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At least 19 records

Effects of physical aging on long-term creep of polymers and polymer matrix composites

For many polymeric materials in use below the glass transition temperature, the long term viscoelastic behavior is greatly affected by physical aging. To use polymer matrix composites as critical structural components in existing and novel technological applications, this long term behavior of the material system must be understood. Towards that end, this study applied the concepts governing the mechanics of physical aging in a consistent manner to the study of laminated composite systems. Even in fiber-dominated lay-ups the effects of physical aging are found to be important in the long-term behavior of the composite. The basic concepts describing physical aging of polymers are discussed. Several aspects of physical aging which have not been previously documented are also explored in this study, namely the effects of aging into equilibrium and a relationship to the time-temperature shift factor. The physical aging theory is then extended to develop the long-term compliance/modulus of a single lamina with varying fiber orientation. The latter is then built into classical lamination theory to predict long-time response of general oriented lamina and laminates. It is illustrated that the long term response can be counterintuitive, stressing the need for consistent modeling efforts to make long term predictions of laminates to be used in structural situations.

Brinson, L. Catherine↗

New Insights into Physical Aging‐Induced Structure Evolution in Carbon Molecular Sieve Membranes

Abstract Carbon molecular sieve (CMS) membranes offer the best available combination of scalable economical processability with excellent separation performance. Physical aging of CMS membranes causes pore structure changes over time that affect CMS membrane performance. To provide fundamental insights into the structure evolution in CMS membranes during physical aging, a combined dual‐mode sorption and transport model is used in this study to characterize the diffusion coefficients of gas molecules in fresh and 7‐day vacuum aged CMS membranes. The results show physical aging of CMS membrane is primarily “diffusion related” and such aging behavior simultaneously causes ultramicropore changes in the continuous phase and Langmuir phase of CMS membrane. The new insights offered in this study suggest strategies to control the physical aging of CMS membranes and even use it as a valuable tool to tune the separation performance of CMS membranes for demanding gas separations.

Liu, Zhongyun↗

Time dependent behavior of a graphite/thermoplastic composite and the effects of stress and physical aging

Two complimentary studies were performed to determine the effects of stress and physical aging on the matrix dominated time dependent properties of IM7/8320 composite. The first of these studies, experimental in nature, used isothermal tensile creep/aging test techniques developed for polymers and adapted them for testing of the composite material. From these tests, the time dependent transverse (S22) and shear (S66) compliance's for an orthotropic plate were found from short term creep compliance measurements at constant, sub-T(sub g) temperatures. These compliance terms were shown to be affected by physical aging. Aging time shift factors and shift rates were found to be a function of temperature and applied stress. The second part of the study relied upon isothermal uniaxial tension tests of IM7/8320 to determine the effects of physical aging on the nonlinear material behavior at elevated temperature. An elastic/viscoplastic constitutive model was used to quantify the effects of aging on the rate-independent plastic and rate-dependent viscoplastic response. Sensitivity of the material constants required by the model to aging time were determined for aging times up to 65 hours. Verification of the analytical model indicated that the effects of prior aging on the nonlinear stress/strain/time data of matrix dominated laminates can be predicted.

Gates, Thomas S.↗

Physical aging in comets

The question of physical aging in cometary nuclei is addressed in order to elucidate the relationship between the past conditions in the protosolar nebula and the present state of the cometary nucleus, and to understand the processes that will physically and chemically alter the nucleus as a function of time. Attention is given to some of the processes that might be responsible for causing aging in comets, namely, radiation damage in the upper layers of the nucleus during the long residences in the Oort cloud, processing from heating and collisions within the Oort cloud, loss of highly volatile species from the nucleus on the first passage through the inner solar system, buildup of a dusty mantle, which can eventually prohibit further sublimation, and a change in the porosity, and hence the thermal properties, of the nucleus. Recent observations suggest that there are distinct differences between 'fresh' Oort cloud comets and thermally processed periodic comets with respect to intrinsic brightness and rate of change of activity as a function of distance.

Meech, Karen J.↗

Time-Dependent Behavior of a Graphite/Thermoplastic Composite and the Effects of Stress and Physical Aging

Experimental studies were performed to determine the effects of stress and physical aging on the matrix dominated time dependent properties of IM7/8320 composite. Isothermal tensile creep/aging test techniques developed for polymers were adapted for testing of the composite material. Time dependent transverse and shear compliance's for an orthotropic plate were found from short term creep compliance measurements at constant, sub-T(8) temperatures. These compliance terms were shown to be affected by physical aging. Aging time shift factors and shift rates were found to be a function of temperature and applied stress.

Gates, Thomas S.↗

Physical aging effects on the compressive linear viscoelastic creep of IM7/K3B composite

An experimental study was undertaken to establish the viscoelastic behavior of 1M7/K3B composite in compression at elevated temperature. Creep compliance, strain recovery and the effects of physical aging on the time dependent response was measured for uniaxial loading at several isothermal conditions below the glass transition temperature (T(g)). The IM7/K3B composite is a graphite reinforced thermoplastic polyimide with a T(g) of approximately 240 C. In a composite, the two matrix dominated compliance terms associated with time dependent behavior occur in the transverse and shear directions. Linear viscoelasticity was used to characterize the creep/recovery behavior and superposition techniques were used to establish the physical aging related material constants. Creep strain was converted to compliance and measured as a function of test time and aging time. Results included creep compliance master curves, physical aging shift factors and shift rates. The description of the unique experimental techniques required for compressive testing is also given.

Veazie, David R.↗

Creation of Self-Semi-Interpenetrating Network Structures in PIM-1 Membranes for Enhanced Physical Aging Resistance

A series of self-semi-interpenetrating network (ssIPN) thin films based on PIM-1 structure were developed by end-cross-linking telechelic PIM-1 oligomers end-capped with curable carboxylic acid groups to form model networks, which are penetrated by linear high-molecular-weight PIM-1 chains. ssIPN films with systematically varied network content ranging from 10 to 30 wt % were comprehensively examined on their microstructure and gas permeation properties. Fresh PIM-1 ssIPN films exhibited gas separation performances close to those of as-cast linear PIM-1, where the films closely followed the upper bound trade-off line, gaining as much selectivity as they lose gas permeability as the network content increases. This indicates that gas permeability is largely preserved despite cross-linking. Wide-angle X-ray scattering supported this observation, with peaks shifting toward lower d-spacing as oligomer content increased, suggesting tighter chain packing with higher cross-linkable oligomer loading. In physical aging studies over two months, all ssIPN films outperform linear PIM-1 for H 2 /CH 4 and O 2 /N 2 separations. Notably, the PIM-1 ssIPN with 10 wt % network content showed the best physical aging resistance, with negligible permeability loss even after one month. Finally, these findings highlight a promising macromolecular strategy for enhancing the physical aging resistance of microporous polymer membranes for gas separation.

PIM-1↗

Physical aging and solvent effects on the fracture of LaRC-TPI adhesives

When amorphous materials are quenched below their glass transition temperature, excess enthalpy is trapped in the glassy material because the viscosity is too great to allow the material to remain in volumetric equilibrium. Over time, this excess free volume is reduced as the material slowly approaches its equilibrium configuration. This process, known as physical aging, leads to substantial changes in the constitutive behavior of polymers, as has been widely discussed in the literature. Less is known about the effects of this physical aging process on fracture and fatigue properties of aged materials. The original goal of the summer was to investigate the effects of physical aging on the fracture and fatigue behavior of LaRC-TPI, a thermoplastic polyimide developed at NASA-Langley. Preliminary results are reported, although a lack of equipment availability prevented completion of this task. In the process of making specimens, the current LaRC-TPI was observed to be extremely susceptible to environmental stress cracking. A study of the unique failure patterns resulting from this degradation process in bonded joints was conducted and is also reported herein.

Dillard, David A.↗

Effects of physical aging on long-term behavior of composites

The HSCT plane, envisioned to have a lifetime of over 60,000 flight hours and to travel at speeds in excess of Mach 2, is the source of intensive study at NASA. In particular, polymer matrix composites are being strongly considered for use in primary and secondary structures due to their high strength to weight ratio and the options of property tailoring. However, an added difficulty in the use of polymer based materials is that their properties change significantly over time, especially at the elevated temperatures that will be experienced during flight, and prediction of properties based on irregular thermal and mechanical loading is extremely difficult. This study focused on one aspect of long-term polymer composite behavior: physical aging. When a polymer is cooled to below its glass transition temperature, the material is not in thermodynamic equilibrium and the free volume and enthalpy evolve over time to approach their equilibrium values. During this time, the mechanical properties change significantly and this change is termed physical aging. This work begins with a review of the concepts of physical aging on a pure polymer system. The effective time theory, which can be used to predict long term behavior based on short term data, is mathematically formalized. The effects of aging to equilibrium are proven and discussed. The theory developed for polymers is then applied first to a unidirectional composite, then to a general laminate. Comparison to experimental data is excellent. It is shown that the effects of aging on the long-term properties of composites can be counter-intuitive, stressing the importance of the development and use of a predictive theory to analyze structures.

Brinson, L. Catherine↗

Glassy polymers: Historical findings, membrane applications, and unresolved questions regarding physical aging

Polymers below their glass transition temperature (Tg) are non-equilibrium glasses because excess free volume “frozen” between kinetically-restricted polymer chains slowly relaxes over time towards equilibrium via local, segmental chain motion. This process, known as physical aging, is observed through time-dependent decreases in a polymer's specific volume, enthalpy, etc. This article focuses on the history of glassy polymers in membrane separation applications. Open questions regarding the influence of thickness (e.g., membrane geometry) and temperature on physical aging in glassy polymers are highlighted.

36 MATERIALS SCIENCE↗

The effect of physical aging on the time-dependent properties of carbon-fiber-reinforced epoxy composites

Annealing in nitrogen below the glass transition temperature T(g) is found to affect the matrix-dominated physical properties of postcured, (+ and -45)2s specimens of Thornel 300 carbon fiber/Fiberite 934 epoxy composite as well as neat Fiberite 934 epoxy resin. The damping behavior, stress-relaxation rate and enthalpic state of the matrix material are found to decrease as functions of annealing time. The time-dependent change in physical properties is explained on the basis of free-volume collapse related to the physical aging of the nonequilibrium glassy network of epoxy. Such physical aging in network epoxy has been demonstrated to be thermoreversible through the monitoring of its kinetics by differential scanning calorimetry, stress relaxation tests, and dynamic mechanical analysis.

Kong, E. S. W.↗

The effects of stress and physical aging on the creep compliance of a polymeric composite

An experimental study was performed to determine the effects of stress and physical aging on the matrix dominated viscoelastic properties of IM7/8320, a high temperature fiber reinforced thermoplastic composite. Established creep/aging test techniques developed for polymers were adapted for testing of the composite material. The transverse and shear compliance for an orthotropic plate were found from creep compliance measurements at constant, sub-Tg temperatures. These compliance terms were shown to be effected by physical aging. Aging time shift factors and shift rates were found to be a function of applied stress.

Gates, Thomas E.↗

Effect of physical aging on stress relaxation of poly/methyl methacrylate/

A study was made on the stress relaxation behavior at 25 C of poly(methyl methacrylate) in uniaxial tension as a function of physical aging at both room temperature and 60 C. Test specimens were compression molded at 165 C, then quenched to room temperature and allowed to age for up to 30 days prior to testing. Stress relaxation curves measured after different aging times could be superposed to a single master curve for each aging temperature. Superposition was achieved by applying vertical and horizontal shifts. Hence, the shape of the response curves was not changed by aging. This is in accordance with observations made by Struik for tensile creep curves. Volume changes as a function of physical aging were also determined. Simple exponential relationships were observed between volume and both horizontal and vertical shifts. The horizontal shift implies a shift in the effective time scale caused by a change in free volume. The vertical shifts could be correlated with changes in Young's modulus caused by a change in density. For the range of aging studied, the response time scale varied over nearly two decades of log-time. For the same conditions modulus varied by 30 percent.

Cizmecioglu, M.↗

The effects of physical aging at elevated temperatures on the viscoelastic creep on IM7/K3B

Physical aging at elevated temperature of the advanced composite IM7/K3B was investigated through the use of creep compliance tests. Testing consisted of short term isothermal, creep/recovery with the creep segments performed at constant load. The matrix dominated transverse tensile and in-plane shear behavior were measured at temperatures ranging from 200 to 230 C. Through the use of time based shifting procedures, the aging shift factors, shift rates and momentary master curve parameters were found at each temperature. These material parameters were used as input to a predictive methodology, which was based upon effective time theory and linear viscoelasticity combined with classical lamination theory. Long term creep compliance test data was compared to predictions to verify the method. The model was then used to predict the long term creep behavior for several general laminates.

Gates, Thomas S.↗

Synergistic Effects of Physical Aging and Damage on Long-Term Behavior of Polymer Matrix Composites

The research consisted of two major parts, first modeling and simulation of the combined effects of aging and damage on polymer composites and secondly an experimental phase examining composite response at elevated temperatures, again activating both aging and damage. For the simulation, a damage model for polymeric composite laminates operating at elevated temperatures was developed. Viscoelastic behavior of the material is accounted for via the correspondence principle and a variational approach is adopted to compute the temporal stresses within the laminate. Also, the effect of physical aging on ply level stress and on overall laminate behavior is included. An important feature of the model is that damage evolution predictions for viscoelastic laminates can be made. This allows us to track the mechanical response of the laminate up to large load levels though within the confines of linear viscoelastic constitutive behavior. An experimental investigation of microcracking and physical aging effects in polymer matrix composites was also pursued. The goal of the study was to assess the impact of aging on damage accumulation, in ten-ns of microcracking, and the impact of damage on aging and viscoelastic behavior. The testing was performed both at room and elevated temperatures on [+/- 45/903](sub s) and [02/903](sub s) laminates, both containing a set of 90 deg plies centrally located to facilitate investigation of microcracking. Edge replication and X-ray-radiography were utilized to quantify damage. Sequenced creep tests were performed to characterize viscoelastic and aging parameters. Results indicate that while the aging times studied have limited ]Influence on damage evolution, elevated temperature and viscoelastic effects have a profound effect on the damage mode seen. Some results are counterintuitive, including the lower strain to failure for elevated temperature tests and the catastrophic failure mode observed for the [+/- 45/9O3](sub s), specimens. The fracture toughness for transverse cracks increases with increasing temperature for both systems: transverse cracking was completely absent prior to failure in [+/- 45/903](sub s), and was suppressed for [02/903](sub s). No significant effect of damage on aging or viscoelastic parameters was observed.

Brinson, L. Cate↗

A Comparison of Tension and Compression Creep in a Polymeric Composite and the Effects of Physical Aging on Creep Behavior

Experimental and analytical methods were used to investigate the similarities and differences of the effects of physical aging on creep compliance of IM7/K3B composite loaded in tension and compression. Two matrix dominated loading modes, shear and transverse, were investigated for two load cases, tension and compression. The tests, run over a range of sub-glass transition temperatures, provided material constants, material master curves and aging related parameters. Comparing results from the short-term data indicated that although trends in the data with respect to aging time and aging temperature are similar, differences exist due to load direction and mode. The analytical model used for predicting long-term behavior using short-term data as input worked equally as well for the tension or compression loaded cases. Comparison of the loading modes indicated that the predictive model provided more accurate long term predictions for the shear mode as compared to the transverse mode. Parametric studies showed the usefulness of the predictive model as a tool for investigating long-term performance and compliance acceleration due to temperature.

Gates, Thomas S.↗

Influence of physical aging on the time-dependent properties of network epoxies and epoxy-matrix composites

The matrix-dominated properties of a network epoxy and its carbon fiber-reinforced composite are noted to be affected by sub-glass transition temperature T(g) annealing in a nitrogen atmosphere. The damping behavior, stress relaxation rate, and enthalpic state of the matrix material were found to decrease as functions of sub-T(g) annealing time. This time-dependent change in physical properties is explained on the basis of a free-volume collapse which is related to the recovery process of the nonequilibrium glassy network of the epoxy. The physical aging in network epoxies has been demonstrated to be thermoreversible. Aging kinetics are studied by means of differential scanning calorimetry, stress relaxation tests, dynamic mechanical analysis, and thermomechanical analysis.

Kong, E. S. W.↗