Highly Thermally Conductive Hybrid Carbon Fiber Polymer Composite for Carbon Dioxide Deposition System
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A realistic release of carbon fibers was established by burning a minimum of 45 kg of carbon fiber composite aircraft structural components in each of five large scale, outdoor aviation jet fuel fire tests. This release was quantified by several independent assessments with various instruments developed specifically for these tests. The most likely values for the mass of single carbon fibers released ranged from 0.2 percent of the initial mass of carbon fiber for the source tests (zero wind velocity) to a maximum of 0.6 percent of the initial carbon fiber mass for dissemination tests (5 to 6 m/s wind velocity). Mean fiber lengths for fibers greater than 1 mm in length ranged from 2.5 to 3.5 mm. Mean diameters ranged from 3.6 to 5.3 micrometers which was indicative of significant oxidation. Footprints of downwind dissemination of the fire released fibers were measured to 19.1 km from the fire.
Recent safety considerations have sought to lower the electrical conductivity of carbon fibers. Carbon fibers produced from polyacrylonitrile at low carbonization temperatures (600-900 C) possess low electrical conductivity but do not possess adequate strength. Low-temperature processes are described which improve fiber strength but do not increase electrical conductivity substantially. The processes result in a carbon fiber with nearly twice the tensile strength compared to the old process. Process development and its effect on fiber properties are reported.
A process for coating carbon fibers with platinum has been developed. The process may also be adaptable to coating carbon fibers with other noble and refractory metals, including rhenium and iridium. The coated carbon fibers would be used as ingredients of matrix/fiber composite materials that would resist oxidation at high temperatures. The metal coats would contribute to oxidation resistance by keeping atmospheric oxygen away from fibers when cracks form in the matrices. Other processes that have been used to coat carbon fibers with metals have significant disadvantages: Metal-vapor deposition processes yield coats that are nonuniform along both the lengths and the circumferences of the fibers. The electrical resistivities of carbon fibers are too high to be compatible with electrolytic processes. Metal/organic vapor deposition entails the use of expensive starting materials, it may be necessary to use a furnace, and the starting materials and/or materials generated in the process may be hazardous. The present process does not have these disadvantages. It yields uniform, nonporous coats and is relatively inexpensive. The process can be summarized as one of pretreatment followed by electroless deposition. The process consists of the following steps: The surfaces of the fiber are activated by deposition of palladium crystallites from a solution. The surface-activated fibers are immersed in a solution that contains platinum. A reducing agent is used to supply electrons to effect a chemical reduction in situ. The chemical reduction displaces the platinum from the solution. The displaced platinum becomes deposited on the fibers. Each platinum atom that has been deposited acts as a catalytic site for the deposition of another platinum atom. Hence, the deposition process can also be characterized as autocatalytic. The thickness of the deposited metal can be tailored via the duration of immersion and the chemical activity of the solution.
Carbon fiber reinforced plastic (CFRP) appears to be the material most suited for the construction of submillimeter telescopes (SMT) not only for ground-based use but also for space applications. The accuracy of the CFRP reflectors needs to be improved beyond value of the 17 micron rms envisaged for the 10 m SMT.
Commercially produced carbon fibers were heat treated to graphitization temperatures. The fibers were characterized for mechanical and physical properties, including density, D0002 spacing, strength, and modulus in both the 'as received' and heat treated conditions. Mechanical property changes were correlated with the physical property changes in the fibers.
The presence of carbon fibers increased the crystallization rates of both PEEK and PPS thermoplastic polymers. The effect was most pronounced at higher crystallization temperatures. Isothermal crystallization rates were analyzed by applying classical phenomenological nucleation theory. Unusually high values of the so-called Avrami exponent were found for neat PEEK. Isothermal crystallization of PEEK and PPS polymers produced crystalline samples having a wide variety of melting temperatures. The melting as observed by differential scanning calorimetry occurred as dual endotherms which were called primary (higher temperature) and secondary melting peaks. Each primary peak accounted for most of the crystallinity present. The secondary peaks represented the melting of crystallites formed later than those attributable to the primary endotherms. The presence of carbon fibers increased the thermal stability of both PEEK and PPS crystallites as manifested by higher temperatures for the primary melting peaks. This may be attributable to increased crystallite size, greater crystallite perfection, and/or favorable modification of the crystallite interface. Over the range studied, crystallization temperature strongly influenced the positions of the secondary peaks but not the primary peaks.
Because carbon fibers are strong, stiff, and lightweight, they are attractive for use in composite structures. Because they also have high electrical conductivity, free carbon fibers settling on electrical conductors can cause malfunctions. If released from the composite by burning, the fibers may become a hazard to exposed electrical and electronic equipment. As part of a Federal study of the potential hazard associated with the use of carbon fibers, NASA assessed the public risk associated with crash fire accidents of civil aircraft. The NASA study projected a dramatic increase in the use of carbon composites in civil aircraft and developed technical data to support the risk assessment. Personal injury was found to be extremely unlikely. In 1993, the year chosen as a focus for the study, the expected annual cost of damage caused by released carbon fibers is only $1000. Even the worst-case carbon fiber incident simulated (costing $178,000 once in 34,000 years) was relatively low-cost compared with the usual air transport accident cost. On the basis of these observations, the NASA study concluded that exploitation of composites should continue, that additional protection of avionics is unnecessary, and that development of alternate materials specifically to overcome this problem is not justified.
Pitch-based nanocomposite carbon fibers were prepared with various percentages of carbon nanofibers (CNFs), and the fibers were used for manufacturing composite structures. Experimental results show that these nanocomposite carbon fibers exhibit improved structural and electrical conductivity properties as compared to unreinforced carbon fibers. Composite panels fabricated from these nanocomposite carbon fibers and an epoxy system also show the same properties transformed from the fibers. Single-fiber testing per ASTM C1557 standard indicates that the nanocomposite carbon fiber has a tensile modulus of 110% higher, and a tensile strength 17.7% times higher, than the conventional carbon fiber manufactured from pitch. Also, the electrical resistance of the carbon fiber carbonized at 900 C was reduced from 4.8 to 2.2 ohm/cm. The manufacturing of the nanocomposite carbon fiber was based on an extrusion, non-solvent process. The precursor fibers were then carbonized and graphitized. The resultant fibers are continuous.
T-300 carbon fibers (BP Amoco Chemicals, Greenville, SC) are a common reinforcement for silicon carbide composite materials, and carbon-fiber-reinforced silicon carbide composites (C/SiC) are proposed for use in space propulsion applications. It has been shown that the time to failure for C/SiC in stressed oxidation tests is directly correlated with the fiber oxidation rate (ref. 1). To date, most of the testing of these fibers and composites has been conducted in oxygen or air environments; however, many components for space propulsion, such as turbopumps, combustors, and thrusters, are expected to operate in hydrogen and water vapor (H2/H2O) environments with very low oxygen contents. The oxidation rate of carbon fibers in conditions representative of space propulsion environments is, therefore, critical for predicting component lifetimes for real applications. This report describes experimental results that demonstrate that, under some conditions, lower oxidation rates of carbon fibers are observed in water vapor and H2/H2O environments than are found in oxygen or air. At the NASA Glenn Research Center, the weight loss of the fibers was studied as a function of water pressure, temperature, and gas velocity. The rate of carbon fiber oxidation was determined, and the reaction mechanism was identified.
A carbon fiber rope thermal barrier is being evaluated as a replacement for the conventional room temperature vulcanizing (RTV) thermal barrier that is currently used to protect o-rings in Reusable Solid Rocket Motor (RSRM) nozzle joints. Performance requirements include its ability to cool any incoming, hot propellant gases that fill and pressurize the nozzle joints, filter slag and particulates, and to perform adequately in various joint assembly conditions as well as dynamic flight motion. Modified National Aeronautics and Space Administration (MNASA) motors, with their inherent and unique ability to replicate select RSRM internal environment features, were an integral step in the development path leading to full scale RSRM static test demonstration of the carbon fiber rope (CFR) joint concept. These 1/4 scale RSRM motors serve to bridge the gap between the other classes of subscale test motors (extremely small and moderate duration, or small scale and short duration) and the critical asset RSRM static test motors. A series of MNASA tests have been used to demonstrate carbon fiber rope performance and have provided rationale for implementation into a full-scale static motor and flight qualification.
The modulus and residual strain in carbon fibers are measured by successively electrochemically milling away the fiber surface. Electrochemical etching is found to remove the carbon fiber surface very uniformly, in contrast to air and wet oxidation. The precision of fiber diameter measurements is improved by using a laser diffraction technique instead of optical methods. More precise diameter measurements reveal that past correlations of diameter and fiber modulus are largely measurement artifact. The moduli of most carbon fibers decrease after the outer layers of the fibers are removed. Owing to experimental difficulties, the moduli and strengths of the fibers at their centers are not determined, and moduli are estimated on the basis of microstructure. The calculated residual stresses are found to be insensitive to these moduli estimates as well as the exact form of regression equation used to describe the moduli and residual strain distributions. Axial compressive residual stresses are found to be very high for some higher modulus carbon fibers. It is pointed out that the compressive stress makes the fibers insensitive to surface flaws when loaded in tension but it may initiate failure by buckling when loaded in compression.
Fluorine stored in graphite or graphitelike carbon fibers for later release and/or use in chemical reactions. Storage in carbon fibers eliminates difficulty and risk of using high-pressure tanks and pipes to hold corrosive gas. Storage in carbon fibers makes fluorine more readily accessible than does storage as constituent of metal fluoride. Carbon fibers heated to release stored fluorine, which draws away to vessel where reacts with material to be fluorinated, possibly at temperature other than release temperature. Alternatively, material to be fluorinated mixed or otherwise placed in contact with fibers and entire mass heated to or beyond release temperature.
Various experimental and analytical studies performed for the NASA carbon fiber risk assessment program are described with emphasis on carbon fiber characteristics, sensitivity of electrical equipment and components to shorting or arcing by carbon fibers, attenuation effect of carbon fibers on aircraft landing aids, impact of carbon fibers on industrial facilities. A simple method of estimating damage from airborne carbon fibers is presented.
The possible effects of free carbon fibers on aircraft avionic equipment operation, removal costs, and safety were investigated. Possible carbon fiber flow paths, flow rates, and transfer functions into the Boeing 707, 727, 737, 747 aircraft and potentially vulnerable equipment were identified. Probabilities of equipment removal and probabilities of aircraft exposure to carbon fiber were derived.
The effects of carbon structure and surface oxygen on the carbon's performance as the anode in lithium-ion battery were studied. Two carbon materials were used for the electrochemical tests: soft carbon made from defluorination of graphite fluoride, and the carbon precursor from which the graphite fluoride was made. In this research the precursor was graphitized carbon fiber P-100. It was first fluorinated to form CF(0.68), then defluorinated slowly at 350 to 450 C in bromoform, and finally heated in 1000 C nitrogen before exposed to room temperature air, producing disordered soft carbon having basic surface oxides. This process caused very little carbon loss. The electrochemical test involved cycles of lithium intercalation and deintercalation using C/saturated LiI-50/50 (vol %) EC and DMC/Li half cell. The cycling test had four major results. (1) The presence of a basic oxide surface may prevent solvent from entering the carbon structure and therefore prolong the carbon's cycle life for lithium intercalation-deintercalation. (2) The disordered soft carbon can store lithium through two different mechanisms. One of them is lithium intercalation. which gives the disordered carbon an electrochemical behavior similar to its more ordered graphitic precursor. The other is unknown in its chemistry, but is responsible for the high-N,oltage portion (less than 0.3V) of the charge-discharge curve. (3) Under certain conditions, the disordered carbon can store more lithium than its precursor. (4) These sample and its precursor can intercalate at 200 mA/g. and deintercalate at a rate of 2000 mA/g without significant capacity loss.
Carbon fiber sampling instruments were developed: passive collectors made of sticky bridal veil mesh, and active instruments using a light emitting diode (LED) source. These instruments measured the number or number rate of carbon fibers released from carbon/graphite composite material when the material was burned in a 10.7 m (35 ft) dia JP-4 pool fire for approximately 20 minutes. The instruments were placed in an array suspended from a 305 m by 305 m (1000 ft by 1000 ft) Jacob's Ladder net held vertically aloft by balloons and oriented crosswind approximately 140 meters downwind of the pool fire. Three tests were conducted during which released carbon fiber data were acquired. These data were reduced and analyzed to obtain the characteristics of the released fibers including their spatial and size distributions and estimates of the number and total mass of fibers released. The results of the data analyses showed that 2.5 to 3.5 x 10 to the 8th power single carbon fibers were released during the 20 minute burn of 30 to 50 kg mass of initial, unburned carbon fiber material. The mass released as single carbon fibers was estimated to be between 0.1 and 0.2% of the initial, unburned fiber mass.
Carbon and graphite fibers are known to be electrically conductive. The rapidly accelerating use of carbon fibers as the reinforcement in filamentary composite materials brought up the possibility of accidental release of carbon fibers from the burning of crashed commercial airliners with carbon composite parts. Such release could conceivably cause widespread damage to electrical and electronic equipment. The experimental and analytical results of a comprehensive investigation of the various elements necessary to assess the extent of such potential damage in terms of annual expected costs and maximum losses at low probabilities of occurrence are presented. A review of NASA materials research program to provide alternate or modified composite materials to overcome any electrical hazards from the use of carbon composites in aircraft structures is described.