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Energy transfer in reacting flow of pyrolysis products through char layer of nylon-phenolic resin charring ablator
Nonequilibrium modeling of pyrolysis gas products flow through char layer of ablative heat shield
The development and verification of the Charring Ablating Thermal Protection Implicit System Solver (CATPISS) is presented. This work concentrates on the derivation and verification of the stationary grid terms in the equations that govern three-dimensional heat and mass transfer for charring thermal protection systems including pyrolysis gas flow through the porous char layer. The governing equations are discretized according to the Galerkin finite element method (FEM) with first and second order fully implicit time integrators. The governing equations are fully coupled and are solved in parallel via Newton s method, while the linear system is solved via the Generalized Minimum Residual method (GMRES). Verification results from exact solutions and Method of Manufactured Solutions (MMS) are presented to show spatial and temporal orders of accuracy as well as nonlinear convergence rates.
The development and verification of the Charring Ablating Thermal Protection Implicit System Solver is presented. This work concentrates on the derivation and verification of the stationary grid terms in the equations that govern three-dimensional heat and mass transfer for charring thermal protection systems including pyrolysis gas flow through the porous char layer. The governing equations are discretized according to the Galerkin finite element method with first and second order implicit time integrators. The governing equations are fully coupled and are solved in parallel via Newton's method, while the fully implicit linear system is solved with the Generalized Minimal Residual method. Verification results from exact solutions and the Method of Manufactured Solutions are presented to show spatial and temporal orders of accuracy as well as nonlinear convergence rates.
Thermomechanical properties, flammability, oxygen index, relative toxicity of pyrolysis effluents, and char yields were studied for 12 advanced polymers which are candidates for use in aircraft interiors as decorative films, compression- and injection-molded parts and thermoplastic parts. Polymers sampled included polyphenylene sulfide, 9,9 bis (4-hydroxyphenol) fluorene polycarbonate-poly (dimethylsiloxane), polyether sulfone, polyvinyl fluoride and polyvinylidene fluoride. Availability of these samples, whether in commercial form or in test quantities, is specified. An estimate of relative fire resistance for the materials was obtained; the five polymers listed above were found to be the most fire resistant of the 12 sampled.
Poly(methylsilane) and poly(vinylsilane) were synthesized using a titanocene catalyst, and their pyrolytic conversion to ceramics was followed using a combination of thermal analysis and infrared spectroscopy. The two polymers have distinctly different backbone structures, as determined by Si NMR; methylsilane polymerizes to a polysilane, while vinylsilane polymers have predominately polycarbosilane backbone, with some polysilane structure as well. The pyrolysis path and char yield were dependent primarily on backbone structure, with little influence of polymer molecular weight. The majority of the weight loss on conversion occurs below 650 degrees C, although bond rearrangement continues to 1400 degrees C. Poly(vinylsilane) produced a C-rich Si-C ceramic in which the carbon was dispersed on a sufficiently fine level to show resistance to oxidation on heating in air to 1400 degrees C.
Polymer combustion is a very complicated process which involves the coupling of gas-phase combustion, melting, pyrolysis, and possible charring of the condensed phase. Although only a few studies on the combustion of a spherically shaped polymer have been conducted, there is renewed interest in the subject. At the Third International Microgravity Combustion Workshop, we presented a preliminary experimental plan and proposed an apparatus to study the combustion of a PolyMethylMethAcrylate (PMMA) sphere at reduced gravity. In this paper, we describe the experimental hardware in detail, summarize our observations since the last workshop, and describe future studies. The main objective is to determine the burning rate of PMMA spheres at reduced gravity under different ambient oxygen concentrations and total pressures. The dependence of the burning rate on the initial sphere diameter will be examined. It is anticipated that the simple spherical geometry in conjunction with reduced gravity will facilitate an assessment of the effect of condensed phase behavior on polymer burning processes and can be used as a means to test polymer combustion models.
The differential equations governing the transient response of a one-dimensional ablative thermal protection system are presented for thermal nonequilibrium between the pyrolysis gases and the char layer and with finite rate chemical reactions occurring. The system consists of three layers (the char layer, the uncharred layer, and an optical insulation layer) with concentrated heat sinks at the back surface and between the second and third layers. The equations are solved numerically by using a modified implicit finite difference scheme to obtain solutions for the thickness of the charred and uncharred layers, surface recession and pyrolysis rates, solid temperatures, porosity profiles, and profiles of pyrolysis-gas temperature, pressure, composition, and flow rate. Good agreement is obtained between numerical results and exact solutions for a number of simplified cases. The complete numerical analysis is used to obtain solutions for an ablative system subjected to a constant heating environment. Effects of thermal, chemical, and mass transfer processes are shown.
Energy transfer in pyrolysis product flow through char layer of nylon phenolic resin ablator
The decomposition of ablative composites is described along with the transport phenomena of pyrolysis gases which result from the decomposition of these plastics as they flow through the porous char of char-forming ablators. The pyrolysis products are those formed by the thermal degradation of nylon-phenolic resin and silicone elastomer composites. Emphasis is placed on the nature and extent of chemical reactions of the pyrolysis products and the char, along with the energy absorbed by the combined pyrolysis and char zone. Chemical reactions with thermodynamically consistent kinetic data are determined in order to develop a realistic analysis for predicting the thermal performance of ablative heat shields.
Attention is given to a theoretical model describing the behavior of a thermally thin cellulosic sheet heated by external thermal radiation in a quiescent microgravity environment. This model describes thermal and oxidative degradation of the sheet and the heat and mass transfer of evolved degradation products from the heated cellulosic surface into the gas phase. Two calculations are carried out: heating without thermal degradation, and heating with thermal degradation of the sheet with endothermic pyrolysis, exothermic thermal oxidative degradation, and highly exothermic char oxidation. It is shown that pyrolysis is the main degradation reaction. Self-sustained smoldering is controlled and severely limited by the reduced oxygen supply.
Amorphous carbonaceous char produced from the pyrolysis of polymer solids has many desirable properties for ablative heat shields for space vehicles. Molecular dynamics simulations are presented to study the transformation of the local atomic structure from virgin polymer to a dense, disordered char [1]. Release of polymer hydrogen is found to be critical to allow the system to collapse into a highly coordinated char structure. Mechanisms of the char formation process and the morphology of the resulting structures are elucidated. Thermal conductivity and mechanical response of the resulting char are evaluated [2]. During reenty, the optical response and oxidative reactivity of char are also important properties. Results of ab initio computations of char optical functions [3] and char reactivity [4] are also presented.
Feedstock attributes of lignocellulosic biomass, such as particle size, compositional makeup, and moisture content, can vary substantially even within pre-processed materials and have a significant effect on conversion in fast pyrolysis-based processes. However, the economic impacts of these attributes are not well understood. To address this, biomass deconstruction phenomena captured with a versatile particle-scale simulation were linked to techno-economic impacts via reduced-order models. Parametric analysis of the particle-scale model, which was validated using literature data, was used in combination with multiple linear regression models to develop correlations between feedstock attributes and yields of pyrolysis oil, gas, and char. Yields were then correlated with the minimum fuel selling price (MFSP) using a techno-economic model, bridging the gap between physics-based biomass conversion simulations and predictions of MFSP for a catalytic fast-pyrolysis process. Empirical correlations derived from the literature regarding the impact of mineral matter (ash) on oil yield were also considered. The model correlations deployed in the integrated framework capture the impacts of variation in feedstock attributes on the MFSP. Variations in ash were shown to have the biggest impact, varying MFSP by -13%/+22% due to catalytic effects and lower relative amounts of convertible lignocellulosic material. It was also found that, if ash can be controlled to low levels, the increased extractives in forest residues can help compensate for some yield losses associated with increased ash. As a result, other inputs considered (particle size, moisture content, and reactor temperature) had relatively negligible effects on process economics within the ranges analyzed considering particle-scale effects alone.
The differential equations governing the transient response of the char layer of an ablating axisymmetric body, internal pyrolysis gas flow effects being considered, have been derived. These equations have been expanded into finite difference form and programed for numerical solution on a digital computer. Numerical results compare favorably with simplified exact solutions. The complete numerical analysis was used to obtain solutions for two representative body shapes subjected to a typical entry heating environment. Pronounced effects of the lateral flow of pyrolysis gases on the mass flow field within the char layer and the associated surface and pyrolysis interface recession rates are shown.
Oxygen depletion effect in chemical reactions between pyrolysis gases and air stream on surface recession of charring ablators
Self-cooled combustion chambers are chambers in which the chamber wall temperature is controlled by methods other than fluid flow within the chamber wall supplied from an external source. In such chambers, adiabatic wall temperature may be controlled by use of upstream fluid components such as the injector or a film-coolant ring, or by internal flow of self-contained materials; e.g. pyrolysis gas flow in charring ablators, and the flow of infiltrated liquid metals in porous matrices. Five types of self-cooled chambers are considered in this monograph. The name identifying the chamber is indicative of the method (mechanism) by which the chamber is cooled, as follows: ablative; radiation cooled; internally regenerative (Interegen); heat sink; adiabatic wall. Except for the Interegen and heat sink concepts, each chamber type is discussed separately. A separate and final section of the monograph deals with heat transfer to the chamber wall and treats Stanton number evaluation, film cooling, and film-coolant injection techniques, since these subjects are common to all chamber types. Techniques for analysis of gas film cooling and liquid film cooling are presented.
Silicon carbide made by pyrolizing polymers. Method conceived for preparation of poly(decamethylcyclohexasilanes) as precursors for preparation of silicon carbide at high yield. Technical potential of polysilanes as precursors of SiC ceramics being explored. Potential limited by intractability of some polysilanes; formation of small, cyclic polycarbosilane fragments during pyrolysis; and overall low char yield and large shrinkage in conversion to ceramics.
The behavior of composite materials, specifically carbon fiber reinforced plastic (CFRP) and glass fiber reinforced plastic (GFRP), under reentry conditions poses a problem for space debris reentry risk modeling. Since these materials pyrolyze rather than melt and their different components demise at different rates, modeling their destruction to determine ground impact risk is complex. Modern spacecraft are using these materials in ever-greater quantities owing to their superior strength-to-weight characteristics, and this has required that the orbital debris community improve its understanding of how these materials demise on reentry. The NASA Orbital Debris Program Office undertook an extensive test campaign to better understand the rate at which several types of GFRP and CFRP materials pyrolyze under reentry heating conditions and how that pyrolysis affects the ultimate strength of the material. GFRP with a polyester resin (G10/FR-4) and CFRP with epoxy, cyanate ester, vinyl ester, and phenolic resins were tested. The test campaign was carried out at the Inductively Coupled Plasma (ICP) Torch Facility at the University of Texas at Austin. Because the ICP facility operates in a shirt-sleeve environment, test samples can be changed within seconds or minutes, allowing many samples to be tested in a short period. Two heat flux rates, 20 W/m2 and 30W/m2, and two oxygen concentration conditions, 0% and 2% of atmospheric, were applied to all five types of material. To measure both the char rate and the effect of pyrolysis on the ultimate material strength, two types of test were carried out for each material: a char rate test on a ~10 mm thick sample of material and an in-situ bending stress test of a ~2 mm thick sample of material. Measurements of the char rate showed very similar average pyrolysis front velocity in epoxy resin CFRP as in G10 at 3.6 mm/min and 3.4 mm/min, respectively. However, the total mass loss rate in theG10 was nearly double that of the CFRP at 3.8 g/min and 2.2 g/min, respectively. This result represented a slow ablation rate of carbon fibers in the CFRP at the temperatures encountered in low Earth orbit reentry and a comparatively rapid removal of the glass fibers in G10 due to melting and spallation. Pyrolysis front velocity was more significantly affected by the type of plastic than the type of fiber, with the cyanate ester CFRP samples displaying an average pyrolysis front velocity of only 1.9 mm/min. Similarly, the effect of thermal exposure on the ultimate strength of the material depended heavily on the type of plastic and very little on the type of fiber in the material. Epoxy, vinyl ester, and polyester resins all behaved very similarly, with complete structural failure at between 400 J/g and 600 J/g of specific absorbed heat. Phenolic and cyanate ester resins, on the other hand, displayed a change in structural properties that was only barely measurable with the current apparatus even after the maximum exposure time tested. These data are being incorporated into a numerical model of the ablation and demise of composite materials that will be used to more accurately calculate the ground casualty risk of future spacecraft.