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
Handbook describes relationship between phase-change materials and more conventional thermal control techniques and discusses materials' space and terrestrial applications. Material properties of most promising phase-change materials and purposes and uses of metallic filler materials in phase-change material composites are provided.
This handbook is intended to provide theory and data needed by the thermal design engineer to bridge the gap between research achievements and actual flight systems, within the limits of the current state of the art of phase change materials (PCM) technology. The relationship between PCM and more conventional thermal control techniques is described and numerous space and terrestrial applications of PCM are discussed. Material properties of the most promising PCMs are provided; the purposes and use of metallic filler materials in PCM composites are presented; and material compatibility considerations relevant to PCM design are included. The engineering considerations of PCM design are described, especially those pertaining to the thermodynamic and heat transfer phenomena peculiar to PCM design. Methods of obtaining data not currently available are presented. The special problems encountered in the space environment are described. Computational tools useful to the designer are discussed. In summary, each aspect of the PCM problem important to the design engineer is covered to the extent allowed by the scope of this effort and the state of the art.
Preliminary results of the research on carbon and graphite accomplished during this report period are presented. Included are: particle characteristics of Santa Maria fillers, compositions and density data for hot-molded Santa Maria graphites, properties of hot-molded Santa Maria graphites, and properties of hot-molded anisotropic graphites. Ablation-resistant graphites are also discussed.
The effects of grinding on Santa Maria coke are considered, as well as the production of resin-bonded graphite from the coke. Kynol fibers, properties and purities of coal tar pitches, carbonization of resin components, synthesis of gamma BL (4-furfuryl 2-pentenoic acid gamma lactone), and a glass-like carbon powder for use as a filler are also discussed. The hydrogen contents of commercial cokes and graphites are tabulated, and a quantimet image-analyzing computer and its operation are described.
A literature survey was conducted to collect material properties data on all advanced high temperature materials. Three of these, Y2O3-stabilized ZrO2, ThO2, and ZrB2 with additives of C and SiC were selected for further study. Stabilized ZrO2 and ThO2 were found to have higher temperature oxidation resistance than any metal and great potential for use in advanced biowaste resistojets. ZrO2 has a lower electrical resistivity and sublimation and a higher creep endurance strength. ZrO2 and ThO2 tubular heat exchangers, electrically heated indirectly, were evaluated in short tests to about 1900 K in flowing CO2. ZrO2 was subjected to N2, H2, H2O and vacuum as well. X-ray diffraction and fluorescence analyses were made. The metal-to-ceramic seal technology for ZrO2 and ThO2 was developed using chemical vapor deposition of tantalum for metallizing and 82 Au - 18 Ni filler braze.
A study to correlate stress wave emission characteristics with fracture in welded and unwelded aluminum alloys tested at room and cryogenic temperature is reported. The stress wave emission characteristics investigated were those which serve to presage crack instability; viz., a marked increase in:(1) signal amplitude; (2) signal repetition rate; and (3) the slope of cumulative count plotted versus load. The alloys were 7075-T73, 2219-T87 and 2014-T651, welded with MIG and TIG using 2319 and 4043 filler wire. The testing was done with both unnotched and part-through-crack (PTC) tension specimens and with 18-in.-dia subscale pressure vessels. In the latter testing, a real time, acoustic emission, triangulation system was used to locate the source of each stress wave emission. With such a system, multiple emissions from a given location were correlated with defects found by conventional nondestructive inspection.
An applied research program is considered for a preliminary design and development of a flexible ablative covering for the space shuttle vehicle that could be easily replaced and/or refurbished. The program was structured to concentrate resources on the major technical problem areas associated with the flexible ablator concept. These areas included: (1) fabrication of a suitable woven carpet reinforcement, (2) modification of a flexible ablator formulation for filling the woven carpet construction, and (3) testing of the flexible ablator concept. Several approaches were evaluated to obtain a flexible ablator. The final recommended solution was one in which the ablative filler was based on a low-density formulation of the elastomeric shield material series (ESM). The preferred approach is one in which a light-weight fabric backing is bonded to preformed and fully cured ESM, and the composite tufted with Astroquartz fiber to the desired tuft or pile density. Ablation tests performed in a hyperthermal arc facility demonstrated the ablation performance of the concept and overshoot capability of the system.
Description of a materials system developed for use as low-cost ablative nozzles for NASA's 260-in. solid rocket motor. Petroleum coke and carbon black fillers were employed; high density was achieved by controlling particle size distribution. An alumina catalyzed furfuryl ester resin which produced high carbon residues after pyrolysis was employed as the binder. Staple carbon fibers improved the strength and crack resistance of molded bodies. In static firing tests of two subscale nozzles, this material compared favorably in erosion rate with several other ablative systems.
Formulation improves compatibility of butyl rubbers with hydrazine while reducing permeation to low levels necessary for prolonged storage in space. This is accomplished by replacing carbon-black filler with inert materials such as hydrated silica or clay. Pressure increases suggest that hydrazine is decomposed only slightly by new type of rubber.
An advanced lightweight insulation system suitable for use in long duration, low pressure planetary orbiter-type motor applications was developed. Experiments included the screening of various filler and binder materials with optimization studies combining the best of each. Small scale test motor data were used to judge the degree of success.
The mullite fiber based hardened compacted fibers (HCF) type of reusable surface insulation was further developed for use in the Space Shuttle Program. Two hundred fifty formulations of fiber mixtures, fillers, binders, and organic processing aids were made using mullite fibers as the basic ingredient. Most of the work was accomplished on 15-lb/cu ft material. It was established that higher density materials are stronger with strength values as high as 250 lb/sq in. in tension. New measurement techniques and equipment were developed for accurate determination of strength and strain to failure. Room temperature to 2300 F stress-strain relationships were made. The room temperature tensile modulus of elasticity is 61,700 lb/sq in. and the strain at failure is 0.165 percent, typically, when measured longitudinally parallel to the long axes of the fibers. Thermal insulating effectiveness was increased 20 percent by reducing the diameter of some of the fibers in the material. Improvements were made in density uniformity and strength uniformity in a block of HCF by mixing improvements and by the use of organic additives. Specifications were established on the materials and processes used in making the insulation.
The research on graphite and carbon for this period is reported. Topics discussed include: effects of grinding on the Santa Marie graphites, properties and purities of coal-tar, resin-bonded graphite, carbonization of resin components, and glass-like carbon filler.
Carbon-graphite seal ring bodies for operation at air temperatures to 1300 F(704 C) were manufactured from three select formulations. Mechanical and thermal properties, porosities, and oxidation rates were measured. The results have shown that: (1) Major property improvements anticipated from the screening studies were not realized because of processing problems associated with the scale-up in material size and probable deterioration of a phenolic resin binder; (2) the mechanical properties of a phenolic resin-bonded, carbon-graphite material can be improved by applying high pressure during carbonization; and (3) the textile form of graphite fiber used as the minor filler component in a carbon-graphite material can beneficially affect mechanical properties.
A screening study was conducted to develop improved carbon-graphite materials for use in self-acting seals at air temperatures to 1300 F (704 C). Property measurements on materials prepared during this study have shown that: (1) The mechanical properties of a carbon-graphite material were significantly improved by using a fine milled artificial graphite filler material and including intensive mixing, warm molding, and pitch impregnation in the processing; and (2) the oxidation resistance of a carbon-graphite material was improved by including fine milled boron carbide as an oxidation-inhibiting additive. These techniques were employed to develop a material that has 10 times more oxidation resistance than that of a widely used commercial grade and mechanical properties that approach those of the commercial grade.
An extensive development and testing program on adhesive systems shows that: (1) A closed cell silicone rubber sponge bonded to substrates with thin bond lines of glass filled adhesive exhibits density and modulus values approximately one third that of solid silicone adhesives; (2) utilization of glass or phenolic microballoons as fillers in silicone adhesives reduces density but increases moduli of the vulcanized materials; (3) the silicone elastomer based adhesives appear to be complex systems rather than homogeneous, isotropic materials. Tensile, shear, and compression properties plotted versus temperature verify this conjecture; and (4) constant strain-stress relaxation tests on glass-filled adhesive show that stress relaxation is most pronounced near the glass transition temperature.
To provide vibration-resistance composition adjust processing techniques, which produces essentially void-free materials and provides for clean removal of finished material from mold. Microsphere filler imparts strength to polymer and sodium carbonate imparts flame-resistance.
Data on binary-metal eutectics and melting-point minimums have been assembled for use in selecting brazing filler compositions for refractory metals. Data are presented in four tables for ready reference. Brief discussion of problems and potentials of metallides is included in appendix.