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At least 19 records

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DOE OSTI2024

The Significant Differences in Solvation Thermodynamics of C1–C3 Oxygenates in Hydrophilic versus Hydrophobic Pores of a Hydrophilic Ti-FAU Zeolite Model

The rates of catalytic reactions have been observed to be dramatically different in zeolites, depending on if they are hydrophobic or hydrophilic. Hypotheses aimed at explaining this behavior have pointed to various solvent molecule and zeolite properties as having influence on entropy. Herein, the influence of various solvent and adsorbate properties on the solvation energies, entropies, and free energies of eleven C1-C3 oxygenates in hydrophobic and hydrophilic pores within a hydrophilic model of Ti-FAU zeolite are tested. The results indicate significant variation in the calculated solvation thermodynamics depending on the adsorbate type, as well as if it is bound within a hydrophobic or hydrophilic pore. Further, while solvation energies are related to solvent-adsorbate interactions, solvation entropies have multiple contributions, and these differ depending on if the adsorbate is in a hydrophobic or hydrophilic pore. Specifically, solvation entropies in hydrophobic pores are related to solvent structural properties, whereas solvation entropies in hydrophilic pores are related to adsorbate polarity. Here, the large range of results obtained from two different pores within one zeolite model with minimal unique adsorption sites suggests that solvation behavior in zeolites is complicated and that the phenomena that control observed performance depend on the zeolite, reaction, and solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1994

Method of making a membrane having hydrophilic and hydrophobic surfaces for adhering cells or antibodies by using atomic oxygen or hydroxyl radicals

A portion of an organic polymer article such as a membrane is made hydrophilic by exposing a hydrophobic surface of the article to a depth of about 50 to about 5000 angstroms to atomic oxygen or hydroxyl radicals at a temperature below 100C., preferably below 40 C, to form a hydrophilic uniform surface layer of hydrophilic hydroxyl groups. The atomic oxygen and hydroxyl radicals are generated by a flowing afterglow microwave discharge, and the surface is outside of a plasma produced by the discharge. A membrane having both hydrophilic and hydrophobic surfaces can be used in an immunoassay by adhering antibodies to the hydrophobic surface. In another embodiment, the membrane is used in cell culturing where cells adhere to the hydrophilic surface. Prior to adhering cells, the hydrophilic surface may be grafted with a compatibilizing compound. A plurality of hydrophilic regions bounded by adjacent hydrophobic regions can be produced such that a maximum of one cell per each hydrophilic region adheres.

Koontz, Steven L.↗

NASA NTRS2016

Hydrophilic-Core Microcapsules and Their Formation

Hydrophilic-core microcapsules and methods of their formation are provided. A hydrophilic-core microcapsule may include a shell that encapsulates water with the core substance dissolved or dispersed therein. The hydrophilic-core microcapsules may be formed from an emulsion having hydrophilic-phase droplets dispersed in a hydrophobic phase, with shell-forming compound contained in the hydrophilic phase or the hydrophobic phase and the core substance contained in the hydrophilic phase. The shells of the microcapsules may be capable of being broken down in response to being contacted by an alkali, e.g., produced during corrosion, contacting the shell.

Calle, Luz M.↗

NASA NTRSDate not supplied

EMU Ventilation Loop Simulation and Assessment of Contamination of the EMU Sublimator Hydrophilic Coating

Controlling moisture is a critical function performed in the space suit during extra vehicular activity (EVA) missions. Currently, this function is carried out by a sublimator, which is coated with a hydrophilic material. Tests have shown that siloxane compounds can off gas from the helmet absorption pad extension (HAP-E) and helmet absorption band (HAB) when they are at elevated temperatures and initial testing indicated that siloxanes could damage the hydrophilic coating. Therefore, more representative testing was needed. Important test considerations were source and destination kinetics, system geometries, scrubbing efficacy by the activated charcoal from the Metox canister, and other benefits that derive from active condensation occurring on the hydrophilic coating during exposure. A ventilation loop that was originally constructed to test hardware for control of CO2 and trace contaminants under EVA conditions was modified to conduct the siloxane off gassing tests. A vacuum compatible acrylic chamber was installed to simulate the suit volume. A steel beaker located in the chamber contained the HAP-E and HAB materials and was heated with two band heaters. The flow exiting the chamber passed through a LiOH cannister, which contained carbon beds to simulate their function in the Metox. The flow then was directed into a smaller volume that contained a coupon, which was coated with the hydrophilic material and was maintained at 10°C (50°F). Moisture was injected upstream of the suit volume simulator to maintain the dew point between 12.7°C (55°F) and 18.3°C (65°F). The pressure was controlled to between 3.8 and 4.4 psia, and the flow was held at 6 acfm. The system was run for an equivalent of 25 ten-hour EVAs, where the HAP-E/HAB materials were changed out after each EVA. The effect of the potential off gassing on the coupon was measured after each EVA period.

PLSS↗

NASA NTRS2004

New Hydrophilic, Composite Membranes for Air Removal from Water Coolant Systems

Liquid coolants are commonly used as thermal transport media to increase efficiency and flexibility in aerospace vehicle design. The introduction of gas bubbles into the coolant can have negative consequences, including: loss of centrifugal pump prime, irregular sensor readings, and blockage of coolant flow to remote systems. One solution to mitigate these problems is the development of a passive gas removal device, or gas trap, installed in the flight cooling system. In this study, a new hydrophilic, composite membrane has been developed for passage of the coolant fluid and retention of gas bubbles. The trapped bubbles are subsequently vented from the system by a thin, hydrophobic, microporous membrane. The original design for this work employed a homogeneous membrane that was susceptible to fouling and pore plugging. Spare gas traps of this variety have degraded during storage, and recreation of the membranes has been complicated due to problems with polymer duplication and property variations in the final membranes. In this work, replacements have been developed based on deposition of a hydrophilic polymer on the bore-side of a porous polyethylene (PE) tube. The tube provides excellent chemical and mechanical stability, and the hydrophilic layer provides retention of gas bubbles. Preliminary results have shown that intimate contact is required between the deposited layer and the substrate to overcome material differences. This has been accomplished by presoaking the membrane tube in the solvent to raise its surface energy. Polymer solutions of various concentrations have been used to promote penetration of the polymer layer into the porous substrate and to control separation layer thickness. The resulting composite membranes have shown repeatable decrease in nitrogen permeability, which is indicative of a decrease in membrane pore size. Studies with water permeation have yielded similar results. We have observed some swelling of the added polymer layer, which causes a slight decrease in membrane pore size, and should result in improved bubble retention. Preliminary studies have also been performed on gas retention in flowing systems. Initial results have been promising, with negligible gas permeation for the coated membranes compared to 100% gas permeation in the uncoated tube.

Ritchie, Stephen M. C.↗

NASA NTRS2013

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-interactive Chemicals Contained in Boundary Layer-targeted Emulsions

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, or water. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Richmond, Robert Chafee↗

NASA NTRS2016

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

Richmond, Robert Chaffee↗

NASA NTRS2017

Friction and Wear Modifiers Using Solvent Partitioning of Hydrophilic Surface-Interactive Chemicals Contained in Boundary Layer-Targeted Emulsions

A wear and/or friction reducing additive for a lubricating fluid in which the additive is a combination of a moderately hydrophilic single-phase compound and an anti-wear and/or anti-friction aqueous salt solution. The aqueous salt solution produces a coating on boundary layer surfaces. The lubricating fluid can be an emulsion-free hydrophobic oil, hydraulic fluid, antifreeze, water, or a water-based lubricant. Preferably, the moderately hydrophilic single-phase compound is sulfonated castor oil and the aqueous salt solution additionally contains boric acid and zinc oxide. The emulsions produced by the aqueous salt solutions, the moderately hydrophilic single-phase compounds, or the combination thereof provide targeted boundary layer organizers that significantly enhance the anti-wear and/or anti-friction properties of the base lubricant by decreasing wear and/or friction of sliding and/or rolling surfaces at boundary layers.

Richmond, Robert Chaffee↗

DOE OSTI2023

Effect of Hydrophilicity-Imparting Substituents on Exciton Delocalization in Squaraine Dye Aggregates Covalently Templated to DNA Holliday Junctions

Molecular aggregates exhibit emergent properties, including the collective sharing of electronic excitation energy known as exciton delocalization, that can be leveraged in applications such as quantum computing, optical information processing, and light harvesting. In a previous study, we found unexpectedly large excitonic interactions (quantified by the excitonic hopping parameter J m,n ) in DNA-templated aggregates of squaraine (SQ) dyes with hydrophilic-imparting sulfo and butylsulfo substituents. Here, we characterize DNA Holliday junction (DNA-HJ) templated aggregates of an expanded set of SQs and evaluate their optical properties in the context of structural heterogeneity. Specifically, we characterized the orientation of and J m,n between dyes in dimer aggregates of non-chlorinated and chlorinated SQs. Here, three new chlorinated SQs that feature a varying number of butylsulfo substituents were synthesized and attached to a DNA-HJ via a covalent linker to form adjacent and transverse dimers. Various characteristics of the dye, including its hydrophilicity (in terms of log P o/w ) and surface area, and of the substituents, including their local bulkiness and electron withdrawing capacity, were quantified computationally.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Influence of ion-pairing reagents on the separation of intact glycoproteins using hydrophilic-interaction liquid chromatography - high-resolution mass spectrometry

Hydrophilic-interaction liquid chromatography (HILIC) of intact proteins offers high-resolution separations of glycoforms of glycoproteins differing in the number of (neutral) glycans. However, to obtain efficient separations it is essential that the positively charged sites of the proteins are shielded by acidic (negative) ion-pair reagents (IPRs), so as to enhance the contribution of the hydroxyl groups of the (neutral) sugars in the glycoprotein. Here, we studied the influence of various IPRs that differ in physico-chemical properties, such as hydrophobicity and acidity, on the capillary-scale HILIC separation of intact (glyco)proteins. We evaluated the use of fluoroacetic acid (MFA), difluoroacetic acid (DFA), trifluoroacetic acid (TFA), and heptafluorobutyric acid (HFBA) as diluents for sample preparation, as solvents for sample loading on a reversed-phase trap prior to the HILIC separation, and as mobile-phase components for HILIC and HILIC-MS. To reduce the contribution of ion-exchange interaction with the (silica-based) stationary phase, we used an acrylamide-based monolithic column. We studied the influence of the different IPRs on each step of the separation of a mixture of proteins of different size and hydrophilicity and on the separation of the five glycoforms of ribonuclease B. The content of IPR in the sample was shown not to affect the separation and the MS detection. However, a low content of TFA and DFA in the mobile phase is favourable, as it reduces adduct formation and leads to higher signal intensity. The optimized HILIC conditions successfully resolved nine major glycoforms groups of a ~40 kDa glycoprotein horseradish peroxidase (HRP), as an example of a complex glycoprotein.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2023

Hydrophilic and Apolar Hydration in Densely Grafted Cationic Brushes and Counterions with Large Mobilities

We employ all-atom molecular dynamics (MD) simulation framework to unravel water microstructure and ion properties for cationic [Poly(2-(methacryloyloxy)ethyl trimethylammonium chloride] (PMETAC) brushes with chloride ions as counterions. First, we identify locally separate water domains (or first hydration shells) each around the {N(CH 3 ) 3 } + and the C=O functional groups of the PMETAC chain and one around the Cl - ion. These first hydration shells around the respective moieties overlap and the extent of the overlap depends on the nature of the species triggering it. Second, despite the overlap, the water molecules in these domains demonstrate disparate properties dictated by the properties of the atoms/groups around which they are located. For example, the presence of the methyl groups make the {N(CH 3 ) 3 } + group trigger apolar hydration as evidenced by the corresponding orientation of the dipole of the water molecules around the {N(CH 3 ) 3 } + moiety. These water molecules around the N(CH 3 ) 3 } + group also have enhanced tetrahedrality as compared to the water molecules constituting the hydration layer around the C=O group and the Cl - counterion. Our simulations also identify that there is an intervening water layer between the Cl - ion and {N(CH 3 ) 3 } + group: this layer prevents the Cl - ion from coming very close to the {N(CH 3 ) 3 } + group. As a consequence, there is a significantly large mobility of the Cl - ions inside the PMETAC brush layer. Furthermore, the C=O group of the PE chain, due to the partial negative charge on the oxygen atom and the specific structure of the PMETAC brush system, demonstrates strongly hydrophilic behavior and enforces a specific dipole response of water molecules analogous to that experienced by water around anionic species of high charge density. As a result, our findings confirm that PMETAC brushes undergo hydrophilic hydration at one site, apolar hydration at another site, and ensures large mobility of the supported Cl- counterions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1978

Enhanced hydrophilicity of chlorided aluminum oxide particulates

An enhancement of hydrophilicity for chlorided aluminas was demonstrated by the results obtained from gaseous H2O sorptions at 70-, 80-, and 86-percent relative humidity on alpha and gamma aluminum oxide particulates and on alpha and gamma aluminum oxide particulates with a chemisorbed surface chloride phase (produced by reactions of gaseous HCl + H2O on alumina). Continuous sorption histories for H2O on chlorided aluminas having specific surface areas that range from 7 to 227 sq m/g before chloriding indicated that initial sorption rates were directly linked to the extent of chemisorbed chlorided coverage and implied the same relationship for sorption capacities. The initial sorption rate on chlorided aluminas was found to be slower for the first exposure to H2O than for subsequent exposures (which reached equilibrated H2O coverages much faster), suggesting that slow chemical reactions between H2O and chlorided alumina may have been operative during initial exposures. Chlorided alumina particles were found to remain very hydrophilic (relative to nonchlorided analogs) for several H2O sorption/desorption cycles.

Cofer, W. R., III↗

NASA NTRS2010

International Space Station Common Cabin Air Assembly Condensing Heat Exchanger Hydrophilic Coating Failures and Lessons Learned

The ability to control the temperature and humidity of an environment or habitat is critical for human survival. These factors are important to maintaining human health and comfort, as well as maintaining mechanical and electrical equipment in good working order to support the human and to accomplish mission objectives. The temperature and humidity of the International Space Station (ISS) United States On-orbit Segment (USOS) cabin air is controlled by the Common Cabin Air Assembly (CCAA). The CCAA consists of a fan, a condensing heat exchanger (CHX), an air/water separator, temperature and liquid sensors, and electrical controlling hardware and software. The CHX is the primary component responsible for control of temperature and humidity. The CCAA CHX contains a chemical coating that was developed to be hydrophilic and thus attract water from the humid influent air. This attraction forms the basis for water removal and therefore cabin humidity control. However, there have been several instances of CHX coatings becoming hydrophobic and repelling water. When this behavior is observed in an operational CHX, the unit s ability to remove moisture from the air is compromised and the result is liquid water carryover into downstream ducting and systems. This water carryover can have detrimental effects on the cabin atmosphere quality and on the health of downstream hardware. If the water carryover is severe and widespread, this behavior can result in an inability to maintain humidity levels in the USOS. This paper will describe the operation of the five CCAAs within in the USOS, the potential causes of the hydrophobic condition, and the impacts of the resulting water carryover to downstream systems. It will describe the history of this behavior and the actual observed impacts to the ISS USOS. Information on mitigation steps to protect the health of future CHX hydrophilic coatings and potential remediation techniques will also be discussed.

Balistreri, Steven F.↗

NASA NTRS2013

International Space Station Common Cabin Air Assembly Condensing Heat Exchanger Hydrophilic Coating Operation, Recovery, and Lessons Learned

The ability to control the temperature and humidity of an environment or habitat is critical for human survival. These factors are important to maintaining human health and comfort, as well as maintaining mechanical and electrical equipment in good working order to support the human and to accomplish mission objectives. The temperature and humidity of the International Space Station (ISS) United States On-orbit Segment (USOS) cabin air is controlled by the Common Cabin Air Assembly (CCAA). The CCAA consists of a fan, a condensing heat exchanger (CHX), an air/water separator, temperature and liquid sensors, and electrical controlling hardware and software. The CHX is the primary component responsible for control of temperature and humidity. The CCAA CHX contains a chemical coating that was developed to be hydrophilic and thus attract water from the humid influent air. This attraction forms the basis for water removal and therefore cabin humidity control. However, there have been several instances of CHX coatings becoming hydrophobic and repelling water. When this behavior is observed in an operational CHX in the ISS segments, the unit s ability to remove moisture from the air is compromised and the result is liquid water carryover into downstream ducting and systems. This water carryover can have detrimental effects on the ISS cabin atmosphere quality and on the health of downstream hardware. If the water carryover is severe and widespread, this behavior can result in an inability to maintain humidity levels in the USOS. This paper will describe the operation of the five CCAAs within the USOS, the potential causes of the hydrophobic condition, and the impacts of the resulting water carryover to downstream systems. It will describe the history of this behavior and the actual observed impacts to the ISS USOS. Information on mitigation steps to protect the health of future CHX hydrophilic coatings as well as remediation and recovery of the full heat exchanger will be discussed.

Balistreri, Steven F.↗

NASA NTRS2014

Condensing Heat Exchanger with Hydrophilic Antimicrobial Coating

A multi-layer antimicrobial hydrophilic coating is applied to a substrate of anodized aluminum, although other materials may form the substrate. A silver layer is sputtered onto a thoroughly clean anodized surface of the aluminum to about 400 nm thickness. A layer of crosslinked, silicon-based macromolecular structure about 10 nm thickness overlies the silver layer, and the outermost surface of the layer of crosslinked, silicon-based macromolecular structure is hydroxide terminated to produce a hydrophilic surface with a water drop contact angle of less than 10.degree.. The coated substrate may be one of multiple fins in a condensing heat exchanger for use in the microgravity of space, which has narrow channels defined between angled fins such that the surface tension of condensed water moves water by capillary flow to a central location where it is pumped to storage. The antimicrobial coating prevents obstruction of the capillary passages.

Thomas, Christopher M.↗

DOE OSTI2023

The Production of Low Ash Coals Using the Hydrophobic-Hydrophilic Separation Process with Novel Developments

Froth flotation is a common mineral processing method in coal preparation. This process becomes less efficient, however, as particle size is reduced, and ultrafine particles are often discarded prior to froth flotation, contributing to a substantial amount of coal waste in impoundments. Because of the land-use and risk of an impoundment failure, these impoundments pose an environmental liability. To address ultrafine coal rejection, researchers at Virginia Tech developed the hydrophobic-hydrophilic separation (HHS) process. Unlike in froth flotation, HHS uses an organic solvent to separate and dewater hydrophobic particles from hydrophilic minerals. Past work on the HHS process yielded promising results. In particular, the HHS process has produced a low-ash (<2%) and low moisture (<8%) product, which is a viable feed stock for carbon products. In this work, an investigation of the effects of auxiliary processes on the HHS process was conducted. The auxiliary processes included grinding, pre-concentration, and reagent conditioning. This work also contains an investigation on the interaction between two primary unit operations in the HHS process: oil agglomeration and de-emulsification. Lastly, to make the HHS process more viable for commercial scale-up, a novel unit operation was developed and tested that performs comparably to the current HHS process.

01 COAL, LIGNITE, AND PEAT↗

DOE OSTI2024

Exploring the Structural Behavior of Hydrophilic Diglycolamide Complexes with the Lanthanides and Actinides

In the ongoing effort to meet the anticipated rise in energy demand while maintaining the full-scale abandonment of natural gas and coal, a substantial shift in our considerations of green energy is required through the wider adoption of nuclear power. However, the advantages of nuclear power are hindered by the challenges of safely managing nuclear waste. Hydrophilic diglycolamides (DGA) ligands have been explored for use as stripping agents in various lanthanide and actinide partitioning processes. Additionally, the separation of lanthanide fission products and transplutonic actinides can serve multifaceted advantages in that the separation neutron poisoning rare earth element (REE) fission products from minor actinides from used nuclear fuel (UNF) can be mutually beneficial to the fundamental research behind REE separations and UNF separations. With this in mind, understanding the bonding differences between the Ln3+ and An3+ ions as a function of DGA structure, such as varying the alkyl groups on each of the amide functional groups, has an influence on the molecule’s selectivity and solubility and whose changes in molecular architecture also impact the radiolytic behavior of these molecules. As such, crystal structures of (Y3+, La-Lu3+, excl. Pm, Pu3+/4+, Am3+, Bk3+, and Cf3+) with hydrophilic diglycolamides show the systematic progression, and changes in coordination habits, as a function of a f-element ions. These coordination complexes see a consistent decrease in bond lengths and changes in the coordination environment while traversing across the f-elements, owing to the effects of the lanthanide contraction as well as local geometry around the metal centers. Direct comparisons of lanthanide with actinide DGA structures display both striking similarities in coordination with earlier actinides of Pu and Am, while later actinides of Bk and Cf display a complete breakdown of these observed trends. This work has also presented the rare opportunity to study homoleptic DGA compounds across multiple oxidation states have provided insight into their nuanced differences in structural chemistry.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2023

Pilot Scale Testing of the Hydrophobic-Hydrophilic Separation Process to Produce Value-Added Products from Waste Coal

The primary objective of this project was to demonstrate the technical and economic feasibility of using the hydrophobic-hydrophilic separation (HHS) process to produce high-purity, value-added clean coal that could serve as feedstock for specialty carbon products from waste coal. An existing one-skid (i.e., the entire unit fits on a single tractor-trailer) HHS pilot-scale facility was used to process bituminous and anthracite waste coals to produce: 1) a clean coal containing less than 5% ash (super-clean) and 2) another containing less than 1.5% ash (ultra-clean), all of which contain single-digit moistures. Sufficient quantities of these products were to be generated to permit detailed evaluations by potential customers producing or developing new, high-value market applications. In addition, the project included the evaluation of several process improvements to reduce the capital and operating costs for a commercial HHS plant. A final objective was to complete an economic analysis, market-penetration analysis, and technology-gap analysis of the HHS technology and its products.

01 COAL, LIGNITE, AND PEAT↗