ALBERT

Description: Since 1997 numerous fires have been reported to the Food and Drug Administration involving cylinder valves installed on medical use oxygen cylinders sold and operated within the United States. All of the cylinder valves in question had polychlorotrifluoroethylene (PCTFE) valve seats. Subsequent failure analysis showed that the main seat was the primary source of ignition. A review of the incidents involving cylinder valve fires indicated three possible ignition mechanisms: contaminant promotion, flow friction, and resonance. However, gas purity analysis showed that uncombusted, residual oxygen was within specification. Infrared and energy dispersive spectroscopy further showed that no contaminants or organic compounds were present in the remaining, uncombusted valve seat material or on seat plug surfaces. Therefore, contaminant-promoted ignition did not appear to be responsible for the failures. Observations of extruded material along the outer edge of the coined or loaded seat area produced by cylinder overuse or poppet overload led to concerns that accelerated gas flow across a deformed seat surface could generate enough localized heating to ignite the polymeric seat. Low molecular weight or highly amorphous quick-quenched PCTFE grades might be expected to be especially prone to this type of deformation. Such a failure mechanism has been described as flow friction; however, the corresponding mechanistic parameters are poorly understood. Subsequent revelation of low-temperature dimensional instability by thermomechanical analysis (TMA) in a variety of PCTFE sheet and rod stock samples led to new concerns that PCTFE valve seats could undergo excessive expansion or contraction during service. During expansion, additional extrusion and accompanying flow friction could occur. During contraction, a gap between the seal and adjacent metal surfaces could form. Gas flowing past the gap could, in turn, lead to resonance heating and subsequent ignition as described in ASTM Guide for Evaluation Nonmetallic Materials for Oxygen Service (G 63). Attempts to uncover the origins of the observed dimensional instability were hindered by uncertainties about resin grade, process history, and post-process heat history introduced by machining, annealing, and sample preparation. An approach was therefore taken to monitor property changes before and after processing and machining using a single, well-characterized lot of Neoflon CTFE.1 M400H resin. A task group consisting of the current PCTFE resin supplier, two molders, and four valve seat manufacturers was formed, and phased testing on raw resin, intermediate rod stock, and finished valve seats initiated. The effect of processing and machining on the properties of PCTFE rod stock and oxygen gas cylinder valve seats was then determined. Testing focused on two types of extruded rod stock and one type of compression-molded rod stock. To accommodate valve seat manufacturer preferences for certain rod stock diameters, two representative diameters were used (4.8 mm (0.1875 in.) and 19.1 mm (0.75 in.)). To encompass a variety of possible sealing configurations, seven different valve seat types with unique geometries or machining histories were tested. The properties investigated were dimensional stability as determined by TMA, specific gravity, differential scanning calorimetry (DSC), compressive strength, zero strength time, and intrinsic viscosity. Findings are discussed in the context of polymer structure-process-property relationships whenever possible.

Description: The permeation resistance of chlorinated polyethylene (CPE) used in totally encapsulating chemical protective suits against the aerospace fuels hydrazine, monomethylhydrazine, and uns-dimethylhydrazine was determined by measuring the breakthrough time (BT) and time-averaged vapor transmission rate (VTR) using procedures consistent with ASTM F 739 and ASTM F 1383. Two exposure scenarios were simulated: a 2 hour (h) fuel vapor exposure, and a liquid fuel "splash" followed by a 2 h vapor exposure. To simulate internal suit pressure during operation, a positive differential pressure of 0.3 in. water (75 Pa) on the collection side of the permeation apparatus was used. Using the available data, a model was developed to estimate propellant concentrations inside an air-line fed, totally encapsulating chemical protective suit. Concentrations were calculated under simulated conditions of fixed vapor transmission rate, variable breathing air flow rate, and variable splash exposure area. Calculations showed that the maximum allowable permeation rates of hydrazine fuels through CPE were of the order of 0.05 to 0.08 ng/sq cm min for encapsulating suits with low breathing air flow rates (of the order of 5 scfm or 140 L min-1). Above these permeation rates, the 10 parts-per-billion (ppb) threshold limit value time-weighted average could be exceeded. To evaluate suit performance at 10 ppb threshold-limiting value/time-weighted average level concentrations, use of a sensitive analytical method such as cation exchange high performance liquid chromatography with amperometric detection was found to be essential. The analytical detection limit determines the lowest measurable VTR, which in turn governed the lowest per meant concentration that could be calculated inside the totally encapsulating chemical protective suit.

Description: Teflon has been identified as suitable material for use in oxygen-enriched atmospheres because of its low specific enthalpy of combustion that is, less than 1500 cal/gram. However, once ignited, Teflon burns in a heterogeneous reaction until total consumption or depletion of oxygen occurs. A model is developed for the burning of Teflon in pure, high-pressure oxygen, 3.4 to 68.9 MPa. The Teflon polymer chain dissociates via monomer units due to pyrolysis. These monomer units diffuse to the surface due to free convection. The model consists of coupled mass and energy balances for the polymer and an energy balance for the free convection of product gases. The model is used to obtain appropriate kinetic parameters for the dissociation and surface reactions. The model is validated against experimental measurements of Teflon discs supported on aluminum rods (2216) at oxygen pressures of 3.4, 6.8, 34.4, and 68.9 MPa. The model simulates the temperature distribution in the product gases above burning Teflon.

Description: The oxygen compatibility of six polymers used in oxygen service was evaluated after exposure for 48 hours to oxygen pressures ranging from 350 to 6200 kPa (50 to 900 psia), and temperatures ranging from 50 to 250 C (122 to 302 F). Three elastomers were tested: CR rubber (C873-70), FKM fluorocarbon rubber (Viton A), and MPQ silicone rubber (MIL-ZZ-765, Class 2); and three thermoplastics were tested: polyhexamethylene adipamide (Zytel 42), polytetrafluoroethylene (Teflon TFE), and polychlorotrifluoroethylene (Neoflon CTFE M400H). Post-aging changes in mass, dimensions, tensile strength, elongation at break, and durometer hardness were determined. Also, the compression set was determined for the three elastomers. Results show that the properties under investigation were more sensitive to oxygen pressure at low to moderate temperatures, and more sensitive to temperature at low to moderate oxygen pressures. Inspection of the results also suggested that both chain scissioning and cross-linking processes were operative, consistent with heterogeneous oxidation. Attempts are underway to verify conclusively the occurrence of heterogeneous oxidation using a simple modulus profiling technique. Finally, the effect of aging at 620 kpa (90 psia) and 121 C (250 F) on ignition and combustion resistance was determined. As expected, aged polymers were less ignitable and combustible (had higher AlTs and lower heats of combustion). Special attention was given to Neoflon CTFE. More specifically, the effect of process history (compression versus extrusion molding) and percent crystallinity (quick- versus slow-quenched) on the AIT, heat of combustion, and impact sensitivity of Neoflon CTFE was investigated. Results show the AIT, heat of combustion, and impact sensitivity to be essentially independent of Neoflon CTFE process history and structure.

Description: The dimensional stability of polychlorotrifluoroethylene (PCTFE) valve seats used in oxygen regulator applications was determined by thermomechanical analysis (TMA). Two traceable grades of PCTFE were tested; Kel-F 81 and Neoflon CTFE M400H. For these particular resins, the effect of percent crystallinity, zero strength time (ZST) molecular weight, resin grade, process history (compression-molded versus extruded) on the dimensional stability and annealing behavior was determined. In addition to the traceable Kel-F 81 and Neoflon CTFE M400H grades, actual PCI'PH valve seats of differing geometry and design were tested by TMA. The PCTFE valve seats were of unspecified resin grade, although certain inferences about the grade could be drawn based on knowledge of the valve seat fabrication date. Results consistently revealed dimensional instability of varying magnitude at temperatures ranging from 40 to 70 degrees Celsius. Furthermore, some of the pre- 1 995 seats appeared to be more dimensionally stable than those fabricated after 1995. The TMA results are discussed in the context of several proposed ignition mechanisms; namely, particle impact, presence of contaminant oils and fibers, and localized heating by flow friction and/or resonance. The effect of metal constraint on the dimensional stability of PCTFE is also discussed. Finally, the effect of percent crystallinity, ZST molecular weight, resin grade, process history (compression-molded versus extruded) on the AIT, delta Hc and impact sensitivity of various types of Neoflon CTFE M400H was determined using Kel-F 81 as a control. Results show that the AIT, delta Hc and impact sensitivity were essentially independent of Neoflon CTFE process history and structure.

Description: Broadband modal acoustic emission (AE) data were acquired during intermittent load hold tensile test profiles on Toray T1000G carbon fiber-reinforced epoxy (C/Ep) single tow specimens. A novel trend seeking statistical method to determine the onset of significant AE was developed, resulting in more linear decreases in the Felicity ratio (FR) with load, potentially leading to more accurate failure prediction. The method developed uses an exponentially weighted moving average (EWMA) control chart. Comparison of the EWMA with previously used FR onset methods, namely the discrete (n), mean (n (raised bar)), normalized (n%) and normalized mean (n(raised bar)%) methods, revealed the EWMA method yields more consistently linear FR versus load relationships between specimens. Other findings include a correlation between AE data richness and FR linearity based on the FR methods discussed in this paper, and evidence of premature failure at lower than expected loads. Application of the EWMA method should be extended to other composite materials and, eventually, composite components such as composite overwrapped pressure vessels. Furthermore, future experiments should attempt to uncover the factors responsible for infant mortality in C/Ep strands.

Description: The Space Radiation Effects on Inflatable Habitat Materials project provides much needed risk reduction data to assess space radiation damage of existing and emerging materials used in manned low-earth orbit, lunar, interplanetary, and Martian surface missions. More specifically, long duration (up to 50 years) space radiation damage will be quantified for materials used in inflatable structures (1st priority), as well as for habitable composite structures and space suits materials (2nd priority). The data acquired will have relevance for nonmetallic materials (polymers and composites) used in NASA missions where long duration reliability is needed in continuous or intermittent radiation fluxes. This project also will help to determine the service lifetimes for habitable inflatable, composite, and space suit materials.

Description: This project is a subtask of a multi-center project to advance the state-of-the-art by developing NDE techniques that are capable of evaluating stress rupture (SR) degradation in Kevlar/epoxy (K/Ep) composite overwrapped pressure vessels (COPVs), and damage progression in carbon/epoxy (C/Ep) COPVs. In this subtask, acoustic emission (AE) data acquired during intermittent load hold tensile testing of K/Ep and C/Ep composite tow materials-of-construction used in COPV fabrication were analyzed to monitor progressive damage during the approach to tensile failure. Insight into the progressive damage of composite tow was gained by monitoring AE event rate, energy, source location, and frequency. Source location based on arrival time data was used to discern between significant AE attributable to microstructural damage and spurious AE attributable to background and grip noise. One of the significant findings was the observation of increasing violation of the Kaiser effect (Felicity ratio 〈 1.0) with damage accumulation.

Description: Acoustic emission (AE) data acquired during intermittent load hold tensile testing of epoxy impregnated Kevlar(Registeres TradeMark) 49 (K/Ep) composite strands were analyzed to monitor progressive damage during the approach to tensile failure. Insight into the progressive damage of K/Ep strands was gained by monitoring AE event rate and energy. Source location based on energy attenuation and arrival time data was used to discern between significant AE attributable to microstructural damage and spurious AE attributable to noise. One of the significant findings was the observation of increasing violation of the Kaiser effect (Felicity ratio 〈 1.0) with damage accumulation. The efficacy of three different intermittent load hold stress schedules that allowed the Felicity ratio to be determined analytically is discussed.

Description: Composite OverWrapped Pressure Vessels (COPVs) are currently accepted by NASA based on design and qualification requirements and generally not verified by NDE for the following reasons: (1) Manufactures and end users generally do not have experience and validated quantitative methods of detecting flaws and defects of concern (1-a) If detected, the flaws are not adequately quantified and it is unclear how they may contribute to degradation in mechanical response (1-b) Carbon-epoxy COPVs also extremely sensitive to impact damage and impacts may be below the visible detection threshold (2) If damage is detected, this generally results in rejection since the effect on mechanical response is generally not known (3) NDE response has not generally been fully characterized, probability of detection (POD) established, and processes validated for evaluation of vessel condition as manufactured and delivered.