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Shape Memory Mechanics of an Elastic Memory Composite Resin

Erik R. Abrahamson, Mark S. Lake, Naseem A. Munshi and Ken Gall Journal of Intelligent Material Systems and Structures 2003 14: 623 DOI: 10.1177/104538903036213 The online version of this article can be found at: http://jim.sagepub.com/content/14/10/623

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Shape Memory Mechanics of an Elastic Memory Composite Resin

ERIK R. ABRAHAMSON,1,* MARK S. LAKE,1 NASEEM A. MUNSHI1 AND KEN GALL2
1

Composite Technology Development, Inc., 2600 Campus Drive, Suite D, Lafayette, Colorado, 80026, USA 2 University of Colorado, Boulder, Colorado, 80303, USA ABSTRACT: Substantially more attention has been given in the past to shape memory alloys and shape memory ceramics than to shape memory polymers because unreinforced shape memory polymers have much lower stiffness and recovery force potential than shape memory alloys and shape memory ceramics. However, when incorporated into a fiber-reinforced composite, both the stiffness and the recovery force of a shape memory polymer can be dramatically improved. This paper presents recent advances in characterizing the shape memory mechanics of a thermoset shape memory polymer resin for Elastic Memory Composite (EMC) materials. In particular, heretofore undocumented response behavior is characterized through a series of thermo-mechanical tests of a commercially available EMC resin, and a lumped parameter model is adapted to accurately correlate this behavior. Through application of this model, it appears that the molecular transition associated with the shape memory effect occurs at a temperature other than the glass transition temperature of the resin. Key Words: shape memory polymer, elastic memory composite, glass transition, shape recovery

BACKGROUND memory polymers are a subset of the broad class of smart materials known as shape memory materials (Otsuka and Wayman, 1998). Substantially more attention has been given in the past to shape memory alloys and shape memory ceramics than to shape memory polymers because unreinforced shape memory polymers have much lower stiffness and recovery force potential than shape memory alloys and shape memory ceramics. However, when incorporated into a fiber-reinforced composite, both the stiffness and the recovery force of a shape memory polymer can be dramatically improved (Liang et al., 1997; Gall et al., 2000; Ni et al., 2000). The key advantages of fiberreinforced shape memory polymer materials (i.e. elastic memory composites) over shape memory alloys and shape memory ceramics are the substantially lower densities and higher strain capacities, and potentially lower processing costs that are achievable with elastic memory composites (EMC). The key advantage of EMC materials over traditional composite materials is that the shape memory polymer resin has a high elasticstrain capacity and the ability to store, and subsequently recover, mechanically induced strain when subjected to a specific thermo-mechanical cycle. Recent studies have identified several interaction phenomena between the reinforcement fibers and the

HAPE

*Author to whom correspondence should be addressed. E-mail: erik@ctd-materials.com

shape memory polymer resin in an EMC laminate that enable the laminate to be bent to relatively small radii of curvature without inducing damage in the fibers. For example, it has been shown that fiber microbuckling allows high compressive strains to occur in uni-axially reinforced EMC laminates, see Figure 1. (Gall et al., 2001; Murphey et al., 2001; Lake and Beavers, 2002). In cross-ply laminates, inter- and intra-laminar resin shearing can be significant. In all laminates, relatively high strains must develop in the shape memory polymer resin in order to avoid fiber breakage. The present study is focused on the shape memory behavior of the bulk resin rather than the behavior of the fiber-reinforced resin. This approach is taken because the strains induced in the resin within a fiberreinforced laminate vary dramatically throughout the laminate, and the shape memory behavior of the resin can vary with the magnitude of induced strain (Lake and Beavers, 2002). In addition, the present study is focused on the shape memory characteristics of a commercially available thermoset resin. Nearly all past work that has been cited in the literature on shape memory polymers is limited to thermoplastic chemistries as opposed to thermoset chemistries (Liang et al., 1997; Tobushi et al., 1997, 1998; Ni et al., 2000) Of course, most structuralgrade composite components for spacecraft applications incorporate thermoset resins rather than thermoplastic resins, due to the better mechanical performance, ease of fabrication, and environmental durability inherent in thermoset resins. STRUCTURES, Vol. 14October 2003 623

JOURNAL

OF INTELLIGENT

MATERIAL SYSTEMS

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1045-389X/03/10 062310 $10.00/0 DOI: 10.1177/104538903036213 2003 Sage Publications

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Figure 1. Microbuckling of fibers in EMC rods: (a) Lateral bending test of 6.35 mm (1/4-in.) dia. EMC rod; (b) Fiber microbuckles in 6.35 mm (1/4-in.) and 1.59 mm (1/16-in.) rods.

MECHANICS OF SHAPE MEMORY POLYMERS The shape memory effect in materials is essentially the capacity to recover mechanically induced and frozen strain upon application of heat, magnetic field, or electric field. The shape memory effect has been demonstrated in ceramics, metals, and polymers, and the molecular mechanisms responsible for the effect have been found to be different for each of these three materials (Otsuka and Wayman, 1998). In metals and ceramics, the shape memory effect is related to a welldefined crystalline phase change in the material, which occurs at a specific temperature and/or stress level. In polymers, the shape memory effect is related to a variety of molecular interactions, which have less well-defined activation temperatures and/or stresses. Tobushi and others have postulated that the shape memory effect in polymers is related to the phase change that occurs through the glass transition (Tobushi et al., 1997, 1998). This postulate leads to an apparent analogy between the martensiteaustenite transformation temperatures in shape memory alloys and the glass transition temperature in shape memory polymers. Indeed, the accepted thermo-mechanical cycles for affecting shape memory response in shape memory polymers and alloys are both defined with respect to these transition temperatures. The commonly accepted thermo-mechanical cycle for testing shape memory polymers is given in Table 1. The present paper includes the results of recent studies that have uncovered an additional similarity between the shape memory behavior of an EMC resin and shape memory alloys. Specifically, it has been found that the phase change, associated with the shape memory effect in this EMC resin, can be excited either under

Table 1. Typical thermo-mechanical cycle for shape memory polymers (SMP) testing.
Step 1 2 3 4 Procedure Mechanically induce strain while the SMP is heated above its Tg Freeze the induced strain by holding the mechanical load and cooling below Tg Remove load and lightly constrain in packaged shape Recover frozen strain by reheating the SMP above Tg

combined thermal and mechanical loading (i.e., using the loading cycle listed above), or under pure mechanical loading. In other words, it has been found that mechanically induced strain can be either frozen in this EMC resin at temperatures well below the Tg of the resin, and recovered by subsequent thermal cycling above the Tg of the resin, or recovered without further heating when strained well above Tg of the resin. This discovery is significant because it has led to the identification of a lumped-parameter viscoelastic model that accurately represents the shape memory mechanics of the EMC resin. Furthermore, through application of this model, it appears that the molecular transition associated with the shape memory effect occurs at a temperature other than the Tg of the resin. Ultimately, it is hoped that this model will lead to better predictions of the shape memory mechanics of fiber-reinforced EMC materials that are made with the resin. The next section of this paper summarizes the experimental procedures and results from testing of the CTD-DP-5.1 resin. Subsequently, the analytical model that describes EMC shape memory behavior is presented and correlated with the experimental results.

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EXPERIMENTAL INVESTIGATION OF THE SHAPE MEMORY MECHANICS OF AN EMC RESIN In the present program, several specimens of CTDDP-5.1 EMC resin were subjected to a variety of thermo-mechanical loading conditions, and the shape memory behavior of the material was characterized. All testing was done in tension, and all specimens were fabricated using an ASTM standard tensile test specimen design (Anon, 1997). New testing procedures were developed and applied, and these procedures are described below. Tests were performed over a range of temperatures through the glass-transition regime of the CTD-DP-5.1 resin. Figure 2 presents data from DMA testing (under torsional loading) of the resin. Plotted in Figure 2 are the shear modulus, G, complex shear modulus (i.e., loss modulus), G*, and the ratio of G*/G. The peak in the G*/G curve is defined as the Tg of the resin, and is at 71 C. It can be seen that most of the variation in modulus for CTD-DP-5.1 occurs between 20 and 80 C. All tests in the present program were conducted with the specimen at temperatures between these two extremes. Description of Test Procedures Shape memory polymers have not received as much attention in the literature as shape memory alloys and shape memory ceramics. Hence, there does not currently exist a standard test procedure for investigating their shape memory behavior. One procedure that is commonly applied incorporates the thermo-mechanical cycle outlined in Table 1 (Ni et al., 2000).In the present program, a new test procedure was developed and applied. The test procedure is based on applying the thermo-mechanical cycle described in Table 2. Unlike the cycle described in Table 1, the new cycle involves straining the EMC resin at temperatures below its Tg and determining whether strain that is frozen at these temperatures is recoverable with subsequent heating

above Tg. A matrix of tension tests were performed to specified strain levels and at specified temperatures. As mentioned previously, the range of test temperatures covered most of the glass-transition regime. The test specimens were fabricated with the ASTMstandard geometry shown in Figure 3 (Anon, 1997). The cross section in the necked region of the specimens measured 6.35 mm (1/4 in.) wide by 3.18 mm (1/8 in.) thick. The specimens were machined from 3.18 mm (1/8 in.) thick flat plates of resin, which were cured in a 15.24 cm (6 in.) by 20.3 cm (8 in.) rectangular mold. The final machining of the specimens to the dog bone profile shown in Figure 3 was performed using an end-mill. Note, the left-hand specimen in Figure 3 has been painted black to facilitate videometric strain measurement (to be discussed later), and the right-hand specimen is unpainted. TEST APPARATUS AND VIDEOMETRY SYSTEM Testing was performed using a servo-hydraulic MTS load frame, with a maximum load capacity of 490 kN (110,000 lbf) and a 4 kN (1000 lbf) load cell installed for adequate load resolution (see Figure 4). Elevatedtemperature tests were performed using an electrically heated thermal shroud (see Figure 4(b)), and roomtemperature tests did not necessitate the thermal shroud (see Figure 4(a)). While performing room-temperature tests, strain within the necked region of the specimen was measured directly using a videometry system
Table 2. New thermo-mechanical cycle for EMC resin testing.
Step 1 2 3 Procedure Mechanically strain the EMC resin to high strain values while it is below its Tg Remove the mechanical load and observe residual frozen strain Recover the frozen strain by reheating the EMC resin back above Tg

Figure 2. CTD-DP-5.1 DMA data.

Figure 3. Test specimens.

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Figure 4. Tension testing setup: (a) Room temperature testing using videometry; (b) Thermal shroud for high temperature testing.

(note cameras in Figure 4(a) and reflective targets on specimens in Figure 3). The videometry system was designed to accurately measure high values of induced strain (i.e., 10%<"<100%). However, it could only be used during room-temperature tests, because the specimen was not visible through the thermal chamber during elevated-temperature tests (see Figure 4(b)). Crosshead displacement of the load frame was used to determine an estimate for the average strain in the specimen for all testing. The crosshead displacement was measured using a Linear Variable Displacement Transducer (LVDT). The average strain in the specimen was estimated by dividing the measured crosshead displacement by an empirically determined gauge length. A derivation of the crosshead gauge length will be presented in the next section. The videometry system included two Sony XC-75 CCD analog cameras, each outfitted with a telephoto lens (see Figure 4(a)). The cameras were mounted such that they viewed opposite sides of the specimen. This enabled the average centerline strain within the specimen to be inferred by averaging the strain measurements from the two cameras. The strain measurements were made by comparing the relative position of two targets positioned one inch apart on each side of the specimen (see Figure 3). In order to maximize image contrast and system accuracy, retro-reflective targets were used, and

the specimens were painted with a high-strain, flat black paint (see left-hand specimen in Figure 3) (Pappa et al., 2002). Targets were placed approximately one inch apart, center to center. An adjustable-focus, fiber optic lighting system was used to illuminate the targets. Data reduction algorithms and a user interface for operation of the videometry system were written in LabVIEW. The user interface allowed real-time monitoring of critical test parameters and provided a realtime, stressstrain plot. The data reduction algorithms compiled load, crosshead displacement, videometry strain measurements, converted load to average stress, and crosshead displacement to average strain. The lateral Poisson contraction in the specimen was also measured using the videometry system, and the corresponding reduction in cross sectional area was computed to more accurately characterize the average stress. Again, this capability could only be used during room-temperature tests. At the beginning of each room-temperature test, the prepared specimen was placed in the load frame, and the LabVIEW image-acquisition software was used to setup the specimen image. The analog image captured by the camera was converted to a 16-bit digital image, with an image resolution of 640 480 pixels. A region of interest was defined around the targets, and everything outside the region of interest was eliminated in subsequent image analyses. To efficiently discern the targets from the background, the image was converted from a 16-bit grayscale to a black and white binary image with the contrast adjusted such that the targets appeared white and the specimen and background appeared black. The image analysis routine was designed to locate the geometric centers of the two targets and to calculate the distance (in pixels) between the centers. Strain was then determined by comparing distance between the targets as the load was applied. TEST PROTOCOL Prior to the start of each test, distance between videometry targets on the specimen was measured and recorded using hand calipers to an accuracy of approximately 0.0254 mm (0.001 in.). This measurement was used at subsequent stages of the testing to determine whether full strain recovery had taken place. During each test, the specimen was loaded in tension by moving the load frame crosshead at a rate of 0.00838 mm/s (0.00033 in/s.). This resulted in an average strain-rate in the specimen of approximately 0.02%/s, which was determined to be well below the strain-rate limit of the material. Crosshead motion was reversed when a predetermined maximum strain was achieved in the specimen, and crosshead motion was stopped when the load returned to zero. Upon completion of the load cycle, all significant data were saved for further analysis.

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After each test was complete, the specimen was removed from the load frame and its length (i.e., distance between videometry targets) was again measured and recorded. The specimen was then heated, above its glass transition temperature, to 120 C and held at that temperature for approximately 30 min. The specimen was then cooled to room temperature, and the distance between videometry targets was again measured and recorded. This heat cycle allowed for recovery of any stored strain. Each specimen was tested only once (i.e., one load cycle and subsequent heat cycle) in order to eliminate any variations in behavior due to multiple load cycles. During elevated-temperature tests, a thermal shroud was fitted around the specimen as discussed earlier (see Figure 4(b)). The thermal shroud incorporated electrical heating elements capable of heating the specimen to the desired test temperatures. Prior to an elevated-temperature test, the load frame and hardware were first brought up to the test temperature, then the specimen was placed into the heated load frame and brought to temperature. With the specimen at temperature, the test protocol described previously was executed. The complete matrix of tests performed during the present program is presented in Table 3 (note an X in Table 3 indicates a test that was performed). Tests were conducted up to three maximum strain values (i.e., 10, 20, and 30%), and at six average temperatures (i.e., 25, 35, 45, 55, 65, and 85 C). In general, the specimen was a few degrees cooler than the average test temperature at the beginning of the test, and a few degrees warmer than the average test temperature at the end, due to buildup of strain energy during loading.
Table 3. Test matrix.
Average Temperature ( C*) "max (%) 10 20 30 25 X X X 35 45 55 65 85

Test Results COMPARISON OF VIDEOMETRY AND CROSSHEAD STRAIN MEASUREMENTS As discussed previously, the videometry system was only used during room temperature tests, so strain measurements during elevated-temperature tests were based on crosshead displacement. Of course, deriving strain from crosshead displacement implicitly assumes that the crosshead and specimen mounting hardware are rigid, and all deformation occurs in the specimen. A key parameter that is needed to estimate strain from crosshead displacement is the effective gauge length on the specimen (i.e., the length across which the deformation is assumed to occur). An empirical value of 3.94 cm (1.55 in.) was determined for this gauge length by correlating the crosshead displacement data and the videometry strain data. To illustrate this correlation, Figure 5 presents the stressstrain response for a specimen tested to 30% strain at room temperature. LVDT strain plotted in Figure 5 was produced by dividing crosshead displacement by the gauge length of 3.94 cm (1.55 in.), and the other value of strain was produced using the videometry system. Note that the crossheadmeasured strain and videometry-measured strain match reasonably well across the range of strain up to 30%. The two strain values differ the most at low strains due to mechanical settling of the load frame, which is sensed by the crosshead-motion measurement. However, the present tests are mainly concerned with highstrain response, so the strain estimates based on crosshead motion were deemed acceptable for all subsequent tests. HIGH-STRAIN RESPONSE AT ROOM TEMPERATURE Figure 6 shows the stressstrain response from roomtemperature tests (i.e., average specimen temperature

*Note the specimen temperature varied by 34 C during each test, so this is an approximate average temperature during the tests.

Table 4. Numerically derived values for CTD-DP-5.1 constitutive parameters.

Temperature ( C) 25 35 45 55 65 85 Eo (MPa) 470 410 76 4.8 6.2 5.4 Et (MPa) 3.7 7.7 5.5 4.4 5.2 5.4  cr (MPa) 20 13 10 0.69 0.69  0.85 0.65 0.15 0.10 0.05

Figure 5. Crosshead and videometry strains at 25 C.

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Figure 6. Comparison of test results at 25 C for three maximum induced strains.

Figure 7. Strain recovery of specimens tested at 25 C.

equal to 25 C) to maximum strains of approximately 10, 20, and 30%, respectively. All three tests show the same trend. At the onset of loading, the material exhibits high stiffness (i.e., E % 690 MPa) up to an induced strain of approximately 3% and an induced stress of approximately 20 MPa (3000 psi). Within a few percent of additional strain, the stiffness of the material drops by approximately two orders of magnitude and remains relatively constant up to the predetermined maximum induced strain. Once maximum strain was reached, crosshead motion was reversed and the load was removed at the same rate it was applied. The stiffness of the specimen during unloading was close to that measured at the onset of loading (i.e., E % 690 MPa). It should be apparent from the data presented in Figure 7 that the specimens exhibited a net (i.e., residual) strain at the end of each room-temperature test. After each test was complete and residual strain was recorded, the specimen was heated well above its Tg (i.e., to 120 C) for a period of 30 min, and then cooled back to room temperature. Once cooled, the remaining residual strain was measured. As mentioned previously, the residual strain after load cycling and heat cycling was determined by measuring the distance between videometry targets on the specimen. Targets were initially spaced at a distance of about 2.54 cm (1 in.) and this distance was measured to an accuracy of approximately 0.0254 mm (0.001 in.) using hand calipers, so the accuracy of the residual strain measurement was approximately 0.1%. Figure 7 shows the recovered strain (i.e., the maximum induced strain minus residual strain), postload and postheat cycling, for the three roomtemperature tests. Six data points are plotted in Figure 7; the x data points correspond to the postload-cycle recovered strain, and data points correspond to the postheat-cycle recovered strain. The amount of strain recovered immediately after load cycling was found to

increase with induced strain in approximately the following proportion: "r % 3:03 0:16"i 1

where "i is the maximum induced strain, and "r is the recovered strain. The relationship in Equation (1) is a near perfect fit to the experimental data, as shown by the dashed line passing though the postload cycle points in Figure 7. The dashed line passing through the postheat-cycle data points has a slope of one, and corresponds to fully recovered strain (i.e., zero residual strain). It is particularly important to note that, for induced strains up to 30% at room temperature, the CTD-DP-5.1 resin exhibits complete strain recovery upon heat cycling above Tg. This result suggests that the significant reduction in stiffness observed in the material for induced strains above 3%, is NOT the result of plastic (i.e., unrecoverable) strain in the material, but rather it is the result of a transition between two different elastic states within the material. HIGH-STRAIN RESPONSE THROUGHOUT THE GLASS TRANSITION REGIME Specimens were strained to approximately 30%, and subsequently unloaded, while held at approximately 35, 45, 55, 65, and 85 C, respectively. This range of specimen temperatures allowed strain recovery to be characterized throughout the glass transition regime of the resin, determined by DMA testing (see Figure 2). Figure 8 shows the stressstrain response measured during elevated-temperature tests. Figure 8(a) presents data from testing at 25, 35, and 45 C, Figure 8(b) presents data from testing at 55 and 65 C, and both plots include data from testing at 85 C. Note that there

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Figure 8. Comparison of stressstrain response at elevated temperatures: (a) Data from moderate-temperature tests; (b) Data from high-temperature tests.

is an order of magnitude difference in the scale of the stress axis in these plots. By comparing the results presented in Figure 8(a), several key aspects of the material behavior become apparent. First, compare the response of the material under increasing load at 25, 35, and 85 C. At the onset of loading, the material then exhibits a high stiffness (i.e., E % 690 MPa) up to strains of about 3% and for temperatures below 45 C. The material exhibits a substantially reduced stiffness (i.e., E % 6.9 MPa) for higher strains and/or temperatures. Now, compare the response of the material under decreasing load at 25, 35, and 45 C. After achieving maximum strain and as the load is being reduced, the material again exhibits a high stiffness (i.e., E % 690 MPa), which gradually decreases as the load is removed. In general, the slope of the unloading curve decreases as the stress approaches zero. By comparing the slopes of the stressstrain curves in several key regions, additional patterns in the material behavior emerge. At the onset of loading and for strains up to about 3%, the material exhibits approximately the same stiffness at both 25 and 35 C. Similarly, as the strain is increased above 5%, the material exhibits the same dramatically reduced stiffness at 25 and 35 C. Furthermore, the material exhibits essentially the same reduced stiffness at all strain levels when heated to 85 C.

It appears from these data, that the material exhibits two different stiffnesses depending on temperature and induced strain level. It is logical to assume that these different stiffnesses are associated with different intrinsic phases or states within the material. Furthermore, transition from the high-stiffness to the low-stiffness state appears to be affected by either elevating the temperature sufficiently or inducing sufficient mechanical strain. In general, transition from the high-stiffness state to the low-stiffness state occurs within a fairly narrow range of induced strain, except for the case of loading at 45 C. At 45 C, the material exhibits a gradual reduction of stiffness with increasing strain, for the entire range of strain up to 30%. Consider now the results presented in Figure 8(b) from testing at 55, 65, and 85 C. First, note the apparent deadband in response (i.e., region of zero stiffness) between approximately 5 and 9% induced strain is an artifact of compliance in the load frame and not a true response of the material (recall that the strain measurements in these tests are based on crosshead motion). Neglecting this artifact in the data, a key feature to note is that the slope of the stressstrain curve, on the portion of the curve corresponding to increasing load, is essentially the same at these three test temperatures. Conversely, the slope of the stressstrain curve, on the portion of the curve corresponding to decreasing load, decreases with increasing temperature. In the limit, at a temperature of 85 C, the slope of the loading and unloading portions of the stressstrain curve are nearly equal and the hysteresis is minimal. This effect at 85 C is exactly the same as the pseudoelastic effect in shape memory alloys whereby the metals are stressed above their phase transition temperature and show complete recovery upon unloading. No documented work on shape memory polymers was found showing the same effect. It should be apparent from the data presented in Figure 8 that the material retains residual strain at the end of each elevated-temperature load-cycle test, except for the test at 85 C. After completion of each of the elevated temperature tests, the residual strain was recorded, the specimen was heated to 120 C for 30 min and cooled back to room temperature, and the remaining residual strain was measured. As mentioned previously, the residual strain after load cycling and heat cycling was determined by measuring the distance between the videometry targets on the specimen. Figure 9 compares the maximum induced strain with the residual strains measured postload and postheat cycling, for the six elevated-temperature tests compared in Figure 8. The amount of strain recovered immediately upon removal of the load generally increases with increasing temperature. As mentioned

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Figure 9. Strain recovery of specimens tested at elevated temperatures.

previously, essentially all of the induced strain is instantaneously recovered upon removal of load with the material at 85 C, which is 14 C above Tg. The residual strain after heat cycling is essentially zero for all test temperatures. Hence, the CTD-DP-5.1 resin exhibits essentially complete strain recovery for all test conditions considered.

Figure 10. Viscoelastic model of EMC resin: (a) Lumped-parameter model; (b) Typical stressstrain response.

MODELING OF SHAPE MEMORY MECHANICS OF AN EMC RESIN The data presented in the last section indicate that the CTD-DP-5.1 resin does not exhibit plastic yielding at strains up to 30%, and within the temperature range of 2585 C. Furthermore, it was deduced that the significant drop in stiffness at an induced strain between 3 and 5% (below 45 C) is the result of a transition between two different elastic states within the material as opposed to plastic deformation. This section presents a lumped-parameter model of the resin that exhibits two elastic states and predicts all of the key response effects seen in the CTD-DP-5.1 resin. Figure 10(a) presents a sketch of the model. It incorporates four elements: two elastic springs, a viscous damper, and a friction slider. The friction slider, which can be stuck or free to slide, represents the two elastic-response states seen in the experimental data. The model is an adaptation of the Valanis Model from viscoplasticity (Valanis, 1971). A key feature is that the friction slider progresses from fully stuck to fully free over a finite range of strain. The primary difference between the present application of the Valanis Model and its traditional application in plasticity theory, is that the values for the four

empirical parameters vary with temperature. In particular, the stick-slip threshold of the friction slider,  cr, decreases with increasing temperature and vanishes at temperatures approaching Tg. This temperature variation is essential to analytically capture the shape memory behavior of the material. The Valanis Model is governed by the following nonlinear first order constitutive equation:  _t=cr Et "t  t 1 sgn" _t t _ t Eo " C"  _t=cr Et "t  t 1 sgn" 2 The stiffnesses, Eo and Et, damping, C, and the stick-slip stress,  cr, in Equation (2) are defined in Figure 10. The parameter, , in Equation (2) controls the rate at which the friction slider progresses from fully stuck to fully slipping. The value of  is restricted to be within the range of 0  1, and high values of  correspond to sudden transition from sticking to slipping, whereas small values of  correspond to gradual transition from sticking to slipping. Figure 10(b) presents a sketch of a typical stressstrain response predicted using Equation (2), and illustrates the effect of  on the response. Consider now the solution of Equation (2). In general, solving Equation (2) requires knowledge of _(t), and the strain history, "(t), strain-rate history, " 

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(t). In the present program, strain-acceleration history, " all testing was conducted at a constant strain rate, _test , hence: " t 0 " _t " _test " _test t "t " With these functions defined, Equation (2) can be integrated numerically using a variety of integration techniques (Burden, 1985). In the present study, Eulers Method was applied to convert the differential equation in Equation (2) to the following difference equation.  _test t n 1 n Eo "  _=cr Et" _test nt n 1 sgn" _=cr Et" _test nt  n 1 sgn" 4

where t is the numerical integration time step, n is the number of the time step, and  n is the stress at the nth time step. For a given set of data, best-fit values for the stiffnesses, Eo and Et, and the stick-slip stress,  cr, can be determined by least-squares fitting of straight lines to the appropriate regions of the data as sketched in Figure 10(b). A best-fit value for  must be determined iteratively by solving Equation (4) for selected values of , and comparing the results to the test data. The best-fit values for these constitutive parameters are presented in Table 4 and Figure 11 for the range of test temperatures considered in the present program. Figure 12 presents a comparison of the test data (presented originally in Figure 8), and the numerical solutions of Equation (4). In general, the numerical model captures all significant trends in the observed behavior, and the numerical and experimental results agree well for all test temperatures. Consider now the variation of the constitutive parameters as a function of temperature shown in Figure 11. For comparison, the shear modulus, G, of

the CTD-DP-5.1 resin (from DMA test data presented in Figure 2) is also plotted in Figure 11. Note that the computed values for Eo,  cr, and  all decrease with increasing temperature, similar to the trend observed for G during DMA testing. On the other hand, the value for Et remains relatively unchanged with temperature. The most notable difference between the trends observed in the DMA data and those observed in the numerically derived constitutive parameters, is that the drop in Eo,  cr, and  occurs at a lower temperature than the drop in G observed in DMA testing. This difference in temperatures, which is between 20 and 25 C, indicates that the molecular transition associated with the shape memory effect in CTD-DP-5.1 occurs below the glass transition temperature, Tg. In particular, it appears that the peak in the shape memory phase transition occurs in the range of 4550 C, rather than at the Tg, which is 71 C. This result implies that the traditional approach of basing the thermo-mechanical cycle for shape memory polymers (e.g., Table 2) on Tg might be inappropriate. It might be more appropriate to define a shape memory transition temperature, on which thermo-mechanical cycles can be based.

Figure 11. Numerically derived values for CTD-DP-5.1 constitutive parameters.

Figure 12. Comparison of test data with model predictions: (a) Moderate-temperature test results; (b) High-temperature test results.

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E. R. ABRAHAMSON ET AL.

One final point must be reiterated regarding the variation in constitutive parameters with temperature, and the resulting ability of the Valanis Model (i.e., Figure 10(b)) to predict shape memory behavior. As mentioned previously, the original application of the Valanis Model for predicting viscoplastic behavior did not require the parameters of the model to vary with temperature. In the present application for predicting shape memory response in EMC resins, the variation of the parameters with temperature is critical to capturing all aspects of the material behavior. Clearly, the variation of the parameters with temperature is necessary to accurately capture the loadcycle response behavior observed at different temperatures. Of equal importance (but possibly less obvious), the stick-slip threshold of the friction slider,  cr, must decrease with increasing temperature and must vanish at temperatures approaching Tg, if the model is to predict the recovery of residual strain described in Figures 7 and 9.

NOMENCLATURE C material damping (Pa s). Eo effective modulus at low strain (Pa) Et effective modulus at high strain (Pa) Tg resin glass transition temperature ( C) "i induced strain "r recovered strain _ constant strain rate during tests (s1) "  applied stress (Pa)  n stress at the nth time step (Pa)  cr stick-slip stress of friction slider (Pa)  microslip parameter

REFERENCES
Anon. 1987. ASTM Designation D638-86 Standard Test Method for Tensile Properties of Plastics, Annual Book of ASTM Standards, Section 8 Plastics, Vol. 8.01, pp. 218, Plastics (I)C117D1600. Burden, R.L. and Faires, J.D. 1985. Numerical Analysis, pp. 205206, PWS-Kent Publishing Company, Boston, MA. Gall, K., Mikulas, M.M., Munshi, N.A., Beavers, F.L. and Tupper, M.L. Nov 2000. Carbon Fiber Reinforced Shape Memory Polymer Composites, Journal of Intelligent Material Systems and Structures, 11:877886. Gall, K., Tupper, M.L., Munshi, N.A. and Mikulas, M.M. 2001. Micro-Mechanisms of Deformation in Fiber Reinforced Polymer Matrix Elastic Memory Composites, Presented at the 42nd AIAA/ASME/ASCE/AHS/ASC SDM Conference, April 1619, Seattle, WA, AIAA Paper No. 2001-1419. Lake, M.S. and Beavers, F.L. 2002. The Fundamentals of Designing Deployable Structures with Elastic Memory Composites, Presented at the 43rd AIAA/ ASME/ASCE/AHS/ ASC SDM Conference, April 2225, Denver, CO, AIAA Paper No. 2002-1454. Liang, C., Rogers, C.A. and Malafeew, E. April 1997. Investigation of Shape Memory Polymers and Their Hybrid Composites, Journal of Intelligent Material Systems and Structures, 8:380386. Murphey, T.W., Meink, T. and Mikulas, M.M. 2001. Some Micromechanics Considerations in the Folding of Rigidizable Composite Materials, Presented at the 42nd AIAA/ASME/ASCE/ AHS/ASC SDM Conference, April 1619, Seattle, WA, AIAA Paper No. 2001-1418. Ni, Q-Q. et al., 2000. Development of Smart Composites Based on Shape Memory Polymer, Presented at the International Symposium on Smart Structures and Microsystems, Oct. 1921, Hong Kong. Otsuka, K. and Wayman, C.M. (eds), 1998. Shape Memory Materials, Cambridge University Press, Cambridge, UK. Pappa, R.S., Jones, T.W., Robson, S. and Shortis, M.R. 2002. Photogrammetry Methodology Development for Gossamer Spacecraft Structures, to be presented at the 43rd AIAA/ASME/ ASCE/AHS/ASC SDM Conference, 2225 April, Denver, CO. Tobushi, H., Hashimoto, T., Hayashi, S. and Yamada, E. August 1997. Thermomechanical Constitutive Modeling in Shape Memory Polymer of Polyurethane Series, Journal of Intelligent Material Systems and Structures, 8:711718. Tobushi, H., Hashimoto, T., Ito, N., Hayashi, S. and Yamada, E. 1998. Shape Fixity and Shape Recovery in a Film of Shape Memory Polymer of Polyurethane Series, Journal of Intelligent Material Systems and Structures, 9:127136. Valanis, K.C. 1971. A Theory of Viscoplasticity Without a Yield Surface, Archive of Mechanics, 23(4):517551.

CONCLUSIONS The present paper was focused on a shape memory polymer resin for Elastic Memory Composite (EMC) materials. Heretofore undocumented response behavior was characterized through a series of thermo-mechanical tests of an EMC resin. Specifically, it was found that the phase change, associated with the shape memory effect in EMC resins, can be excited either under combined thermal and mechanical loading (i.e., using the loading cycle listed above), or under pure mechanical loading. In other words, it was found that large mechanically induced strains can be induced and recovered due solely to mechanical loads. Shape memory alloys exhibit behavior similar to this. The discovery of this intrinsic behavior has led to the identification of a simple lumped-parameter model that accurately represents the thermo-mechanical and shape memory response of EMC resins. The so-called Valanis Model has been shown to correlate very well with measured stressstrain response over a range of temperatures encompassing the glass transition regime of the resin. Through application of this model, it appears that the molecular transition associated with the shape memory effect occurs at a temperature other than the glass transition temperature, Tg. This result implies that the traditional approach of basing the thermomechanical cycle for shape memory polymers on Tg might be inappropriate. It might be more appropriate to define a shape memory transition temperature, on which thermo-mechanical cycles can be based. Ultimately, it is hoped that the present work will improve the ability to model and predict the shape memory mechanics of fiber-reinforced EMC materials that are made with these shape memory resins.

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