Theoretical analysis of the kinetics of the first reactions in peroxide-based explosives
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Shrestha, Krishna Prasad↗
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A METHOD TO REDUCE BIOBURDEN IN ASTROMATERIALS CURATION FACILITIES WITHOUT INTRODUCING UNWANTED CONTAMINATION
Introduction: NASA curates its Astromaterials collections in cleanrooms that are carefully monitored for particulate, inorganic and trace metal contamination. Current sample collections are not particularly susceptible to organic contamination or biological alteration. However, new collections like those from the OSIRIS-REx and Hayabusa2 missions will have organic contamination requirements and are susceptible to biodegradation. It will be necessary sterilize or at least disinfect curation labs, as well as tools and equipment in a manner that does not introduce additional contamination and does not affect the samples 1. Current curation cleaning procedures utilize isopropyl alcohol which offers some bioburden reduction, but is not effective against spore-forming bacteria or fungal spores 2. We present a modified disinfection method that uses ultrapure hydrogen peroxide to reduce bioburden inside curation labs and glove boxes without introducing contamination or damaging curation equipment. We tested this method in the meteorite processing lab as well as on a glovebox being cleaned for use in processing ANGSA (Apollo Next Generation Sample Analysis) samples and present the results of those tests. We discuss the limitations of this method and describe potential situations in which it will not be applicable. The CDC guidelines for disinfection andsterilization in healthcare facilities discusses over 15different methods for reducing bioburden in hospitalsettings 3. The most common method, steamsterilization, is well suited to sterilizing curationprocessing tools but cannot easily be used to sterilizecleanroom surfaces or large equipment likegloveboxes. Chemical sterilization with bleach(NaOCl) is also a common strategy in healthcare andpharmaceutical settings that presents materialcompatibility issues as well as serious inorganiccontamination concerns for curation facilities.Introducing a new source of Na and Cl into curationlabs is not acceptable. Other chemical methods likeethylene oxide, formaldehyde, iodophors andquaternary ammonium compounds could introduceorganic and inorganic contamination. We chose tofocus on hydrogen peroxide because it is generallycompatible with commonly used curation materialslike stainless steel, aluminum and Teflon and becauseit decomposes to oxygen and water. The CDCguidelines for hydrogen peroxide specify using a 7.5wt% solution at 25 ̊C with a contact time of 30 minutesfor high level disinfection and 6 hours for sterilization.High level disinfection is defined as a technique thatwill kill all microorganisms except large numbers ofbacterial spores 3. Methods: We prepared a solution of 7.5 wt%hydrogen peroxide from a stock solution of ultrapure30 wt% peroxide (JT Baker) and curation gradeultrapure water. This ultrapure water is already used incuration cleaning procedures and thus is not consideredand additional source of contamination. We conducteda materials compatibility test by exposing unanodizedand anodized 6061 T6 Al alloy to the peroxide solutionfor up to six hours and periodically inspecting thesurfaces for visible defects. We used this peroxide todisinfect the floor of the meteorite processing lab andthe interior of a curation glovebox by exposing thesesurfaces to the peroxide solution for 30 min. Thesurfaces were swabbed with a dry macrofoam swabbefore (Puritan Brand 2518051PFRNDFD) and afterperoxide treatment to collect microbes present on thesurfaces. Microbes were extracted by sonication fromthe swab into 15 ml of PBS (phosphate buffered saline)and inoculated onto the following media: TSA (trypticsoy agar) BA (blood agar), R2A (Reasoners 2 agar),Potato Dextrose Agar, Saboraud Dextrose Agar andSaboraud Dextrose Agar with 0.1 mg/ mlchloramphenicol. Four TSA plates and two BA plateswere inoculated with 0.1 ml of PBS each andincubated at 35 and 37 for 48 hours. Two R2A°C°Cplates (0.1 ml of PBS each) were incubated at 25 .°CThe remaining plates were inoculated with 0.2ml ofPBS and incubated at 30 ̊C for seven days. Afterincubation bacterial and fungal isolates were countedand transferred to new plates for identification usingthe VITEK24 automated system or by sequencing aportion of the barcode gene (16S rRNA for bacteria,small subunit gene for fungi) on an ABI 3500 Sangersequencer. Negative controls consisted of swabs thatwere opened in the sampling environment andanalyzed alongside the experimental samples.Results: A 6 hour exposure to hydrogen peroxideresulted in visible pitting on un-anodized 6061 Al, butnot on anodized surfaces. No visible pitting occurredafter a 30 minute exposure. Therefore, we decided tolimit our experimental tests to 30 min. exposures. 17bacterial CFU (colony forming units) representing 4distinct organisms were isolated from the meteorite processing lab floor prior to hydrogen peroxidetreatment. We were unable culture any organisms afterperoxide treatment. In the glovebox we were able toculture three bacterial CFU representing three distinctspecies, including a spore forming bacterium prior todisinfection with peroxide. After the peroxidetreatment we were unable to culture any organisms.Routine monitoring of the meteorite processing lab andthe glovebox did not indicate any increase in unwantedinorganic contamination after these peroxidetreatments. Discussion: A 30 minute treatment with 7.5 wt%peroxide appears to be an effective method forreducing bioburden on typical cleanroom surfaces. Themethod does not introduce unwanted organic orinorganic contamination and is compatible withcommonly used curation materials like stainless steel,Teflon and anodized aluminum alloys. Special careshould be taken with un-anodized aluminum.Prolonged exposure to hydrogen peroxide can causepitting on this material. We recommend using thismethod to disinfect curation labs and equipment whenbiological alteration is a concern. This method iseffective at room temperature and cannot be used todisinfect labs and equipment where the ambienttemperature is < 0 ̊C. Astromaterials samples shouldbe removed from the area where disinfection is tooccur. Hydrogen peroxide is a powerful oxidizingagent and will react with any organic carbon present inthe sample. References: [1.] Mccubbin, F. M. et al.Sp. Sci Rev(2019) doi:10.1007/s11214-019-0615-9. [2.] Mogul, R.et al.Astrobiology 18, ast.2017.1814 (2018). [3.]Rutala, W. A. & Weber, D. J. Guideline for Disinfection and Sterilization in Healthcare Facilities, 2008. [4.] Pincus, D. H. in Encyclopedia of Rapid Microbiological Methods (2005).
A. B. Regberg↗
Handling Procedures of Vegetable Crops
The National Aeronautics and Space Administration (NASA) is working towards future long duration manned space flights beyond low earth orbit. The duration of these missions may be as long as 2.5 years and will likely include a stay on a lunar or planetary surface. The primary goal of the Advanced Food System in these long duration exploratory missions is to provide the crew with a palatable, nutritious, and safe food system while minimizing volume, mass, and waste. Vegetable crops can provide the crew with added nutrition and variety. These crops do not require any cooking or food processing prior to consumption. The vegetable crops, unlike prepackaged foods, will provide bright colors, textures (crispy), and fresh aromas. Ten vegetable crops have been identified for possible use in long duration missions. They are lettuce, spinach, carrot, tomato, green onion, radish, bell pepper, strawberries, fresh herbs, and cabbage. Whether these crops are grown on a transit vehicle (e.g., International Space Station) or on the lunar or planetary surface, it will be necessary to determine how to safely handle the vegetables while maintaining acceptability. Since hydrogen peroxide degrades into water and oxygen and is generally recognized as safe (GRAS), hydrogen peroxide has been recommended as the sanitizer. The objective of th is research is to determine the required effective concentration of hydrogen peroxide. In addition, it will be determined whether the use of hydrogen peroxide, although a viable sanitizer, adversely affects the quality of the vegetables. Vegetables will be dipped in 1 % hydrogen peroxide, 3% hydrogen peroxide, or 5% hydrogen peroxide. Treated produce and controls will be stored in plastic bags at 5 C for up to 14 days. Sensory, color, texture, and total plate count will be measured. The effect on several vegetables including lettuce, radish, tomato and strawberries has been completed. Although each vegetable reacts to hydrogen peroxide differently, the data suggest that 5% hydrogen peroxide reduces the shelf life of the vegetable. A dip of either 1 % or 3% hydrogen peroxide helps reduce the microbial total count while not adversely affecting the quality of the vegetable.
Perchonok, Michele↗
Methods that purify uranium
A method for purifying uranium includes forming primary uranyl peroxide precipitates (UO 2 O 2 .4H 2 O). Forming the primary uranyl peroxide precipitates includes obtaining impure uranium dissolved in an acidic solution, evaporating the acidic solution to increase uranium concentration and to form a concentrated solution, mixing a hydrogen peroxide (H 2 O 2 ) solution with the concentrated solution in a first container, and forming uranyl peroxide precipitates in the first container. The method includes collecting the uranyl peroxide precipitates and washing and drying the uranyl peroxide precipitates. The method also includes converting the washed and dried uranyl peroxide precipitates into triuranium octoxide (U 3 O 8 ).
Du, Miting↗
Lessons Learned (3 Years of H2O2 Propulsion System Testing Efforts at NASA's John C. Stennis Space Center)
John C. Stennis Space Center continues to support the Propulsion community in an effort to validate High-Test Peroxide as an alternative to existing/future oxidizers. This continued volume of peroxide test/handling activity at Stennis Space Center (SSC) provides numerous opportunities for the SSC team to build upon previously documented 'lessons learned'. SSC shall continue to strive to document their experience and findings as H2O2 issues surface. This paper is intended to capture all significant peroxide issues that we have learned over the last three years. This data (lessons learned) has been formulated from practical handling, usage, storage, operations, and initial development/design of our systems/facility viewpoint. The paper is intended to be an information type tool and limited in technical rational; therefore, presenting the peroxide community with some issues to think about as the continued interest in peroxide evolves and more facilities/hardware are built. These lessons learned are intended to assist industry in mitigating problems and identifying potential pitfalls when dealing with the requirements for handling high-test peroxide.
Taylor, Gary O.↗
Methods and devices for sterilizing medical equipment
A hydrogen peroxide sterilization device for sterilizing a medical device, the hydrogen peroxide sterilization device including a hermetic outer container, a hydrogen peroxide pouch, and a hydrogen peroxide solution in the solution chamber. The hermetic outer container includes a sterilization enclosure configured to receive the medical device. The hydrogen peroxide pouch includes a permeable membrane enclosing a solution chamber and is configured to be positioned in the sterilization enclosure of the outer container. The permeable membrane is configured to allow hydrogen peroxide vapor to diffuse from the solution chamber through the permeable membrane into the sterilization enclosure.
Bohnert, George William↗
YPK9 and WHI2 Negatively Interact during Oxidative Stress
Yeast PARK9 (YPK9) shares homology with human ATP13A2, which encodes a polyamine transporter implicated in juvenile forms of Parkinson’s disease. We used YPK9 to gain insight into how ATP13A2 affects cell growth and sensitivity to oxidative stress. Surprisingly, the YPK9 deletion strain from the Saccharomyces cerevisiae deletion collection (YKO) in wildtype BY4741 (mating type a) grew faster and was more resistant to hydrogen peroxide than a commercial, putative parental BY4741 wildtype strain (BY4741 COM ). In contrast, deleting YPK9 from BY4741 COM rendered it very sensitive to hydrogen peroxide, suggesting its background is different from that of the deletion collection. Whole-genome sequencing revealed that BY4741 COM and BY4741 COM ypk9Δ contain a novel premature stop codon near the 3' end of WHI2 (WHI2 G1324T ), whereas the collection’s YPK9 deletion strain contains WHI2, which encodes a 486 amino acid protein, Whi2p. Replacing full-length WHI2 with the sequence coding for the predicted truncation (Whi2p E442* ) rendered strains more sensitive to hydrogen peroxide, whereas the converse replacement rendered them more resistant. The sequences of WHI2 in 20 randomly chosen strains from the collection encode the full-length protein, indicating that the putative parental BY4741 WHI2 G1324T strain’s genetic background differs from that of the deletion collection. Examination of WHI2 sequences in several commonly used wildtype S. cerevisiae strains and isolates revealed other Whi2p truncations that might yield altered phenotypes. Together, these results demonstrate a novel premature stop codon in WHI2 that renders yeast sensitive to hydrogen peroxide; they also reveal a negative genetic interaction between WHI2 and YPK9 in the presence of hydrogen peroxide in the BY4741 background.
59 BASIC BIOLOGICAL SCIENCES↗
Direct insights into the role of epoxy groups on cobalt sites for acidic H 2 O 2 production
Hydrogen peroxide produced by electrochemical oxygen reduction reaction provides a potentially cost effective and energy efficient alternative to the industrial anthraquinone process. In this study, we demonstrate that by modulating the oxygen functional groups near the atomically dispersed cobalt sites with proper electrochemical/chemical treatments, a highly active and selective oxygen reduction process for hydrogen peroxide production can be obtained in acidic electrolyte, showing a negligible amount of onset overpotential and nearly 100% selectivity within a wide range of applied potentials. Combined spectroscopic results reveal that the exceptionally enhanced performance of hydrogen peroxide generation originates from the presence of epoxy groups near the Co–N 4 centers, which has resulted in the modification of the electronic structure of the cobalt atoms. Computational modeling demonstrates these electronically modified cobalt atoms will enhance the hydrogen peroxide productivity during oxygen reduction reaction in acid, providing insights into the design of electroactive materials for effective peroxide production.<
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A search for a nonbiological explanation of the Viking Labeled Release life detection experiment
The possibility of nonbiological reactions involving hydrogen peroxide being the source of the positive response detected by the Viking Labeled Release (LR) life detection experiment on the surface of Mars is assessed. Labeled release experiments were conducted in the LR Test Standards Module which replicates the Viking flight instrument configuration on analog Martian soils prepared to match the Viking inorganic analysis of Mars surface material to which an aqueous solution of hydrogen peroxide had been added. Getter experiments were also conducted to compare several reactions simultaneously in the presence and absence of UV radiation prior to the addition of nutrient. Hydrogen peroxide on certain analog soils is found to be capable of reproducing the kinetics and thermal information contained in the Mars data. The peroxide concentration necessary for this response, however, is shown to require a chemical stability or production rate much greater than seems likely in the Mars environment. As previous experiments have shown hydrogen peroxide to be the most likely nonbiological source of the positive LR response, it is concluded that the presence of a biological agent on Mars must not yet be ruled out.
Levin, G. V.↗
Photodissociation of Cl2O2 in the spring Antarctic lower stratosphere
The likely photodissociation pathways of chlorine peroxide are examined. Reasoning by analogy between hydrogen peroxide and chlorine peroxide, it is shown that photodissociation of chlorine peroxide at wavelengths longer than 250 nm is not likely to give chlorine atoms as a primary product. Reasoning by analogy with molecules whose visible spectra are known, it is concluded that chlorine peroxide is also likely to photodissociate in the visible to give ClO radicals as primary products.
Eberstein, Igor J.↗
BOREAS TGB-10 Oxidant Flux Data over the SSA
The BOREAS TGB-10 team collected several trace gas data sets in its efforts to determine the role of biogenic hydrocarbon emissions with respect to boreal forest carbon cycles. This oxidant data set contains measured peroxide (H2O2 and total organic peroxides (ROOH)) and ozone concentrations as well as H2O2 and ROOH deposition velocities. These data were obtained at the SSA-OJP site during the summer of 1994. Measurements were made from May to September 1994. The data are stored in tabular ASCII files. Some important results were: (1) Ozone concentrations were consistently low, 20-30 ppb, during the summer of 1994. (2) Peroxide concentrations showed a seasonal variation with highest concentrations occurring in July (IFC-2). (3) Midday H2O2 levels averaged around 1.4 ppb during IFC-2 and 0.4 - 0.5 ppb during IFC's 1 and 3. (4) Midday organic peroxide concentrations were lower, averaging 0.8 ppb during IFC-2, and 0.4 - 0.5 ppb during IFC's 1 and 3. (5) The rough pine forest canopy serves as a significant sink for H2O2. (6) Midday H2O2 deposition velocities averaged 4 - 7 cm/s. (7) Organic peroxide deposition velocities (measured as total ROOH) were approximately 40% as large as those of H2O2.
Hall, Forrest G.↗
BOREAS TGB-10 Oxidant Concentration Data over the SSA
The BOREAS TGB-10 team collected several trace gas data sets in its efforts to determine the role of biogenic hydrocarbon emissions with respect to boreal forest carbon cycles. This data set contains measured peroxide (H2O2 and total organic peroxides (ROOH)) and ozone concentrations as well as H2O2 and ROOH deposition velocities. These data were obtained at the SSA-OJP site from May to September 1994. The data are stored in tabular ASCII files. Some important results were: (1) Ozone concentrations were consistently low, 20-30 ppb, during the summer of 1994. (2) Peroxide concentrations showed a seasonal variation with highest concentrations occurring in July (IFC-2). (3) Midday H2O2 levels averaged around 1.4 ppb during IFC-2 and 0.4 - 0.5 ppb during IFC's 1 and 3. (4) Midday organic peroxide concentrations were lower, averaging 0.8 ppb during IFC-2, and 0.4 - 0.5 ppb during IFC's 1 and 3. (5) The rough pine forest canopy serves as a significant sink for H2O2. (6) Midday H2O2 deposition velocities averaged 4 - 7 cm/s. (7) Organic peroxide deposition velocities (measured as total ROOH) were approximately 40% as large as those of H2O2.
Hall, Forrest G.↗
Efficacy of Various Chemical Disinfectants on Biofilms Formed in Spacecraft Potable Water System Component
As the provision of potable water is critical for successful habitation of the International Space Station (ISS), life support systems were installed in December 2008 to recycle both humidity from the atmosphere and urine to conserve available water in the vehicle. Pre-consumption testing from the dispensing needle at the Potable Water Dispenser (PWD) indicated that bacterial concentrations exceeded the current ISS specifications of 50 colony forming units (CFU) per ml. Subsequent investigations revealed that a corrugated stainless steel flex hose upstream of the dispensing needle in the PWD was filled with non-sterile water and left at room temperature for over one month before launch. To simulate biofilm formation that was suspected in the flight system, sterile flex hoses were seeded with a consortium of bacterial isolates previously recovered from other ISS water systems, which included Ralstonia pickettii, Burkholderia multivorans, Caulobacter vibrioides., and Cupriavidus pauculus. After 5 days of incubation, these hoses were challenged with various chemical disinfectants including hydrogen peroxide, colloidal silver, and buffered pH solutions to determine the ability of the disinfectants to decrease and maintain bacterial concentrations below ISS specifications. Disinfection efficacy over time was measured by collecting daily heterotrophic plate counts following exposure to the disinfectants. A single flush with either 6% hydrogen peroxide solution or a mixture of 3% hydrogen peroxide and 400 ppb colloidal silver effectively reduced the bacterial concentrations to less than 1 CFU/ml for a period of up to 2 months. Testing results indicated that hydrogen peroxide and mixtures of hydrogen peroxide and colloidal silver have tremendous potential as alternative disinfectants for ISS water systems.
Wong, Willy↗
Composite-Material Tanks with Chemically Resistant Liners
Lightweight composite-material tanks with chemically resistant liners have been developed for storage of chemically reactive and/or unstable fluids . especially hydrogen peroxide. These tanks are similar, in some respects, to the ones described in gLightweight Composite-Material Tanks for Cryogenic Liquids h (MFS-31379), NASA Tech Briefs, Vol. 25, No. 1 (January, 2001), page 58; however, the present tanks are fabricated by a different procedure and they do not incorporate insulation that would be needed to prevent boil-off of cryogenic fluids. The manufacture of a tank of this type begins with the fabrication of a reusable multisegmented aluminum mandrel in the shape and size of the desired interior volume. One or more segments of the mandrel can be aluminum bosses that will be incorporated into the tank as end fittings. The mandrel is coated with a mold-release material. The mandrel is then heated to a temperature of about 400 F (approximately equal to 200 C) and coated with a thermoplastic liner material to the desired thickness [typically approxiamtely equal to 15 mils (approximately equal to 0.38 mm)] by thermal spraying. In the thermal-spraying process, the liner material in powder form is sprayed and heated to the melting temperature by a propane torch and the molten particles land on the mandrel. The sprayed liner and mandrel are allowed to cool, then the outer surface of the liner is chemically and/or mechanically etched to enhance bonding of a composite overwrap. The etched liner is wrapped with multiple layers of an epoxy resin reinforced with graphite fibers; the wrapping can be done either by manual application of epoxy-impregnated graphite cloth or by winding of epoxy-impregnated filaments. The entire assembly is heated in an autoclave to cure the epoxy. After the curing process, the multisegmented mandrel is disassembled and removed from inside, leaving the finished tank. If the tank is to be used for storing hydrogen peroxide, then the liner material should be fluorinated ethylene/propylene (FEP), and one or more FEP O ring(s) should be used in the aluminum end fitting(s). This choice of materials is dictated by experimental observations that pure aluminum and FEP are the only materials suitable for long-term storage of hydrogen peroxide and that other materials tend to catalyze the decomposition of hydrogen peroxide to oxygen and water. Other thermoplastic liner materials that are suitable for some applications include nylon 6 and polyethylene. The processing temperatures for nylon 6 are lower than those for FEP. Nylon 6 is compatible with propane, natural gas, and other petroleum-based fuels. Polyethylene is compatible with petroleum- based products and can be used for short-term storage of hydrogen peroxide.
DeLay, Thomas K.↗
Bubble-Free Frontal Polymerization of Acrylates via Redox-Initiated Free Radical Polymerization
Thermal frontal polymerization (FP) of acrylate monomers mixed with conventional peroxide initiators leads to significant bubble formation at the polymerizing front, limiting their practical applications. Redox initiators present a promising alternative to peroxide initiators, as they prevent the formation of gaseous byproducts during initiator decomposition and lower the front temperature, thereby enabling bubble-free FP. In this study, we investigate the FP of acrylate monomers of varying functionalities, including methyl methacrylate (MMA), 1,6-hexanediol diacrylate (HDDA), and trimethylolpropane triacrylate (TMPTA), using N,N -dimethylaniline/benzoyl peroxide (DMA/BPO) redox couple at room temperature and compare their front behavior, pot life, and bubble formation with those of same resin systems mixed with a conventional peroxide initiator, Luperox 231. The use of redox couples in FP of acrylates shows promise for rapid, energy-efficient manufacturing of polyacrylates and can enable new applications such as 3D printing and composite manufacturing.
36 MATERIALS SCIENCE↗
Investigation of the structure, filler interaction and degradation of disulfide elastomers made by Reversible Radical Recombination Polymerization (R3P)
In this paper we report the synthesis and analysis of cyclic polydisulfides, their redox depolymerization as well as their interaction with carbon black. Cyclic poly(3,6-dioxa-1,8-octanedithiol)s (pDODT) were synthesized by Reversible Radical Recombination Polymerization (R3P). R3P is a scalable “green” polymerization process using triethylamine (TEA), H 2 O 2 and air for the polymerization of dithiol monomers. pDODTs were synthesized in 5 and 20 g batches. The effect of peroxide concentration (3, 5, 10, 20, 30%) was investigated. It was found that the molecular weights increased exponentially with increasing peroxide concentrations. At 30% peroxide concentration pDODTs with M n up to 400,000 g/mol and polydispersity of 2 were obtained. 700 and 800 MHz NMR were used for investigating the chemical structure of the polymers. The absence of thiol end group signals in polymers made with > 10wt % H 2 O 2 and M n < 100,000 g/mol, including a sample of a fractionated polymer with starting Mn = 600,000 g/mol, verified cyclic structures. Dithiothreitol reduced the polymers to monomer and a small percentage of oligomers. Carbon black was shown to increase the moduli of high molecular weight pDODTs. Swelling tests in chloroform showed that polymers made with 20 and 30w% peroxide swelled 14 and 10 times of their starting weight without dissolving, indicating chemical interaction between the polymers and carbon black. In conclusion, further analysis of these interesting elastomers, available at the 20 g scale, is in progress.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Physical, Chemical, and Mineralogical Characterizations of MSWI Ash Product and Recommendations for Downstream Processing
The primary objectives of this project are to (1) systematically characterize MSWI ash, and (2) based on characterization findings, design preliminary flowsheets for downstream processing. To achieve these objectives, a total of ten tasks were completed, including sample collection, physical separation tests, liberation tests, synthetic MSWI ash preparation, elemental composition analysis, sequential chemical extraction, mineralogical characterization, pozzolanic activity characterization, thermal stability characterization, processing flowsheet design, TEA and T2M, and project performance reporting. Many useful findings and conclusions were obtained from the exhaustive efforts of this project from several different aspects, including: a) Valuable Metals in MSWI Ash: MSWI ash contains a diverse array of valuable metals. Based on potential recoverable values, the most valuable metals present in MSWI ash include Fe, Ti, Mn, Cu, Zn, V, Co, Ni, Sr, Sn, Ag, Mo, and Sc. Some of these metals have been identified as critical minerals by DOE and DOI, suggesting that MSWI is a promising feedstock for critical mineral recovery. Noticeable graphical and seasonable variations in the valuable metal content of MSWI ash were observed. Nevertheless, it was challenging to discern any clear, definitive patterns for conclusions from those observations. Compared with bottom ash, fly ash contains more volatile metals, such as Zn and Sn, but less nonvolatile metals, such as Fe, Mn, Cu, Zn, Co, and Ni. Mineralogical analyses showed that MSWI ash contains a substantial amount of calcium minerals, such as portlandite, lime, gypsum, and calcite. In addition, it was found that different types of valuable metals often exist in the same particles. b) Physical Separation of MSWI Ash: Both dry sieving and wet sieving were performed on MSWI ash. A notable disparity in the size distribution of the same material was observed when using the two different sieving methods. The disparity is due to the agglomeration of small particles. For the valuable metals investigated, no significant enrichment in a specific size fraction was observed, suggesting that it is challenging to preconcentrate the valuable metals through size fractionation. Due to the presence of ferromagnetic materials, such as Fe, most of the materials reported to the magnetic products obtained by dry magnetic separation. However, the enrichment effect is minimal due to the existence of particle agglomerates. Density separation at a cut-off density of 2.7 SG or higher led to noticeable enrichment of selected valuable metals, particularly Ti. The unburned carbon present in MSWI ash was effectively removed by flotation using diesel as the collector. A novel reagent scheme, Na2S plus cationic collectors, that can efficiently beneficiate nonferrous metals plus Co was developed. c) Liberation Tests: The particle size of MSWI ash was effectively reduced by grinding, and as a result, the encapsulated valuable metal particles (if any) were liberated to a certain degree. However, particle size reductions did not noticeably enhance the beneficiation performance using the physical separation methods, primarily due to the inefficiency of these methods in processing fine particles and/or a possibility that insufficient liberation is not a limiting factor for achieving satisfactory physical separation performance. Valuable metals were classified into water leachable, ion-exchangeable, acid soluble, reducible, oxidable, and insoluble forms. It was found that the distributions in the different categories, i.e., the occurrence modes of the valuable metals, were not affected by the particle size. d) Leaching Characteristics of Metals from MSWI Ash: Most of the valuable metals were extracted from the fly ash samples when using 1 M HCl or HNO3 as the lixiviant. The leaching reaction is a very fast process, which can reach equilibrium within the first 5 min. The releasing of Co, Ni and Ag are sensitive to leaching temperature, a higher recovery value could be obtained when using relatively higher leaching temperatures. The leachability of the valuable metals present in MSWI bottom ash is relatively lower than that of fly ash. Leaching recoveries increased with elevations in the acid concentration. Relatively high leaching recoveries were obtained for REEs, Mn, Co, Ni, Cu, and Zn using 1 M HCl or HNO3 as the lixiviant. Elevations in the reaction temperature noticeably increased the leachability of the valuable metals, whereas the leachability was barely influenced by oxidizing and reducing agents. Similar to fly ash, leaching valuable metals from bottom ash is a rapid process, with most of the leaching reaction completed within the first 5 minutes. e) Combusted iPhones: The original structure of iPhones was remained after treating at 400 ºC and 600 ºC, while after being treated at 800℃, the screen bent, and the back cover of iPhone melted. Increasing the combustion temperature to 1000℃, the screen scattered, and most of the components turned into ashes. Combustion enhanced the leachability of REEs, while the leachability of the other valuable metals, except for Zn, was barely affected. Most of the REEs present in the original iPhones occurred as oxidizable forms. With elevations in the combustion temperature up to 600 ºC, the oxidizable REEs were transformed to acid soluble forms. However, further elevations in temperature resulted in decreases in the acid soluble fraction and corresponding increases in the reducible and oxidizable forms. Additionally, combustion temperature also significantly altered the occurrence modes of other metals present in the iPhones. f) Synthetic MSWI Ash: It was found that in the absence of hydrogen peroxide, all the elements except for Si were leached to certain degrees. It is noteworthy that approximately 80% of Zn was leached with 1.2 M HCl. When hydrogen peroxide was added to the reaction system, noticeable increases in the leaching recovery of Fe, Mn, Co, Ni, and Cu were observed. The leaching recovery of Al and Si was barely affected by adding hydrogen peroxide. These results suggested that the majority of Zn in the synthetic MSWI ash existed as metal oxide, a portion of Fe, Mn, Co, Ni, and Cu existed as metal oxide, and Al and Si are associated with glasses which are difficult to leach. Additionally, the remaining Fe, Mn, Co, Ni, and Cu in the metallic form were efficiently oxidized in the presence of hydrogen peroxide. g) Pozzolanic Activity and Thermal Stability of MSWI Ash: MSWI fly ash has higher pozzolanic activity compared to the bottom ash sample, which indicates that the fly ash sample consumed more portlandite because of its smaller particle size as reactivity fundamentally relates to reaction surface area. However, after the recovery of valuable elements, the pozzolanic activity of both the valuable elements fraction and the less valuable elements-rich products decreased significantly, which means that the valuable elements recovery lowers the Ca(OH)2 consumption, thus leading to the low activity of SCM. h) Flowsheet Design for Metal Recovery from MSWI Ash: Based on the results of the comprehensive physical separation and acid leaching tests, circuits that enable the beneficiation of the valuable metals were developed. In these circuits, the valuable metals are recovered into nonferrous, ferrous, and other valuable metal concentrates, which are processed separately in the acid leaching step. The subsequent separation and purification steps are simplified due to the physical beneficiation step. In addition, the overall recovery cost is reduced since physical beneficiation is much cheaper compared with chemical processing. Using different technologies, such as selective precipitation and solvent extraction, a comprehensive hydrometallurgical circuit was designed, and compounds of Cu, Zn, Mn, Co, and Ni with a purity close to or even higher than 95% were successfully generated.
36 MATERIALS SCIENCE↗
The synthesis of higher oxides of alkali and alkaline earth metals in an electric discharge: Theoretical and experimental studies
Potassium hydroxide was subjected to the products of an electrical discharge sustained in oxygen and produced both potassium peroxide and superoxide. The conversion to higher oxides was shown to strongly depend upon the particle size of KOH, the position of KOH in the discharge zone, and the operating conditions of the discharge. Similar experiments were performed with hydroxides of lithium and calcium which do not form superoxides, but are converted to peroxides. The yields of peroxides were shown to strongly depend upon the operating conditions of the discharge. The absence of superoxides and the presence of peroxides of lithium and calcium was explained from the consideration of relative thermodynamic stability of the oxides of lithium and calcium. Thermogravimetric analysis was shown to provide a more accurate means for determining the amount of KO2 than previous methods.
Bell, A. T.↗