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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Evaluation of HAN-TEAN Stabilizers using Microcalorimetry

HAN-TEAN (hydroxylammonium nitrate - triethanolammonium nitrate - in water) is being considered for various propellant applications. This propellant has advantages in terms of insensitivity to impact and fire, low vapor pressure and environmentally benign reaction products. One office concerns with HAN-TEAN is its stability and shelf-life, especially when contaminated with trace metals. Stabilizer systems, consisting of anti-oxidants and/or chealating agents were investigated for their ability to control the decomposition of HAN-TEAN. Isothermal microcalorimetry, an ultrasensitive heat measurement technique, was used to monitor the decomposition of HANTEAN at near ambient temperatures. Isothermal microcalorimetry measures the heat flow from a reaction vessel into a surrounding heat sink. Microcalorimetry is approximately 1,000 times more sensitive than accelerating rate calorimetry (ARC) or differential scanning calorimetry (DSC) for measuring heat flow. Samples of HAN-TEAN containing the stabilizers were spiked with 50 ppm iron and the heat evolution monitored for a period of at least 30 days. Ten stabilizer combinations were tested and the rates of HAN-TEAN decomposition were lowered by 74 to 95 percent in the presence of iron.

Hornung, Steven D.↗

Microcalorimetry study of Ni/H2 battery self-discharge mechanism

The results of the present effort to elucidate the self-discharge mechanism show that: (1) there is a good correlation between the amount of heat evolved during the self-discharge reaction as measured by microcalorimetry and amount of self-discharge as determined by capacity measurements, indicating that the microcalorimetry is a useful technique for investigation of the self-discharge reaction of a Ni/H2 cell; (2) the self-discharge rate decreased pronouncedly as the amount of electrolyte around the electrode (degree of wetness) decreased indicating that diffusion of dissolved H2 in the electrolyte significantly affects the rate of the self-discharge reaction; (3) the self-discharge rate is higher with the beta-phase active material than with the beta-phase active material. Preliminary results also showed that a cadmium additive to the nickel electrode reduces the self-discharge rate.

Visintin, Arnaldo↗

Microcalorimetry: The First Two Decades

Our group at GSFC began experimental and theoretical work on microcalorimetry almost twenty years ago, in August of 1982. Over the next 10 months, we completed the initial demonstration of a Si impurity thermometer-based calorimeter as an X-ray spectrometer. This successful demonstration resulted in the development by many investigators of scientific applications for microcalorimeters, ranging from optical spectroscopy to dark matter detection to particle physics applications. Many new technical approaches for cryogenic detectors were proposed by investigators and have been developed. In this presentation, I will describe the early development of microcalorimeters at GSFC and University of Wisconsin and the subsequent rapid growth of this work around the world The key milestones in the early development were the initial spectroscopy demonstrations and the selection of XRS, our microlcalorimeter-based instrument for the Advanced X-ray Astrophysics Facility (AXAF) and ultimately for ASTRO-E. An additional key event was the development of the direct detection of dark matter experiment and the formation of the Center for Particle Astrophysics. Both of these programs provided long term support for this technology in its precarious early days. A major additional technical step in the development of detectors was the demonstration of devices based on superconducting transition edge sensors (TES). These detectors promised (and have delivered) improved energy resolution and higher event rate capabilities. They couple naturally to SQUIDS, which operate well at the low temperatures where the detectors must operate. The past two decades have taken microcalorimeters from their infancy to applications in real experiments. I will provide an overview of the early development of the devices and review the breadth of the present technology and applications.

Moseley, Harvey↗

Using Isothermal Microcalorimetry to Determine Compatibility of Structural Materials with High-Test Hydrogen Peroxide (HTP) Propellant

High-Test Hydrogen Peroxide (HTP) propellant (equal to or greater than 70%) offers many advantages in space launch applications. However, materials used in construction of propulsion systems must be shown to be compatible with HTP. Isothermal Microcalorimetry (IMC) was used to determine the compatibility of several metallic and non-metallic materials with 90% HTP. The results of these experiments agreed with those from immersion bath tests when the values were converted to % Active Oxygen Loss per week (%AOL/wk).

Gostowski, Rudy↗

Using Isothermal Microcalorimetry to Determine Compatibility of Structural Materials with High Test Hydrogen Peroxide (HTP) Propellant

High-Test Hydrogen Peroxide (HTP) propellant (greater than or equal to 70%) offers many advantages in space launch applications; however, materials used in construction of propulsion systems must be shown to be compatible with HTP. Isothermal Microcalorimetry (IMC) was used to determine the compatibility of several metallic and non-metallic materials with 90% HTP. The results of these experiments agreed with those from immersion bath tests when the values were converted to %Active Oxygen Loss per week (%AOL/wk).

Gostowski, Rudy↗

Hydrogen Peroxide - Material Compatibility Studied by Microcalorimetry

Environmental and toxicity concerns with current hypergolic propellants have led to a renewed interest in propellant grade hydrogen peroxide (HP) for propellant applications. Storability and stability has always been an issue with HP. Contamination or contact of HP with metallic surfaces may cause decomposition, which can result in the evolution of heat and gas leading to increased pressure or thermal hazards. The NASA Johnson Space Center White Sands Test Facility has developed a technique to monitor the decompositions of hydrogen peroxide at temperatures ranging from 25 to 60 C. Using isothermal microcalorimetry we have measured decomposition rates at the picomole/s/g level showing the catalytic effects of materials of construction. In this paper we will present the results of testing with Class 1 and 2 materials in 90 percent hydrogen peroxide.

Homung, Steven D.↗

A new thermal sensor for X-ray microcalorimetry

A concept for a detector is introduced which exploits the significant temperature dependence of the dielectric constant in ferroelectric materials. The concept permits the use of a microcalorimeter without the resistive sensors which are associated with heat dissipation and increased Johnson noise in the electronic conversion circuit. General calorimeter features are listed, and the concepts related to dielectric calorimeters are discussed in terms of operational and detection advantages. The use of the device is delineated both theoretically and experimentally with the results of an operational dielectric material. The mixed-crystal quantum ferroelectric is employed and detects 6 MeV alpha particles while operating at 1.2 K in the first detection conducted. The temperature dependence of the dielectric constant in the materials allows for the elimination of resistive sensors in microcalorimeters, thereby improving the ultimate sensitivity of the instrument.

Silver, Eric↗

Blocking Filters with Enhanced Throughput for X-Ray Microcalorimetry

New and improved blocking filters (see figure) have been developed for microcalorimeters on several mission payloads, made of high-transmission polyimide support mesh, that can replace the nickel mesh used in previous blocking filter flight designs. To realize the resolution and signal sensitivity of today s x-ray microcalorimeters, significant improvements in the blocking filter stack are needed. Using high-transmission polyimide support mesh, it is possible to improve overall throughput on a typical microcalorimeter such as Suzaku s X-ray Spectrometer by 11%, compared to previous flight designs. Using polyimide to replace standard metal mesh means the mesh will be transparent to energies 3 keV and higher. Incorporating polyimide s advantageous strength-to-weight ratio, thermal stability, and transmission characteristics permits thinner filter materials, significantly enhancing through - put. A prototype contamination blocking filter for ASTRO-H has passed QT-level acoustic testing. Resistive traces can also be incorporated to provide decontamination capability to actively restore filter performance in orbit.

Grove, David↗

Microcalorimetric Measurements of Hydrogen Peroxide Stability

Recent interest in propellants with nontoxic reaction products has led to a resurgence of interest in hydrogen peroxide for various propellant applications. Because hydrogen peroxide is sensitive to contaminants and materials interactions, stability and shelf life are issues. A relatively new, ultrasensitive heat measurement technique, isothermal microcalorimetry, is being used at the White Sands Test Facility to monitor the decomposition of hydrogen peroxide at near ambient temperatures. Isothermal microcalorimetry measures the beat flow from a reaction vessel into a surrounding heat sink. In these applications, microcalorimetry is approximately 1,000 times more sensitive than accelerating rate calorimetry or differential scanning calorimetry for measuring thermal events. Experimental procedures have been developed for the microcalorimetric measurement of the ultra-small beat effects caused by incompatible interactions of hydrogen peroxide. The decomposition rates of hydrogen peroxide at the picomole/sec/gram level have been measured showing the effects of stabilizers and peroxide concentration. Typical measurements are carried out at 40 C over a 24-hour period, This paper describes a method for the conversion of the heat flow measurements to chemical reaction rates based on thermochemical considerations. The reaction rates are used in a study of the effects of stabilizer levels on the decomposition of propellant grade hydrogen peroxide.

Davis, Dennis D.↗

Reactivity of nonaqueous organic electrolytes towards lithium

The successful operation of an ambient temperature secondary lithium cell is primarily dependent on the stability of the electrolyte towards lithium. The lithium electrode on open circuit must be inert towards the electrolyte to achieve a long shelf life. The reactivity of tetrahydrofuran and 2-methyltetrahydrofuran based electrolytes with additives such as 2-methylfuran, ethylene carbonate, propylene carbonate, and 3-methylsulfolane was investigated by microcalorimetry and ac impedance spectroscopy techniques. Also the stability of electrolytes by open circuit stand tests was studied. Addition of ethylene carbonate and 2-methylfuran additives was found to improve the stability of tetrahydrofuran and 2-methyltetrahydrofuran based electrolytes. Long term microcalorimetry and ac impedance data clearly confirmed the higher stability of ethylene carbonate/2-methyltetrahydrofuran electrolyte compared to the 2-methyltetrahydrofuran and propylene carbonate/2-methyltetrahydrofuran electrolytes.

Shen, D. H.↗

Performance characteristics of lithium primary cells after controlled storage

A program was initiated to investigate the effects of storage on the performance of lithium primary cells. Two types of liquid cathode cells were chosen to investigate these effects. The cell types included Li-SOCl2/BCX cells, Li-SO2 cells from two different manufacturers, and a small sample size of 8-year-old Li-SO2 cells. The following measurements are performed at each test interval: open circuit voltage, resistance and weight, microcalorimetry, ac impedance, capacity, and voltage delay. The authors examine the performance characteristics of these cells after one year of controlled storage at two temperatures (10 and 30 C). The Li-SO2 cells experienced little to no voltage and capacity degradation after one year storage. The Li-SOCl2/BCX cells exhibited significant voltage and capacity degradation after 30 C storage. Predischarging shortly prior to use appears to be an effective method of reducing the initial voltage drop. Studies are in progress to correlate ac impedance and microcalorimetry measurements with capacity losses and voltage delay.

Deligiannis, F.↗

Effect of cycling on the lithium/electrolyte interface in organic electrolytes

Nondestructive methods such as ac impedance spectroscopy and microcalorimetry are used to study the effect of cell cycling on the lithium/electrolyte interface. The reactivity of both uncycled and cycled lithium towards various electrolytes is examined by measuring the heat evolved from the cells under open-circuit conditions at 25 C by microcalorimetry. Cycled cells at the end of charge/discharge exhibited considerably higher heat output compared with the uncycled cells. After 30 d of storage, the heat output of the cycled cells is similar to that of the uncycled cells. The cell internal resistance increases with cycling, and this is attributed to the degradation of the electrolyte with cycling.

Surampudi, S.↗

Effects of NaCl on metabolic heat evolution rates by barley roots

The effect of salinity stress on metabolic heat output of barley (Hordeum vulgare L.) root tips was measured by isothermal microcalorimetry. Several varieties differing in tolerance to salinity were compared and differences quantified. Two levels of inhibition by increasing salt were found. Following the transition from the initial rate of the first level, inhibition remained at about 50% with further increases in salt concentration up to 150 millimolar. The concentration of salt required to inhibit to this level was cultivar dependent. At highter concentrations (>150 millimolar) of salt, metabolism was further decreased. This decrease was not cultivar dependent. The decreased rate of metabolic heat output at the first transition could be correlated with decreases in uptake of NO3-, NH4+, and Pi that occurred as the salt concentration was increased. The high degree of dependence of the inhibition of metabolic heat output on NaCl concentration points to a highly cooperative reaction responsible for the general inhibition of metabolism and nutrient uptake. The time required to attain the first level of salt inhibition is less than 20 minutes. Inhibition of root tips was not reversible by washing with salt free solutions. In addition to revealing these features of salt inhibition, isothermal microcalorimetry is a promising method for convenient and rapid determination of varietal differences in response to increasing salinity.

NASA Discipline Life Support Systems↗

Kinetics of Open Circuit Processes in Undischarged Li/SOC12 Cells

The kinetics of the heat producing processes in undischarged Li/SOCl2 cells under open circuit conditions were measured by heat-conduction microcalorimetry. The cells studied, Honeywell type G2666 reserve cells, were activated as needed and the rate of open circuit heat output determined as a function of time since activation and temperature. The results at each temperature can be described by an equation of the form q = Bktx where q is the rate of heat output, B is the heat produced per unit of reaction, k and x are empirical constants, and t is the time since activation. Both x and k are found to be functions of temperature; therefore, accelerated testing at elevated temperatures is probably not valid for these cells until the processes involved are better understood.

Hansen, L. D.↗

The application of thermodynamic and spectroscopic techniques to adhesion in the polyimide/Ti 6-4 and polyphenylquinoxaline/Ti 6-4 systems

The results of calorimetric measurements of Ti adherend surfaces are presented. The measurements were carried out after several chemical pretreatments and after fracture of several lap shear samples aged at high temperature. The exact composition of the Ti samples was Ti(6 percent Al-4 percent V). The adhesives used were polyimides and polyphenylquinoxalines (PPQ). Each chemical pretreatment was accompanied by a unique spectroscopic feature which was characterized by XPS, SEM, and specular reflectance infrared spectroscopy. The energetics of the interaction between primer solutions and the Ti adherend were evaluated by microcalorimetry. Changes in the structure of the surface oxide layer upon heating of the adherend were deduced from immersion temperatures of the PI and PPQ solutions. The XPS and SEM data are given is a table.

Dias, S.↗

High resolution X-ray spectroscopy using microcalorimeters

The use of microcalorimeters for high-resolution, high quantum efficiency, nondispersive X-ray spectroscopy has been demonstrated over the past few years. In this paper, the principles of X-ray calorimetry are reviewed, and the results of ongoing X-ray tests using microcalorimetry are summarized. An approach to building an X-ray calorimeter spectrometer is discussed.

Kelley, R. L.↗