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313 records · Page 18

All sources NASA NTRS DOE OSTI

NASA NTRS2006

4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives investigated previously include alkyl pyrocarbonates. Those additives help to improve low-temperature performances by giving rise to the formation of SEIs having desired properties. The formation of the SEIs is believed to be facilitated by products (e.g., CO2) of the decomposition of these additives. These decomposition products are believed to react to form Li2CO3-based films on the carbon electrodes. The present additive, 4-vinyl-1,3-dioxolane-2-one, also helps to improve lowtemperature performance by contributing to the formation of SEIs having desired properties, but probably in a different manner: It is believed that, as part of the decomposition process, the compound polymerizes on the surfaces of carbon electrodes.

Smart, Marshall↗

NASA NTRS2003

Environmentally Safer, Less Toxic Fire-Extinguishing Agents

Fire-extinguishing agents comprising microscopic drops of water microencapsulated in flame-retardant polymers have been proposed as effective, less toxic, non-ozone-depleting, non-globalwarming alternatives to prior fire-extinguishing agents. Among the prior fire-extinguishing agents are halons (various halocarbon fluids), which are toxic and contribute both to depletion of upperatmospheric ozone and to global warming. Other prior fire-extinguishing agents are less toxic and less environmentally harmful but, in comparison with halons, are significantly less effective in extinguishing fires. The proposal to formulate new waterbased agents is based on recent success in the use of water mist as a fire-suppression agent. Water suppresses a flame by reducing the flame temperature and the concentration of oxygen available for the combustion process. The temperature is reduced because the water droplets in the mist absorb latent heat of vaporization as they evaporate. The concentration of oxygen is reduced because the newly generated water vapor displaces air. Unfortunately, water mists are difficult to produce in confined spaces and can evaporate before they reach the bases of flames. The proposal addresses both of these issues: The proposed fire-extinguishing agents would be manufactured in microencapsulated form in advance, eliminating the problem of generating mists in confined spaces. Because of the microencapsulation, the droplets would not evaporate until exposed directly to the heat of flames. In addition, the proposal calls for the introduction of free radicals that would inhibit the propagation of the chemical reactions of the combustion reactions. Manufacturing of a fire-extinguishing agent according to the proposal would begin with the formulation of a suitable polymer (e.g., a polybromostyrene) that would contribute free radicals to the combustion process. The polymer would be dissolved in a suitable hydrocarbon liquid (e.g., toluene). Water would be dispersed in the polymer/toluene solution, then another hydrocarbon liquid (e.g., hexane) that is not a solvent for the polymer would be added to the mixture to make the dissolved polymer precipitate onto the water droplets. The resulting polymer-coated droplets would be removed from the coating mixture by filtration, dried, and stored for use.

Parrish, Clyde F.↗

NASA NTRS1993

Joint pain and Doppler-detectable bubbles in altitude (Hypobaric) decompression

The observation that altitude decompression sickness (DCS) is associated with pain in the lower extremities is not new, although it is not a consistent finding. DCS in divers is generally in the upper body, an effect often attributed to non-loading of the body while immersed. In caisson workers, DCS is reported more in the lower extremities. Surprisingly, many researchers do not mention the location of DCS joint pain, apparently considering it to be random. This is not the case for the tissue ratios encountered in studying decompression associated with simulated EVA. In NASA/JSC tests, altitude DCS generally presented first in either the ankle, knee, or hip (83 percent = 73/88). There was a definite statistical relation between the maximum Spencer precordial Doppler Grade and the incidence of DCS in the extremity, although this is not meant to imply a casual relation between circulating gas bubbles and joint pain. The risk of DCS with Grade 4 was considerably higher than that of Grades 0 to 3. The DCS risk was independent of the 'tissue ratio.' There was a predominance of lower extremity DCS even when exercise was performed with the upper body. The reason for these locations we hypothesize to be attributed to the formation of tissue gas micronuclei from kinetic and tensile forces (stress-assisted nucleation) and are the result of the individuals ambulating in a 1g environment. Additionally, since these showers of Doppler bubbles can persist for hours, it is difficult to imagine that they are emanating solely from tendons and ligaments, the supposed site of joint pain. This follows from Henry's law linking the volume of joint tissue (the solvent) and the solubility coefficient of inert gas; there is volumetrically insufficient connective tissue to produce the prolonged release of gas bubbles. If gas bubbles are spawned and released from connective tissue, their volume is increased by those from muscle tissue. Therefore, the nexus between Doppler-detectable gas bubbles and joint-pain decompression sickness is essentially a statistical, rather than a direct, one.

Powell, Michael R.↗

NASA NTRS2009

Microfluidic Extraction of Biomarkers using Water as Solvent

A proposed device, denoted a miniature microfluidic biomarker extractor (mu-EX), would extract trace amounts of chemicals of interest from samples, such as soils and rocks. Traditionally, such extractions are performed on a large scale with hazardous organic solvents; each solvent capable of dissolving only those molecules lying within narrow ranges of specific chemical and physical characteristics that notably include volatility, electric charge, and polarity. In contrast, in the mu-EX, extractions could be performed by use of small amounts (typically between 0.1 and 100 L) of water as a universal solvent. As a rule of thumb, in order to enable solvation and extraction of molecules, it is necessary to use solvents that have polarity sufficiently close to the polarity of the target molecules. The mu-EX would make selection of specific organic solvents unnecessary, because mu-EX would exploit a unique property of liquid water: the possibility of tuning its polarity to match the polarity of organic solvents appropriate for extraction of molecules of interest. The change of the permittivity of water would be achieved by exploiting interactions between the translational states of water molecules and an imposed electromagnetic field in the frequency range of 300 to 600 GHz. On a molecular level, these interactions would result in disruption of the three-dimensional hydrogen-bonding network among liquid-water molecules and subsequent solvation and hydrolysis of target molecules. The mu-EX is expected to be an efficient means of hydrolyzing chemical bonds in complex macromolecules as well and, thus, enabling analysis of the building blocks of these complex chemical systems. The mu-EX device would include a microfluidic channel, part of which would lie within a waveguide coupled to an electronically tuned source of broad-band electromagnetic radiation in the frequency range from 300 to 600 GHz (see figure). The part of the microfluidic channel lying in the waveguide would constitute an interaction volume. The dimensions of the interaction volume would be chosen in accordance with the anticipated amount of solid sample material needed to ensure extraction of sufficient amount of target molecules for detection and analysis. By means that were not specified at the time of reporting the information for this article, the solid sample material would be placed in the interaction volume. Then the electromagnetic field would be imposed within the waveguide and water would be pumped through the interaction volume to effect the extraction.

Amashukeli, Xenia↗

NASA NTRS2024

Current Status of Martian Moons eXploration (MMX) Contamination Control and Curation Activity

Martian Moons eXploration (MMX) is a sample return mission from the Martian moon Phobos. The MMX spacecraft is scheduled to launch in 2026 and return to Earth in 2031. The main science goals of MMX are “to reveal the origin of the Martian moons and make progress in the understanding of planetary system formation and material transport in the solar system, and to observe processes that impact the circumplanetary and surface environments of Mars”. MMX has two sampling systems: coring (C)-sampler and pneumatic (P)-sampler and plans to bring back >10 g of Phobos sample. The retuned sample in the sample capsule will be transferred to the curation facility in ISAS/JAXA for sample curation and subsequent sample analysis. Contamination control of the sample return mission requires special care to prevent terrestrial contamination to the spacecraft, which would ruin the scientific value of the returned sample. Retaining the pristineness of the retuned sample is an important task of the MMX Curation and Sampler Science teams. The basis of the contamination control is (1) to minimize and understand the nature and amount of contaminants, (2) to perform contamination assessment and evaluate the effect of contaminants in the spacecraft on the retuned sample, (3) to employ a contamination knowledge (CK) material coupon in the spacecraft to identify the contaminants in the returned samples. In the MMX contamination control plan, the allowable contamination level for each contaminant is carefully defined. They are mostly set to be 1/1000 of the expected amount of each material in the returned sample and are divided into two main categories: organic and inorganic. The allowable atmospheric leakage rate to the sample container is also defined. The allowable contamination level of the organic materials is based on the composition of carbonaceous chondrites. The target contaminants are amino acids, aliphatic and aromatic hydrocarbons, carboxylic acids, etc. In case of the inorganic materials, the target contaminants are important elements to permit distinguishing the origin of the Martian moon by nucleosynthetic isotope anomalies (Cr, Ti, and Mo) and to reveal the evolution of the Martian moon by chronology (Hf, W, U, Pb, Rb, Sr, Sm, and Nd). The key instrument of contamination control in the sample return mission is the sampler system. The C-sampler has been developed by JAXA and the P-sampler was provided by Honeybee/NASA. In MMX, materials used in the two samplers (C- and P- sampler) were carefully selected to avoid potential contamination from the design stage of the system. The individual parts of the C-sampler FM (Flight Model) were thoroughly cleaned at the curation facility in ISAS/JAXA by the full-course cleaning procedure, which is an ultrasonic cleaning with organic solvents and ultrapure water in several steps. The equivalent level of cleaning was also carried out on the P-Samper FM as well by Honeybee Robotics in the USA. Now, MMX is in the critical phase for contamination control called ATLO: Assembly, Test, and Launch Operations. During the ATLO phase, sampler FM is constantly purged with nitrogen gas and maintained at positive pressure to prevent environmental contamination. The surrounding environments of the sampler FM are also simultaneously monitored using the CK Monitoring Coupon Set, which consists of several witness materials such as a glass petri dish, sapphire glass disk, and carbon adhesive tape (Figure 1). The detailed environmental assessment of each clean room used for the assembly and test of the sampler FM has also been conducted. This assessment includes microbial analysis, which was performed for OSIRIS-REx. Regarding the sample recovery and sample curation, we have started the designing of Sample Container Disassembling Instrument for the sample recovery from the sample container and the MMX curation chamber for sample curation. The curation protocol for the Phobos returned sample has also been discussed by the MMX Sample Analysis Working Team (SAWT). The MMX curation protocol consists of three phases: (1) quick analysis, (2) pre-basic characterization, and (3) basic characterization. (1) is extraction of the sample gas from the sample container and analysis by mass spectrometry, (2) is observation in bulk level, and (3) is observation in grain level and allocation of the sample aliquots. In parallel with the curation protocol, the returned sample undergoes preliminary examination for scientific investigations to achieve science goals. In addition, the CK witness plates made of sapphire glass are on board the sampler system. The CK witness plates will be recovered from the sampler system and analyzed by SAWT for the assessment of in-flight contamination.

Haruna Sugahara↗

NASA NTRS2003

Self-Propagating Frontal Polymerization in Water at Ambient Pressure

Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High boiling point solutions are needed because in order to produce a propagating front, a high front temperature is needed to produce sufficiently rapid decomposition of the free radical initiator and subsequent free radical polymerization and heat release at a rate faster than heat losses remove thermal energy from the system. (While the conduction heat loss rate increases linearly with temperature, the free radical initiator decomposition is a high activation energy process whose rate increases much more rapidly than linearly with temperature, thus as the temperature decreases, the ratio of heat loss to heat generation increases, eventually leading to extinction of the front if the temperature is too low.) In order to obtain atmospheric pressure frontal polymerization in water, it is necessary to identify a monomer/initiator combination that is water soluble and will not extinguish even when the peak temperature (T*) is less than 100 C. In this work acrylic acid (AA) was chosen as the monomer because is it one of the most reactive monomers and can polymerize readily at low temperatures even without initiators. Ammonium persulfate (AP) was chosen as the initiator because it decomposes readily at low temperatures, produces relatively few bubbles and is commercially available. The propagation rates and extinction conditions of the fronts are studied for a range of AA and AP concentrations. Small amounts of fumed silica powder (Cab-o-sil, Cabot Corporation) were added to the solutions to inhibit buoyancy induced convection in the solutions; future studies will investigate the effects of buoyant convection within the solutions.

Olten, Nesrin↗

NASA NTRS2010

Fabrication and Modification of Nanoporous Silicon Particles

Silicon-based nanoporous particles as biodegradable drug carriers are advantageous in permeation, controlled release, and targeting. The use of biodegradable nanoporous silicon and silicon dioxide, with proper surface treatments, allows sustained drug release within the target site over a period of days, or even weeks, due to selective surface coating. A variety of surface treatment protocols are available for silicon-based particles to be stabilized, functionalized, or modified as required. Coated polyethylene glycol (PEG) chains showed the effective depression of both plasma protein adsorption and cell attachment to the modified surfaces, as well as the advantage of long circulating. Porous silicon particles are micromachined by lithography. Compared to the synthesis route of the nanomaterials, the advantages include: (1) the capability to make different shapes, not only spherical particles but also square, rectangular, or ellipse cross sections, etc.; (2) the capability for very precise dimension control; (3) the capacity for porosity and pore profile control; and (4) allowance of complex surface modification. The particle patterns as small as 60 nm can be fabricated using the state-of-the-art photolithography. The pores in silicon can be fabricated by exposing the silicon in an HF/ethanol solution and then subjecting the pores to an electrical current. The size and shape of the pores inside silicon can be adjusted by the doping of the silicon, electrical current application, the composition of the electrolyte solution, and etching time. The surface of the silicon particles can be modified by many means to provide targeted delivery and on-site permanence for extended release. Multiple active agents can be co-loaded into the particles. Because the surface modification of particles can be done on wafers before the mechanical release, asymmetrical surface modification is feasible. Starting from silicon wafers, a treatment, such as KOH dipping or reactive ion etching (RIE), may be applied to make the surface rough. This helps remove the nucleation layer. A protective layer is then deposited on the wafer. The protective layer, such as silicon nitride film or photoresist film, protects the wafer from electrochemical etching in an HF-based solution. A lithography technique is applied to pattern the particles onto the protective film. The undesired area of the protective film is removed, and the protective film on the back side of the wafer is also removed. Then the pattern is exposed to HF/surfactant solution, and a larger DC electrical current is applied to the wafers for a selected time. This step removes the nucleation layer. Then a DC current is applied to generate the nanopores. Next, a large electrical current is applied to generate a release layer. The particles are mechanically suspended in the solvent and collected by filtration or centrifuge.

Ferrari, Mauro↗