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Research and Development History of Glass Bubbles Bulk-Fill Thermal Insulation Systems for Large-Scale Cryogenic Liquid Hydrogen Storage Tanks

Based on the published literature record, this document provides an overview of the research and development of glass bubbles bulk-fill thermal insulation systems for cryogenic equipment in general and, in particular, for large-scale cryogenic liquid hydrogen (LH2) storage spheres. Glass bubbles (also known as hollow glass microspheres) are used in place of perlite powder which began use in double-wall cryogenic tanks in the 1930s. Included in this overview is a historical summary, a development timeline, a selected publications list, and the key technical points from those publications.

Cryogenic storage tanks↗

Moisture-Induced Alumina Scale Spallation: The Hydrogen Factor

For some time the oxidation community has been concerned with interfacial spallation of protective alumina scales, not just upon immediate cool down, but as a time-delayed phenomenon. Moisture-induced delayed spallation (MIDS) and desktop spallation (DTS) of thermal barrier coatings (TBCs) refer to this process. It is most apparent for relatively adherent alumina scales that have survived initial cool down in a dry environment, have built up considerable thickness and strain energy, and have been somewhat damaged, such as by cyclic oxidation cracking. Indeed, a "sensitive zone" can be described that maximizes the observed effect as a function of all the relevant factors. Moisture has been postulated to serve as a source of interfacial hydrogen embrittlement. Hydrogen is derived from reaction with aluminum in the alloy at an exposed interface. The purpose of this monograph is to trace the close analogy of this phenomenon to other hydrogen-induced effects, such as embrittlement of aluminides and blistering of alloys and anodic alumina films. A formalized, top-down, logic-tree structure is presented as a guide to this discussion. A theoretical basis for interfacial weakening by hydrogen is first cited, as are demonstrations of hydrogen detection as a reaction product or interfacial species. Further support is provided by critical experiments that recreate the moisture effect, but by isolating hydrogen from other potential causative factors. These experiments include tests in H 2-containing atmospheres or cathodic hydrogen charging. Accordingly, they strongly indicate that interfacial hydrogen, derived from moisture, is the key chemical species accounting for delayed alumina scale spallation.

Smialek, James L.↗

Moisture-Induced Alumina Scale Spallation: The Hydrogen Factor

For some time our community has been concerned with interfacial spallation of protective alumina scales, not just upon immediate cooldown, but as a time-delayed phenomenon. Moisture-induced delayed spallation (MIDS) and desktop spallation (DTS) of TBC's refer to this process. It is most apparent for relatively adherent alumina scales that have survived cool down in a dry environment, built up considerable thickness and strain energy, and have been somewhat damaged, such as by cyclic oxidation cracking. Indeed, a "sweet zone" can be defined that maximizes the observed effect as a function of all the relevant factors. Moisture has been postulated to serve as a source of interfacial hydrogen embrittlement derived from reaction with aluminum in the alloy at an exposed interface. The purpose of this monograph is to trace the close analogy of this phenomenon to other hydrogen effects, such as embrittlement of aluminides and blistering of alloys and anodic alumina films. A formalized, top-down, logic tree structure is presented as a guide to this discussion. A theoretical basis for interfacial weakening by hydrogen is first cited, as are demonstrations of hydrogen as a reaction product or detected interfacial species. Further support is provided by critical experiments that produce the same moisture effect, but by isolating hydrogen from other potential causative factors. These experiments include tests in H2-containing atmospheres or cathodic hydrogen charging.

Smialek, James L.↗

Large time scale variation in hydrogen emission from Jupiter and Saturn

The IUE and Voyager spacecraft observations of Jupiter and Saturn were combined to obtain a consistent measurement of temporal variation of the equatorial subsolar hydrogen emission. The outer planets appear to have rather independent behavior over time scales of the order of 10 yr, particularly in emission from the H Ly alpha line. The time interval from 1978 to the present shows variation of mean equatorial H Ly alpha brightness of 2 at Jupiter and 5 at Saturn. The relative magnitudes of the variations is sufficiently different to suggest that response to input from the Sun is at least nonlinear. The brightness of H2 band emission appears to be relatively more stable than H Ly alpha. There is evidence in IUE observations of a moderate increase in H2 band brightness with increasing time at Jupiter, in opposition to the variation in H Ly alpha.

Shemansky, D. E.↗

H2 emission as a tracer of molecular hydrogen: Large-scale observations of Orion

We have detected extremely extended (greater than 1.5 deg, or 12 pc) near-infrared H2 line emission from the Orion A molecular cloud. We have mapped emission in the 1.601 micrometer(s) upsilon = 6 - 4 Q(1) and 2.121 micrometer(s) upsilon = 1 - 0 S(1) lines of H2 along a approx. 2 deg R.A. cut and from a 6' x 6' region near theta(sup 1) Ori C. The surface brightness of the extended H2 line emission is 10(exp -6) to 10(exp -5) ergs/s/sq. cm/sr. Based on the distribution and relative strengths of the H2 lines, we conclude that UV fluorescene is most likely the dominant H2 emission mechanism in the outer parts of the Orion cloud. Shock-heated gas does not make a major contribution to the H2 emission in this region. The fluorescent component of the total H2 upsilon = 1 - 0 S(1) luminosity from Orion is 30-40 solar luminosity. Molecular hydrogen excited by UV radiation from nearby OB stars contributes 98%-99% of the global H2 line emission from the Orion molecular cloud, even though this cloud has a powerful shock-excited H2 source in its core. The ability to detect large-scale H2 directly opens up new possibilities for the study of molecular clouds.

Luhman, M. L.↗

Evaluating Lunar Water Processing System Model Configurations for Small Scale Oxygen and Hydrogen Production Within JAXA’s ISRU Technology Demonstration Plant

In-Situ Resource Utilization (ISRU) refers to novel methods of extracting and processing local resources for use in life support and propulsion systems, reducing or eliminating the required consumables to be transferred from Earth. Current estimates of water-ice availability embedded in regolith within the Moon’s permanently shadowed regions (PSR’s)range between 1-5% by weight. However, the composition and characteristics of the “wet” regolith is unknown. Alternate ISRU excavation techniques and Concept of Operations (ConOps) must be explored to optimize surface system operations based on these factors. To assess the feasibility of different ISRU subsystem technologies and compare system architecture configurations, an interchangeable system model was generated to incorporate technologies spanning excavation of raw materials to storage of products and determine optimal arrangement of total system processing needs. Total Mass, Volume, and Power (M/V/P) requirements were computed for 168 design iterations of this water processing plant.

ISRU↗

Evaluating Lunar Water Processing System Model Configurations for Small Scale Oxygen and Hydrogen Production Within JAXA'S ISRU Technology

Introduction: In-Situ Resource Utilization (ISRU) refers to novel methods of extracting and processing local resources for use in life support and propulsion systems, reducing or eliminating the required consumables to be transferred from Earth. Current estimates of water-ice availability embedded in regolith within the Moon’s permanently shadowed regions (PSR’s) range between 1-5% by weight. However, the composition and characteristics of the “wet” regolith is unknown. Alternate ISRU excavation techniques and Concept of Operations (ConOps) must be explored to optimize surface system operations based on these factors. To assess the feasibility of different ISRU subsystem technologies and compare system architecture configurations, an interchangeable system model was generated to incorporate technologies spanning excavation of raw materials to storage of products and determine optimal arrangement of total system processing needs. Total Mass, Volume, and Power (M/V/P) requirements were computed for 168 design iterations of this water processing plant. System Model: In FY24, the System Engineering and Integration (SE&I) ISRU Modeling and Analysis (SIMA) team developed a lunar water processing system model using the Mission Analysis and Integration Tool (MAIT) to estimate the M/V/P for ISRU subsystems operating under a wide range of Hydrogen (H2) and Oxygen (O2) production targets for the Space Technology Mission Directorate (STMD) [1]. Based on Japan Aerospace Exploration Agency’s (JAXA) surface operational requirements, this system architecture was modified to include the ability to excavate consolidated icy regolith (versus granular ice excavation using Kennedy Space Center’s (KSC) ISRU Pilot Excavator, IPEx) and explore the feasibility of processing the lunar water both inside and outside of the PSR. For the consolidated icy regolith case study, excavation was performed via a mobility transport chassis outfitted with The Regolith Ice Drill for Exploring New Terrain (TRIDENT) for drilling [2] and the Cold Operable Lunar Deployable Arm (COLDArm) [3] for regolith transfer. The system model determines the required rover and payload. M/V/P to handle the required regolith processing rates. The regolith is then sorted and heated to sublimate the ice (via an auger dryer). The exiting high temperature, low pressure vapor is cleaned of volatiles (via cold trap) and electrolyzed to produce H2 and O2. These products are then dried, liquified with 20 K and 90 K cryocoolers (for H2 and O2, respectively), and stored in cylindrical tanks. Study Goals: Due to the different ConOps options of regolith transport to the ridge for processing versus processing it directly inside the PSR, as well as the unknown regolith/water-ice composition, new excavation techniques and their power configurations are being evaluated within a ISRU system architecture for production targets less than NASA’s pilot plant (1 mT). This analysis investigates the feasibility of numerous excavation techniques, power architectures, and logistical operations and determines an optimal system configuration with regards to M/V/P. It aims to investigate which parameters, both locally and globally, have the greatest effect on each subsystem within the plant. This can be used to identify the most critical components of the plant, and guide future decisions on allocating funding for research and development. The results from this study may provide subsystem developers with appropriate interfaces with excavation subsystems and downstream processes, and assessing the overall feasibility of each excavation technique, power architecture, and logistical timeframe. References: [1] Carlson, A. et. al. (2024) ICES. [2] Zacny, K., et. al. (2024) “ASCE Earth and Space”. [3] McCormick, R., et. Al. (2024) IEEE Xplore.

ISRU↗

Testing of Densified Liquid Hydrogen Stratification in a Scale Model Propellant Tank

Propellant densification has been identified as a critical technology in the development of a single stage to orbit (SSTO) launch vehicle. The densification of cryogenic propellant through sub-cooling allows more propellant to be stored in a given volume. This allows for higher propellant mass fractions than would otherwise be possible with conventional, normal boiling point, cryogenic fluids. One critical step in determining the viability of densified propellant technology for launch vehicles is to perform the sequential process necessary to load a propellant tank with densified propellants. This paper describes a test program that was conducted at NASA to demonstrate the ability to load densified LH2 into a sub-scale propellant rank. This work was done through a collaborative effort between NASA Lewis Research Center and the Lockheed Martin Michoud Space Systems (LMMSS). The tank, is made from composite materials similar to that to be used on X-33, is formed from two lobes with a center seprum. Test results are shown for data that was collected on filling the sub-scale tank with densified liquid hydrogen propellant that was produced at the NASA Plum Brook Station. Data is compared to analytical predictions.

Greene, W. D.↗

Moisture-Induced Delayed Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

While interfacial sulfur is the primary chemical factor affecting Al2O3 scale adhesion, moisture-induced delayed spallation appears as a secondary, but impressive, mechanistic detail. Similarities with bulk metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al(sub alloy)+3(H2O)(sub air) = Al(OH)(-) (sub 3) +3H(+) may be the operative mechanism. This proposal was tested on pre-oxidized Rene N5 by standard cathodic hydrogen charging in 1N H2SO4, as monitored by weight change, induced current, and microstructure. Cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the acid electrolyte produced neither scale spallation nor alloy dissolution. Thus, hydrogen charging was detrimental to alumina scale adhesion. Moisture-induced interfacial hydrogen embrittlement is concluded to be the cause of delayed scale spallation and desktop thermal barrier coating failures.

Smialek, James L.↗

Moisture-Induced Spallation and Interfacial Hydrogen Embrittlement of Alumina Scales

Thermal expansion mismatch stresses and interfacial sulfur activity are the major factors producing primary Al2O3 scale spallation on high temperature alloys. However, moisture-induced delayed spallation appears as a secondary, but often dramatic, illustration of an additional mechanistic detail. A historical review of delayed failure of alumina scales and TBC s on superalloys is presented herein. Similarities with metallic phenomena suggest that hydrogen embrittlement from ambient humidity, resulting from the reaction Al+3H2O=Al(OH)3+3H(+)+3e(-), is the operative mechanism. This proposal was tested by standard cathodic hydrogen charging in 1N H2SO4, applied to Rene N5 pre-oxidized at 1150 C for 1000 1-hr cycles, and monitored by weight change, induced current, and microstructure. Here cathodic polarization at -2.0 V abruptly stripped mature Al2O3 scales at the oxide-metal interface. Anodic polarization at +2.0 V, however, produced alloy dissolution. Finally, with no applied voltage, the electrolyte alone produced neither scale spallation nor alloy dissolution. These experiments thus highlight the detrimental effects of hydrogen charging on alumina scale adhesion. It is proposed that interfacial hydrogen embrittlement is produced by moist air and is the root cause of both moisture-induced, delayed scale spallation and desktop TBC failures.

Smialek, James L.↗

Small scale bipolar nickel-hydrogen testing

Bipolar nickel-hydrogen batteries, ranging in capacity from 6 to 40 A-hr, have been tested at the NASA Lewis Research Center over the past six years. Small scale tests of 1 A-hr nickel-hydrogen stacks have been initiated as a means of screening design and component variations for bipolar nickel-hydrogen cells and batteries. Four small-scale batteries have been built and tested. Characterization and limited cycle testing were performed to establish the validity of test results in the scaled down hardware. The results show characterization test results to be valid. LEO test results in the small scale hardware have limited value.

Manzo, Michelle A.↗

Small scale bipolar nickel-hydrogen testing

Bipolar nickel-hydrogen batteries, ranging in capacity from 6 to 40 A-hr, have been tested at the NASA Lewis Research Center over the past six years. Small scale tests of 1 A-hr nickel-hydrogen stacks have been initiated as a means of screening design and component variations for bipolar nickel-hydrogen cells and batteries. Four small-scale batteries have been built and tested. Characterization and limited cycle testing were performed to establish the validity of test results in the scaled down hardware. The results show characterization test results to be valid. LEO test results in the small scale hardware have limited value.

Manzo, Michelle A.↗

Large-Scale Demonstration of Liquid Hydrogen Storage with Zero Boiloff for In-Space Applications

Cryocooler and passive insulation technology advances have substantially improved prospects for zero-boiloff cryogenic storage. Therefore, a cooperative effort by NASA s Ames Research Center, Glenn Research Center, and Marshall Space Flight Center (MSFC) was implemented to develop zero-boiloff concepts for in-space cryogenic storage. Described herein is one program element - a large-scale, zero-boiloff demonstration using the MSFC multipurpose hydrogen test bed (MHTB). A commercial cryocooler was interfaced with an existing MHTB spray bar mixer and insulation system in a manner that enabled a balance between incoming and extracted thermal energy.

Hastings, L. J.↗

Oxygen-hydrogen torch is a small-scale steam generator

Standard oxygen-hydrogen torch generates steam for corrosion-rate analysis of various metals. The steam is generated through local combustion inside a test chamber under constant temperature and pressure control.

Maskell, C. E.↗

Testing of Densified Liquid Hydrogen Stratification in a Scale Model Propellant Tank

This paper describes a test program that was conducted at NASA to demonstrate the ability to load densified LH2 into a subscale propellant tank. This work was done through a collaborative effort between NASA Glenn Research Center and the Lockheed Martin Michoud Space Systems (LMMSS). The Multilobe tank, which was made from composite materials similar to that to be used on X-33, was formed from two lobes with a center septum. Test results are shown for data that was collected on filling the subscale tank with densified liquid hydrogen (DLH2) propellant that was produced at the NASA Plum Brook Station. Data is compared to analytical predictions. Data collected for this test series agrees well with analytical predictions of the environmental heat leak into the tank and the thermal stratification characteristics of the hydrogen propellant in the tank as it was filled with DLH2.

Jurns, John M.↗

Low gravity reorientation in a scale-model Centaur liquid-hydrogen tank

An experiment was conducted to investigate the process of liquid reorientation from one end of a scale-model Centaur liquid-hydrogen tank to the other end by means of low-level accelerations. Prior to reorientation, the liquid was stabilized at the top of the tank at a Bond number of 15. Tanks both with and without ring baffles and with tank radii of 5.5 and 7.0 centimeters were used in the study. Reorientation acceleration values were varied to obtain Bond numbers of 200 and 450. Liquid fill levels of 20 and 70 percent were used. From the data in this study, relations were developed to estimate reorientation event times in unbaffled tanks through the point of final liquid clearing from the top of the tank. The insertion of ring baffles drastically changed the reorientation flow profiles but resulted in only minor differences in the times of tank-top uncovering and liquid collection.

Salzman, J. A.↗