’s development after the conclusion of this project. Year 1 will focus on adaptation and modification of the existing SLIC coating system to optimize drag reduction and assessment and quantification of drag reduction on relevant materials in a laboratory setting. Year 2 will focus on optimizing and demonstrating drag reduction with preferred coatings. The manufacturability, ease of application, adhesion to relevant surfaces, and consistency will be assessed. Quantification of drag reduction on prototype materials in a relevant marine field setting will be executed.

16 TIDAL AND WAVE POWER↗