The synthesis and characterization of some potential ablative polymers
Ablative polymers synthesis from formaldehyde, phenols and ethers reaction products, discussing char yield, thermally stable fillers incorporation and thermogravimetric analysis
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Ablative polymers synthesis from formaldehyde, phenols and ethers reaction products, discussing char yield, thermally stable fillers incorporation and thermogravimetric analysis
Development of ablative materials based on modification of polyphenylene compounds is discussed. Chemical and physical properties are analyzed for application as heat resistant materials. Synthesis of linear polyphenylenes is described. Effects of exposure to oxyacetylene flame and composition of resultant char layer are presented.
The curing and decompositions of polyphenylenes and several nitrogen-containing condensation polymers, particularly polybenzimidazoles and pyrones, are reviewed critically. It is concluded that the condensations are usually imperfect and incomplete and that in most of the published work the late stages of the condensation are complicated by the beginnings of the charring and carbonization processes. Most discussions of mechanisms in this range are highly speculative and of little value. The most promising fields for further research are at lower temperatures, where slow oxidation processes deserve study, and at higher temperatures, where it may be possible to influence carbonization processes to obtain better products.
A study was conducted to correlate Apollo ablation and thermal response flight data using advanced state-of-the-art analytical procedures. The agreement between flight data and predictions is consistently excellent for in-depth temperature distributions, char density profiles, and surface ablation, thus validating the analytical procedures.
Analytical trade studies are presented that consider passive TPS configurations using the following material categories: (1) reuseable surface insulation - surface-coated rigidized ceramic fiber; (2) low density charring ablators; and (3) carbon-carbon and high density ablators for leading edge areas. Emphasized are effects on TPS weight by variations in entry trajectories and material thermal characteristics.
A very low density ablative material, a silicone-phenolic composite, was flight tested on a recoverable spacecraft launched by a Pacemaker vehicle system; and, in addition, it was tested in an arc heated wind tunnel at three conditions which encompassed most of the reentry heating conditions of the flight tests. The material was composed, by weight, of 71 percent phenolic spheres, 22.8 percent silicone resin, 2.2 percent catalyst, and 4 percent silica fibers. The tests were conducted to evaluate the ablator performance in both arc tunnel and flight tests and to determine the predictability of the albator performance by using computed results from an existing one-dimensional numerical analysis. The flight tested ablator experienced only moderate surface recession and retained a smooth surface except for isolated areas where the char was completely removed, probably following reentry and prior to or during recovery. Analytical results show good agreement between arc tunnel and flight test results. The thermophysical properties used in the analysis are tabulated.
Heat shielding for planetary entry probes of future Jovian and Venusian missions will encounter heating levels well beyond those previously experienced. These entries are typically dominated by radiative heating from the shock layer. This paper demonstrates the potential of reflecting this incident radiation diffusely from an ablating material. This technique contrasts with the absorption experienced by char-forming or graphitic ablators. Two dielectric materials, Teflon (polytetra-fluoroethylene) and boron nitride, are examined for their ablative performance, including reflection, in a combined convective- and radiative-heating environment. For Teflon, at the conditions obtained, superimposition of radiative heating upon a convective stream causes no additional increase in surface recession over the convective only results. For boron nitride, an excellent room-temperature reflector in the visible spectrum, a decrease in reflectivity from 90 to 55 percent is experienced when the surface undergoes sublimation at high temperatures. The process of reflection in each of these materials is described in terms of backscattering from crystals. The significance of a sizable reflection as a mode of energy accommodation is demonstrated for Venusian entries as a potential reduction in mass loss due to ablation.
Coupled nonlinear partial differential equations describing heat and mass transfer in a porous matrix are solved in finite difference form with the aid of a new iterative technique (the strongly implicit procedure). Example numerical results demonstrate the characteristics of heat and mass transport in a porous matrix such as a charring ablator. It is emphasized that multidimensional flow must be considered when predicting the thermal response of a porous material subjected to nonuniform boundary conditions.
Parabolic reflectors fabricated from Carbon Fiber Reinforced Plastic (CFRP) composite material will not distort their shape by more than 3 percent of millimeter wavelength, despite large temperature differences on reflector surfaces. CFRP has zero thermal expansion. It is derived from charred polyacrylonitrite plastic filaments that are combined with epoxy resin.
A study performed to continue development of computational techniques for the Space Shuttle Thermal Protection System is reported. The resulting computer code was used to perform some additional optimization studies on several TPS configurations. The program was developed in Fortran 4 for the CDC 6400, and it was converted to Fortran 5 to be used for the Univac 1108. The computational methodology is developed in modular fashion to facilitate changes and updating of the techniques and to allow overlaying the computer code to fit into approximately 131,000 octal words of core storage. The program logic involves subroutines which handle input and output of information between computer and user, thermodynamic stress, dynamic, and weight/estimate analyses of a variety of panel configurations. These include metallic, ablative, RSI (with and without an underlying phase change material), and a thermodynamic analysis only of carbon-carbon systems applied to the leading edge and flat cover panels. Two different thermodynamic analyses are used. The first is a two-dimensional, explicit precedure with variable time steps which is used to describe the behavior of metallic and carbon-carbon leading edges. The second is a one-dimensional implicity technique used to predict temperature in the charring ablator and the noncharring RSI. The latter analysis is performed simply by suppressing the chemical reactions and pyrolysis of the TPS material.
Experimental results are presented for a long-duration-capability (1000-sec), space-storable, bipropellant liquid rocket motor burning fluorine/hydrazine or FLOX/monomethylhydrazine. The interrelationship between injected mixture ratio and the per cent film cooling on vacuum specific impulse performance and chamber heat transfer is given. Experimental sea level measurements are used to predict space vacuum performance based upon simplified JANNAF reference procedures. Dynamic combustion stability is demonstrated over a wide range of operating conditions. Analytical results of char penetration, erosion, and ablative wall temperature distributions are presented for prototype chamber designs.
A polymer has been developed that has excellent potential for use as windows in spacecraft as well as conventional aircraft. This polymer, phenolphthalein polycarbonate, has outstanding thermal properties, e.g., in place of melting or burning, it produces an insulating charred foam that closes off transmission of radiant heat through the window. This fact, coupled with an oxygen index of 0.43 and a 177 C tensile strength of 58 mega Newtons/sq m, makes this polymer a prime candidate for further development. Pilot plant preparation in a 20 gallon Pfaudler kettle was accomplished and large test specimens were prepared for evaluations.
Large-diameter carbon composite monofilaments with high strength and high modulus were produced by pregging multifiber carbon bundles with suitable organic resins and pyrolysing them together. Two approaches were developed to increase the utilization of fiber tensile strength by minimizing stress concentration defects induced by dissimilar shrinkage during pyrolysis. These were matrix modification to improve char yield and strain-to-failure and fiber-matrix copyrolysis to alleviate matrix cracking. Highest tensile strength and modulus were obtained by heat treatments to 2873 K to match fiber and matrix strain-to-failure and develop maximum monofilament tensile-strength and elastic modulus.
The thermochemical response of Coating 313 when exposed to a fuel fire environment was studied to provide a tool for predicting the reaction time. The existing Aerotherm Charring Material Thermal Response and Ablation (CMA) computer program was modified to treat swelling materials. The modified code is now designated Aerotherm Transient Response of Intumescing Materials (TRIM) code. In addition, thermophysical property data for Coating 313 were analyzed and reduced for use in the TRIM code. An input data sensitivity study was performed, and performance tests of Coating 313/steel substrate models were carried out. The end product is a reliable computational model, the TRIM code, which was thoroughly validated for Coating 313. The tasks reported include: generation of input data, development of swell model and implementation in TRIM code, sensitivity study, acquisition of experimental data, comparisons of predictions with data, and predictions with intermediate insulation.
Analytical studies had found the employment of an aerobraking trajectory for return of a reusable Space Tug from geosynchronous missions to be feasible and practical. To establish the minimum-weight ablative dome heat shield, trajectories involving 2 and 30 perigee passes were investigated both analytically and by plasma arc testing. Silicone-base ablators with densities of 15, 30, and 50 lb/cu ft were selected for evaluation. All models withstood the multipass exposures without deleterius surface recession or char erosion. Dome heat shield weights based on optimum ablative compositions indicated that ablators are a highly efficient thermal protection system for these missions.
Solutions are presented for the material thermal response for heat shields of blunt probes entering Saturn and Uranus. Both monolithic and sandwich concepts were considered having exposed charring ablative or reflective materials. The solutions show that (1) Teflon heat shields are sized by mass loss considerations, other materials (unless entering the Uranus cold-dense atmosphere) by heat soak considerations, (2) steeper entries require less heat shield mass, (3) sizing requirements vary little about the bodies for heat soak dominated materials, and (4) carbon-phenolic appears superior overall, but silica is superior for the steeper entries and the high helium content atmospheres.
A single motor was cast and static fired to demonstrate the performance of high energy crosslinked double base (XLDB) propellant in standard X259 rocket motor hardware. Prior to motor fabrication, the motor was analyzed to predict the results of static firing the X259 motor loaded with XLDB propellant. As a result of the analyses, a forward dome shrinkage liner was added to the design. With this design change it was determined that adequate margins of safety existed. The motor, designated the X259-E6 model with serial number XJ04/0001, was fabricated using a slurry-casting technique and was assembled with a standard X259-B4 nozzle which had the nozzle throat machined to a smaller inside diameter than the B4 model and the exit cone cut short for Bacchus Works altitude expansion. The motor was static fired on 20 February 1974 with the nozzle failing during motor operation. Nozzle failure was attributed to spalling of the throat material leading to complete nozzle break-up. However, the propellant functioned as predicted in the motor chamber, ignition was normal, and char and erosion of the internal insulator were as expected.
The feasibility of retaining the heat shield for outer planet probes was investigated as a potential source of atmospheric sample contamination by outgassing. The onboard instruments which are affected by the concept are the pressure sensor, temperature sensor, IR detector, nephelometer, and gas sampling instruments. It was found that: (1) The retention of the charred heatshield and the baseline atmospheric sampling concepts are compatible with obtaining noncontaminated atmospheric samples. (2) Increasing the sampling tube length so that it extends beyond the viscous boundary layer eliminates contamination of the atmospheric sample. (3) The potential for contamination increases with angle of attack.