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Common scaling criterion found to relate some physical quantities characterizing tensile failures of three different solid propellant materials. Tensile failures of different rubbery propellants characterized by similar plots.
The following is a design for a tensile tester which will be used to test the tensile strength and anisotropic properties of simple composites. These simple composites are suspected to be anisotropic primarily in a single plane. When the composites undergo a tensile force, they will undergo deformation, causing movement either to the left or right. The composites are suspect due to their method of construction. Each sample has a single layer of unidirectional continuous fibers embedded in a rubbery resin. It has been well established that a serious limitation of unidirectional fiber composites is the very large in-plane anisotropy. The design presented here incorporates a single degree of freedom such that distortion (to the left or right) due to anisotropic tendencies may be measured. The device will spend the vast majority of its time in an undergraduate materials lab. As a result, ease of use and durability are valued more highly than research grade accuracy. Additional concerns focus on the fact that this machine will be built as a student project. Issues which are dealt with during this design include: specimen configuration or shape; a method of applying consistent, linear tension force; a method of gripping specimen without affecting its overall properties; a method of collecting data; repeatability of data; ease of use; ease of construction; and cost. After the device has been constructed, it will be used to test the simple composites which were fabricated in house. A comparison will be made between composites manufactured using aluminum screening as the strengthening fibers and those manufactured using fiberglass screening.
Novel p-ethynyl-substituted rigid rod monomers were studied by pressure Differential Scanning Calorimetry (DSC), ThermoGravimetric Analysis (TGA), IsothermoGravimetric Analysis (IGA), and TGA-IR. These monomers, 4,4'-bis(((4-ethynylphenyl)carbonyl)oxy)biphenyl, designated 1, 1,5-bis-(((4-ethynylphenyl)carbonyl)oxy)naphthalene, designated 2, and bis(4-ethynylphenyl)pyromellitimide, designated 3, were polymerized in the solid state. Thermal polymerization in N2 or air produced highly cross-linked resins with polymerization exotherms centered between 212 and 276 C. The (delta)H's of polymerization of these resins in air were found to be double those in N2. When monomers 1 and 2 were heated in air from 23 to 750 C at 10 C/min, the main decomposition product was carbon dioxide, evolving at a maximum rate between 500 and 600 C; water was also detected as a decomposition product. Void-free neat resin moldings, designated lp to 3p, were made by compression molding the monomers and then heating them. The resulting polymers were highly cross-linked, and their glass transition temperatures (T(sub g)) were much higher than their polymerization temperatures. Using ThermoMechanical Analysis (TMA), we found that polymers lp to 3p had T(sub g)'s of 422, 329, and 380 C, respectively. The thermal and thermooxidative stabilities improved when lp to 3p were postcured in N2 (the postcured polymers were designated 1pp to 3pp). The Linear Thermal Expansions (LTE) for lp and 3p were 1% between 23 and 420 C. Using rheological analysis, we could not clearly detect the T(sub g)'s of lp to 3p because their moduli dropped only slightly between 23 and 490 C and the changes in tan beta were very low. Because of high cross-link density, their moduli changed little as the resins went from a glassy to a rubbery state. Their shear storage moduli in air ranged from 0.82 (3p, 3pp) to 1.6 GPa (lpp) at 23 C, from 0.16 (2p) to 0.7GPa(lpp) at 380 C, and from 0.18(lpp)to 0.6GPa(2p) at 490 C. Finally, these novel-p-ethynyl polymers exhibited an excellent combination of high T(sub g), low LTE, and high thermooxidative stability. Most notably, 3pp lost only 3% of its initial weight when it was aged for 500 h at 288 C in air.
Structural performance (integrity, durability and damage tolerance) of fiber reinforced composite pressure vessels, designed for pressured shelters for planetary exploration, is investigated via computational simulation. An integrated computer code is utilized for the simulation of damage initiation, growth, and propagation under pressure. Aramid fibers are considered in a rubbery polymer matrix for the composite system. Effects of fiber orientation and fabrication defect/accidental damages are investigated with regard to the safety and durability of the shelter. Results show the viability of fiber reinforced pressure vessels as damage tolerant shelters for planetary colonization.
We analyze the onset of "necking" and subsequent filament failure during the transient uniaxial elongation of viscoelastic fluid samples in extensional rheometers. In the limit of rapid elongation (such that no molecular relaxation occurs), the external work applied is all stored elastically and the Considere criterion originally developed in solid mechanics can be used to quantitatively predict the critical Hencky strain to failure. By comparing the predictions of the Doi-Edwards model for linear homopolymer melts with those of the "Pom-Pom" model for prototypical branched melts we show that the critical strain to failure in rapid elongation of a rubbery material is intimately linked to the molecular topology of the chain, especially the degree of chain branching. The onset of necking instability is monotonically shifted to larger Hencky strains as the number of branches is increased. Numerical computations at finite Deborah numbers also show that there is an optimal range of deformation rates over which homogeneous extensions can be maintained to large strain. We also consider other rapid homogeneous stretching deformations, such as biaxial and planar stretching, and show that the degree of stabilization afforded by inclusion of material with long-chain branching is a sensitive function of the imposed mode of deformation.
A two-year research plan was undertaken in association with Polymers Branch, NASA Glenn Research Center, to carry out experimental and modeling work relating stress and strain behavior of polymeric materials, especially elastomers and vulcanized rubber. An experimental system based on MTS (Mechanical Testing and Simulation) A/T-4 test facility environment has been developed for a broader range of polymeric materials in addition to a design of laser compatible temperature control chamber for online measurements of various strains. Necessary material processing has been accomplished including rubber compounding and thermoplastic elastomer processing via injection molding. A broad suite of testing methodologies has been identified to reveal the complex non-linear mechanical behaviors of rubbery materials when subjected to complex modes of deformation. This suite of tests required the conceptualization, design and development of new specimen geometries, test fixtures, and test systems including development of a new laser based technique to measure large multi-axial deformations. Test data has been generated for some of these new fixtures and has revealed some complex coupling effects generated during multi-axial deformations. In addition, fundamental research has been conducted concerning the foundation principles of rubber thermodynamics and resulting theories of rubber elasticity. Studies have been completed on morphological properties of several thermoplastic elastomers. Finally, a series of steps have been identified to further advance the goals of NASA's ongoing effort.
The present series of three consecutive papers develops a general theory for linear and finite solid viscoelasticity. Because the most important object for nonlinear studies are rubber-like materials, the general approach is specified in a form convenient for solving problems important for many industries that involve rubber-like materials. General linear and nonlinear theories for non-isothermal deformations of viscoelastic solids are developed based on the quasi-linear approach of non-equilibrium thermodynamics. In this, the first paper of the series, we analyze non-isothermal linear viscoelasticity, which is applicable in a range of small strains not only to all synthetic polymers and bio-polymers but also to some non-polymeric materials. Although the linear case seems to be well developed, there still are some reasons to implement a thermodynamic derivation of constitutive equations for solid-like, non-isothermal, linear viscoelasticity. The most important is the thermodynamic modeling of thermo-rheological complexity , i.e. different temperature dependences of relaxation parameters in various parts of relaxation spectrum. A special structure of interaction matrices is established for different physical mechanisms contributed to the normal relaxation modes. This structure seems to be in accord with observations, and creates a simple mathematical framework for both continuum and molecular theories of the thermo-rheological complex relaxation phenomena. Finally, a unified approach is briefly discussed that, in principle, allows combining both the long time (discrete) and short time (continuous) descriptions of relaxation behaviors for polymers in the rubbery and glassy regions.
The objective of CAM is to develop, test, and analyze thin film membrane materials for separation and purification of carbon dioxide (CO2) from mixtures of gases, such as those found in the Martian atmosphere. The membranes are targeted toward In Situ Resource Utilization (ISRU) applications that will operate in extraterrestrial environments and support future unmanned and human space missions. A primary application is the Sabatier Electrolysis process that uses Mars atmosphere CO2 as raw material for producing water, oxygen, and methane for rocket fuel and habitat support. Other applications include use as an inlet filter to collect and concentrate Mars atmospheric argon and nitrogen gases for habitat pressurization, and to remove CO2 from breathing gases in Closed Environment Life Support Systems (CELSS). CAM membrane materials include crystalline faujasite (FAU) zeolite and rubbery polymers such as silicone rubber (PDMS) that have been shown in the literature and via molecular simulation to favor adsorption and permeation of CO2 over nitrogen and argon. Pure gas permeation tests using commercial PDMS membranes have shown that both CO2 permeance and the separation factor relative to other gases increase as the temperature decreases, and low (Delta)P(Sub CO2) favors higher separation factors. The ideal CO2/N2 separation factor increases from 7.5 to 17.5 as temperature decreases from 22 C to -30 C. For gas mixtures containing CO2, N2, and Ar, plasticization decreased the separation factors from 4.5 to 6 over the same temperature range. We currently synthesize and test our own Na(+) FAU zeolite membranes using standard formulations and secondary growth methods on porous alumina. Preliminary tests with a Na(+) FAU membrane at 22 C show a He/SF6 ideal separation factor of 62, exceeding the Knudsen diffusion selectivity by an order of magnitude. This shows that the membrane is relatively free from large defects and associated non-selective (viscous flow) transport mechanisms. The Membrane Test Facility (MTF) has been developed to measure membrane permeance over a wide range of temperature and pressure. The facility uses two volume compartments separated by the membrane that are instrumented to measure temperature, delta pressure across the membrane, and gas composition. A thermal shroud supports and encloses the membrane, and provides temperature control. Methods were developed to determine membrane permeance using the first order decay of the pressure difference between the sealed compartments, using the total pressure for pure gases, and partial pressure of each species in gas mixtures. The technique provides an end-to-end measurement of gas permeance that includes concentration polarization effects. Experiments have shown that in addition to membrane permeance properties, the geometry and design of associated structures play an important role in how membrane systems will function on Mars.
The physical state of food components affects their properties during processing, storage, and consumption. Removal of water by evaporation or by freezing often results in formation of an amorphous state (Parks et al., 1928; Troy and Sharp, 1930; Kauzmann, 1948; Bushill et al., 1965; White and Cakebread, 1966; Slade and Levine, 1991). Amorphous foods are also produced from carbohydrate melts by rapid cooling after extrusion or in the manufacturing of hard sugar candies and coatings (Herrington and Branfield, 1984). Formation of the amorphous state and its relation to equilibrium conditions are shown in Fig. 1 [see text]. The most important change, characteristic of the amorphous state, is noticed at the glass transition temperature (Tg), which involves transition from a solid "glassy" to a liquid-like "rubbery" state. The main consequence of glass transition is an increase of molecular mobility and free volume above Tg, which may result in physical and physico-chemical deteriorative changes (White and Cakebread, 1966; Slade and Levine, 1991). We have conducted studies on phase transitions of amorphous food materials and related Tg to composition, viscosity, stickiness, collapse, recrystallization, and ice formation. We have also proposed that some diffusion-limited deteriorative reactions are controlled by the physical state in the vicinity of Tg (Roos and Karel, 1990, 1991a, b, c). The results are summarized in this article, with state diagrams based on experimental and calculated data to characterize the relevant water content, temperature, and time-dependent phenomena of amorphous food components.
Nitrous oxide/paraffin (N2OP) hybrid rocket engines have been invented as alternatives to other rocket engines especially those that burn granular, rubbery solid fuels consisting largely of hydroxyl- terminated polybutadiene (HTPB). Originally intended for use in launching spacecraft, these engines would also be suitable for terrestrial use in rocket-assisted takeoff of small airplanes. The main novel features of these engines are (1) the use of reinforced paraffin as the fuel and (2) the use of nitrous oxide as the oxidizer. Hybrid (solid-fuel/fluid-oxidizer) rocket engines offer advantages of safety and simplicity over fluid-bipropellant (fluid-fuel/fluid-oxidizer) rocket en - gines, but the thrusts of HTPB-based hybrid rocket engines are limited by the low regression rates of the fuel grains. Paraffin used as a solid fuel has a regression rate about 4 times that of HTPB, but pure paraffin fuel grains soften when heated; hence, paraffin fuel grains can, potentially, slump during firing. In a hybrid engine of the present type, the paraffin is molded into a 3-volume-percent graphite sponge or similar carbon matrix, which supports the paraffin against slumping during firing. In addition, because the carbon matrix material burns along with the paraffin, engine performance is not appreciably degraded by use of the matrix.
For angleply composites, lamina tension and compression strengths are commonly determined by applying classical lamination theory to test data obtained from testing of angleply composite specimens. For textile composites such as 2D triaxial braids, analysis is more complex and standard test methods do not always yield reliable strength measurements. This paper describes recent research focused on development of more reliable tensile test methods for braided composites and presents preliminary data for various approaches. The materials investigated in this work have 0deg+/-60 2D triaxial braid architecture with nearly equal fiber volume fraction in each of the three fiber directions. Flat composite panels are fabricated by resin transfer molding (RTM) using six layers of the braided preform aligned along the 0deg fiber direction. Various epoxy resins are used as matrix materials. Single layer panels are also fabricated in order to examine local variations in deformation related to the braid architecture. Specimens are cut from these panels in the shape of standard straight-sided coupons, an alternative bowtie geometry, and an alternative notched geometry. Axial tensile properties are measured using specimens loaded along the 0deg fiber direction. Transverse tensile properties are measured using specimens loaded perpendicular to the 0deg fibers. Composite tubes are also fabricated by RTM. These tubes are tested by internal pressurization using a soft rubbery material sealed between the inside diameter of the tube and the load fixtures. The ends of the tube are unconstrained, so the primary load is in the hoop direction. Tubes are fabricated with the 0deg fibers aligned along the tube axis by overbraiding the preform on a mandrel. Since the loading is in the hoop direction, testing of the overbraided tube provides a measure of transverse tensile strength. Previous work has indicated that straight-sided coupons yield a transverse tensile strength that is much lower than the expected material strength because of premature edge-initiated failure. Full-field strain measured during transverse tensile tests clearly showed accumulation of edge damage prior to failure. In the current work, high speed video and testing of single layer specimens are used to investigate potential failure mechanisms in more detail. High speed video clearly shows the edge initiation in six layer transverse tensile test coupons. Specimens with the bowtie geometry and the notched geometry minimize this edge effect and yield significantly higher transverse tensile strength values compared to the straight-sided coupons. However, bowtie and notched specimens geometries are not ideal because of the non-uniform stress and strain fields in the region of failure. Testing of tubes using internal pressurization eliminates edge-initiated failure and provides a more uniform state of stress and strain. Preliminary results indicate that bowtie, notched, and tube specimens yield comparable values for transverse tensile strength and that these values are much higher than the strength measured using a straight-sided coupon.
Lightweight, deployable antennas for a variety of outer-space and terrestrial applications would be designed and fabricated according to the concept of cold hibernated elastic memory (CHEM) structures, according to a proposal. Mechanically deployable antennas now in use are heavy, complex, and unreliable, and they utilize packaging volume inefficiently. The proposed CHEM antenna structures would be simple and would deploy themselves without need for any mechanisms and, therefore, would be more reliable. The proposed CHEM antenna structures would also weigh less, could be packaged in smaller volumes, and would cost less, relative to mechanically deployable antennas. The CHEM concept was described in two prior NASA Tech Briefs articles: "Cold Hibernated Elastic Memory (CHEM) Expandable Structures" (NPO-20394), Vol. 23, No. 2 (February 1999), page 56; and "Solar Heating for Deployment of Foam Structures" (NPO-20961), Vol. 25, No. 10 (October 2001), page 36. To recapitulate from the cited prior articles: The CHEM concept is one of utilizing opencell foams of shape-memory polymers (SMPs) to make lightweight, reliable, simple, and inexpensive structures that can be alternately (1) compressed and stowed compactly or (2) expanded, then rigidified for use. A CHEM structure is fabricated at full size from a block of SMP foam in its glassy state [at a temperature below the glass-transition temperature (Tg) of the SMP]. The structure is heated to the rubbery state of the SMP (that is, to a temperature above Tg) and compacted to a small volume. After compaction, the structure is cooled to the glassy state of the SMP. The compacting force can then be released and the structure remains compact as long as the temperature is kept below Tg. Upon subsequent heating of the structure above Tg, the simultaneous elastic recovery of the foam and its shape-memory effect cause the structure to expand to its original size and shape. Once thus deployed, the structure can be rigidified by cooling below Tg. Once deployed and rigidified, the structure could be heated and recompacted. In principle, there should be no limit on the achievable number of compaction/deployment/ rigidification cycles. Thus far, several different designs of a 3.5-m-long CHEM conical corrugated horn antenna have been analyzed (see figure). A small CHEM structural antenna model was fabricated and a thin, electrically conductive layer of aluminum was deposited on the inner surface of the model. This structural model was then subjected to the compaction and deployment treatments described above to demonstrate the feasibility of a CHEM corrugated horn antenna.
Conventional toughening agents are typically rubbery materials or small molecular weight molecules, which mostly sacrifice the intrinsic properties of a matrix such as modulus, strength, and thermal stability as side effects. On the other hand, high modulus inclusions tend to reinforce elastic modulus very efficiently, but not the strength very well. For example, mechanical reinforcement with inorganic inclusions often degrades the composite toughness, encountering a frequent catastrophic brittle failure triggered by minute chips and cracks. Thus, toughening generally conflicts with mechanical reinforcement. Carbon nanotubes have been used as efficient reinforcing agents in various applications due to their combination of extraordinary mechanical, electrical, and thermal properties. Moreover, nanotubes can elongate more than 20% without yielding or breaking, and absorb significant amounts of energy during deformation, which enables them to also be an efficient toughening agent, as well as excellent reinforcing inclusion. Accordingly, an improved toughening method is provided by incorporating nanotubular inclusions into a host matrix, such as thermoset and thermoplastic polymers or ceramics without detrimental effects on the matrix's intrinsic physical properties.
Conventional toughening agents are typically rubbery materials or small molecular weight molecules, which mostly sacrifice the intrinsic properties of a matrix such as modulus, strength, and thermal stability as side effects. On the other hand, high modulus inclusions tend to reinforce elastic modulus very efficiently, but not the strength very well. For example, mechanical reinforcement with inorganic inclusions often degrades the composite toughness, encountering a frequent catastrophic brittle failure triggered by minute chips and cracks. Thus, toughening generally conflicts with mechanical reinforcement. Carbon nanotubes have been used as efficient reinforcing agents in various applications due to their combination of extraordinary mechanical, electrical, and thermal properties. Moreover, nanotubes can elongate more than 20% without yielding or breaking, and absorb significant amounts of energy during deformation, which enables them to also be an efficient toughening agent, as well as excellent reinforcing inclusion. Accordingly, an improved toughening method is provided by incorporating nanotubular inclusions into a host matrix, such as thermoset and thermoplastic polymers or ceramics without detrimental effects on the intrinsic physical properties of the matrix.
A molecular formulation of the onset of plasticity is proposed to assess temperature and strain rate effects in anisotropic semi-crystalline rubbery films. The presented plane stress criterion is based on the strain rate-temperature superposition principle and the cooperative theory of yielding, where some parameters are assumed to be material constants, while others are considered to depend on specific modes of deformation. An orthotropic yield function is developed for a linear low density polyethylene thin film. Uniaxial and biaxial inflation experiments were carried out to determine the yield stress of the membrane via a strain recovery method. It is shown that the 3% offset method predicts the uniaxial elastoplastic transition with good accuracy. Both the tensile yield points along the two principal directions of the film and the biaxial yield stresses are found to obey the superposition principle. The proposed yield criterion is compared against experimental measurements, showing excellent agreement over a wide range of deformation rates and temperatures.
Room temperature vulcanizing (RTV) silicone is a high-temperature adhesive used as a gap-filler between heatshield tiles in numerous entry missions. Its propensity to intumesce, or swell upon exposure to heat, is a well-known effect that needs to be carefully quantified during design. At tile interfaces of charring ablators, intumescence, combined with differential recession, could cause the gap filler to protrude past the ablator outer mold line, forming a “fence”. Fencing can in turn cause transition to turbulence of the flow wetting the heat shield, leading to augmented surface heating. Recent experiments conducted at the Plasmatron X facility, the high enthalpy wind tunnel of the Center for Hypersonics and Entry Systems Studies, have shown prominent fencing of RTV gap fillers in PICA, under both nitrogen and air plasmas. Similar observations are well known in the arcjet literature. Further experiments under controlled environment, performed using in situ X-ray micro-computed tomography (micro-CT) at the Advanced Light Source (ALS), have shown heating rate-dependent swelling and shrinkage of RTV during pyrolysis. To simulate RTV intumescence, a novel model was introduced in the Porous Materials Analysis Toolbox based on OpenFOAM, PATO, to account for pore-pressure buildup within both closed- and open-pores. The governing equation for the thermo-poro-mechanical response were developed, assuming linear elasticity for the charring silicone. A new multi-pyrolysis model that tracks non-monotonic advancement of material properties with pyrolysis was proposed. This model addresses the limitations of state-of-the-art ablator models to capture the different stages of thermal degradation and coupled thermomechanics. Swelling of RTV was simulated using the new thermo-poro-mechanical model and compared against in situ micro-CT data. Results showed good agreement in intumescence height and temperature profiles at all heating rates, indicating that the key factor contributing to RTV swelling is the internal pressure build-up within closed- and open-pores. As RTV is cured into a soft (rubbery) compound with low-porosity and permeability, initial temperature increase and pyrolysis gas production cause a significant increase of internal pressure, causing a pronounced volume growth. As thermal degradation progresses, rigidization of the silicone occurs due to char hardening which counteract volume shrinkage after gas pressure relief. Overall, our model shows that accounting for changes in properties such porosity, permeability and key thermomechanical coefficients is crucial for capturing the RTV volume change during ablation and enable a predictive capability for heatshield tile interface response. A plan for future calibration of thermomechanical properties evolution during degradation is discussed, as a key next step to close the new model.
Room temperature vulcanizing (RTV) silicone is a high-temperature adhesive used as a gap-filler between heatshield tiles in numerous entry missions. Its propensity to intumesce, or swell upon exposure to heat, is a well-known effect that needs to be carefully quantified during design. At tile interfaces of charring ablators, intumescence, combined with differential recession, could cause the gap filler to protrude past the ablator outer mold line, forming a “fence”. Fencing can in turn cause transition to turbulence of the flow wetting the heat shield, leading to augmented surface heating. Recent experiments conducted at the Plasmatron X facility, the high enthalpy wind tunnel of the Center for Hypersonics and Entry Systems Studies, have shown prominent fencing of RTV gap fillers in PICA, under both nitrogen and air plasmas. Similar observations are well known in the arcjet literature. Further experiments under controlled environment, performed using in situ X-ray micro-computed tomography (micro-CT) at the Advanced Light Source (ALS), have shown heating rate-dependent swelling and shrinkage of RTV during pyrolysis. To simulate RTV intumescence, a novel model was introduced in the Porous Materials Analysis Toolbox based on OpenFOAM, PATO, to account for pore-pressure buildup within both closed- and open-pores. The governing equation for the thermo-poro-mechanical response were developed, assuming linear elasticity for the charring silicone. A new multi-pyrolysis model that tracks non-monotonic advancement of material properties with pyrolysis was proposed. This model addresses the limitations of state-of-the-art ablator models to capture the different stages of thermal degradation and coupled thermomechanics. Swelling of RTV was simulated using the new thermo-poro-mechanical model and compared against in situ micro-CT data. Results showed good agreement in intumescence height and temperature profiles at all heating rates, indicating that the key factor contributing to RTV swelling is the internal pressure build-up within closed- and open-pores. As RTV is cured into a soft (rubbery) compound with low-porosity and permeability, initial temperature increase and pyrolysis gas production cause a significant increase of internal pressure, causing a pronounced volume growth. As thermal degradation progresses, rigidization of the silicone occurs due to char hardening which counteract volume shrinkage after gas pressure relief. Overall, our model shows that accounting for changes in properties such porosity, permeability and key thermomechanical coefficients is crucial for capturing the RTV volume change during ablation and enable a predictive capability for heatshield tile interface response. A plan for future calibration of thermomechanical properties evolution during degradation is discussed, as a key next step to close the new model.
Experiments and analyses have confirmed the feasibility of an innovative, new class of very simple, reliable, low mass, low packaging volume, and low-cost self-deployable structures for space and commercial applications.