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Journal of the Mechanics and Physics of Solids 56 (2008) 17661778 www.elsevier.com/locate/jmps

A constitutive theory for shape memory polymers. Part II A linearized model for small deformations
Yi-Chao Chena,, Dimitris C. Lagoudasb
b

Department of Mechanical Engineering, University of Houston, Houston, Texas 77204, USA Aerospace Engineering Department, Texas A&M University, College Station, Texas 77843, USA

Received 2 April 2007; received in revised form 3 December 2007; accepted 13 December 2007

Abstract A constitutive theory is developed for shape memory polymers. It is to describe the thermomechanical properties of such materials under large deformations. The theory is based on the idea, which is developed in the work of Liu et al. [2006. Thermomechanics of shape memory polymers: uniaxial experiments and constitutive modelling. Int. J. Plasticity 22, 279313], that the coexisting active and frozen phases of the polymer and the transitions between them provide the underlying mechanisms for strain storage and recovery during a shape memory cycle. General constitutive functions for nonlinear thermoelastic materials are used for the active and frozen phases. Also used is an internal state variable which describes the volume fraction of the frozen phase. The material behavior of history dependence in the frozen phase is captured by using the concept of frozen reference conguration. The relation between the overall deformation and the stress is derived by integration of the constitutive equations of the coexisting phases. As a special case of the nonlinear constitutive model, a neo-Hookean type constitutive function for each phase is considered. The material behaviors in a shape memory cycle under uniaxial loading are examined. A linear constitutive model is derived from the nonlinear theory by considering small deformations. The predictions of this model are compared with experimental measurements. r 2008 Elsevier Ltd. All rights reserved.
Keywords: Shape memory polymers; Nonlinear constitutive theory; Large deformations; Neo-Hookean model; Linearization

1. Introduction In Part I of this work, a three-dimensional constitutive theory for large deformations of shape memory polymers (SMPs) is developed. The theory is built on the framework of nonlinear thermoelasticity, with sufcient structures to describe thermomechanical properties of the active and frozen phases of the material, as well as the corresponding phase transitions. Such transitions are mathematically formulated based on two basic assumptions concerning the storage and release of deformations when the material passes through the transition temperature: rst, the deformation must be continuous during cooling, and second, the deformation stored in the material at freezing is instantaneously released when the material is heated to the glass transition temperature. These assumptions lead to the derivation of a mathematical model for the constitutive behavior
Corresponding author.

E-mail addresses: chen@uh.edu (Y.-C. Chen), lagoudas@aeromail.tamu.edu (D.C. Lagoudas). 0022-5096/$ - see front matter r 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.jmps.2007.12.004

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of SMPs under arbitrary temperature/loading paths. The main constitutive equation (Eq. (21) in Part I) so obtained reads Z t ~ 0 t dt, ^ 1 St; ytF ^ a St; ytf0 yty ^ a St; yt ^ f St; ytF (1) Ft 1 fytF F f
0

where Ft is the average deformation gradient, St the PiolaKirchhoff stress, yt the temperature, fy the ^ a S; y and F ^ f S; y are, respectively, the constitutive functions of the volume fraction of the frozen phase, F ~ active and frozen phases, and yt is the net cooling history obtained by replacing each cooling/heating portion of the original temperature history yt with a constant temperature. In this second part of the paper, we derive a linear constitutive model from Eq. (1) by considering small deformations. This derivation, presented in Section 2, is carried out by following the standard procedure of linearizing the constitutive functions about the zero stress state while leaving temperature as the variable of the linearized constitutive functions. The resulting constitutive equation bears some similarities to that in Liu et al. (2006), and at the same time possesses some differences. The sources and implications of such differences are discussed. In Section 3, the linear constitutive model is further reduced for isotropic materials. The resulting model involves seven scalar constitutive functions: the frozen volume fraction, as well as the thermal strains, Youngs moduli and Poissons ratios of the active and frozen phases, respectively. They are all functions of temperature. The uniaxial tension of such a material is considered, for which the axial and lateral strains can be computed from the histories of the axial stress and temperature. In Section 4, a detailed analysis of using the experimental measurements to calibrate the model is presented. It is found that not all seven constitutive functions can be determined from the experimental data acquired by Liu et al. (2006). However, certain combinations of the constitutive functions can be determined from the experimental data, and such combinations are sufcient to make predictions of the material behavior of the SMP for the same type of experiments. Comparisons of the theoretical predictions and the experimental measurements are presented in the concluding Section 5. Reasonably good agreements are found, which serves as validation of the model.

2. Derivation of a linear constitutive model from the nonlinear theory In the classical theory of mechanics, the innitesimal strain tensor E is used, which is related to the deformation gradient through
T E1 2 F F I.

(2)

The constitutive equation for a thermoelastic material is given by ^ SX; t; yX; t, EX; t E ^ S; y gives the strain in terms of the stress and temperature. For small where the constitutive function E strains, we have the rst order approximation of the constitutive function: ^ ^ S; y E ^ O; y qE O; yS. E qS (3)

The rst term on the right-hand side of Eq. (3) is the so-called thermal strain, and the fourth order tensor in the second term is the elastic compliance tensor. We shall introduce the following notations for these two tensors: ^ O ; y ; Et y E M y ^ qE O ; y . qS (4)

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t For an SMP material, we have two thermal strains Et a y; Ef y and two compliance tensors Ma y; Mf y for the active phase and the frozen phase, respectively. We then have, keeping Eq. (2) in mind, 1 ^ 2Fa S; y 1 ^ 2Ff S; y

^ S; y I E ^ a S; y Et y Ma yS, F a a ^ T S; y I E ^ f S; y Et y Mf yS: F f f (5)

Since the deformation gradient tensor is close to the identity tensor for small deformations, the rst order approximation of Eq. (1) reads ^ a St; yt Ft 1 fytF Z t ~ 0 t dt ^ 1 St; ytF ^ a St; ytf0 yty ^ f St; ytF F f
0

^ a St; yt 1 fytF Z t ~ 0 t dt ^ f St; yt F ^ f St; yt F ^ a St; ytf0 yty F

0

^ f St; yt ^ a St; yt fytF 1 fytF Z t ~ 0 t dt. ^ a St; yt F ^ f St; ytf0 yty F

0

(6)

Here we have used the assumption that the material is initially in the active phase, fy0 0. Now combining Eqs. (2), (5) and (6), we arrive at ^ a St; yt fytE ^ f St; yt Et 1 fytE Z t ~ 0 t dt ^ a St; yt E ^ f St; ytf0 yty E
0 t 1 fytfEt a yt Ma ytStg fytfEf yt Mf ytStg Z t 0 t ~0 fEt a yt Ma ytSt Ef yt Mf ytStgf yty t dt. 0

(7)

Using the terminology in the paper by Liu et al. (2006), we rewrite Eq. (7) as Et Ee t Et t Es t, where Ee t 1 fytMa ytSt fytMf ytSt is the elastic strain,
t Et t 1 fytEt a yt fytEf yt

(8) (9) (10)

corresponds to the thermal strain, and Z t 0 s t ~0 E t fEt a yt Ma ytSt Ef yt Mf ytStgf yty t dt

0

(11)

corresponds to the stored strain. Eqs. (9) and (10) for the elastic strain and the thermal strain are identical to those in the work of Liu et al. (2006). However, the expression for the stored strain given in Eq. (11) has some differences from theirs (see Eq. (8) of their paper), as discussed below.

The integral variable of the stored strain in Liu et al. (2006) is the frozen fraction f, and their expression for the stored strain is valid for cooling processes only. In the present work, the release of the stored strain during ~ in Eq. (11). The present mathematical heating is also accounted for by using the net cooling history y development is in agreement with the following statement (with the present notation) in Liu et al. (2006, p. 299) The change of Es during heating inherits the resultant Es determined previously during the cooling process.

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The integrand of Eq. (11) includes the thermal strains at freezing, which are absent in Liu et al. (2006). The present form reects the idea that the strain, whether it is mechanical or thermal, is being stored during the glass transition. Conceptually, this appears to be consistent with the freezing mechanism of the material, as alluded by the following statement in Liu et al. (2006, p. 291): in addition to the pre-deformation, some of the thermal stress-induced tensile conformational changes are also stored during the cooling process. Of signicant importance is the term Mf ytSt in Eq. (11). This term, absent in Liu et al. (2006), stems from the concept, which has been discussed in detail in Part I Section 3, that a further deformation after freezing should have the frozen state, not the initial state, as the reference conguration. The use of this frozen reference conguration is essential for a consistent theory. As an illustrative example, consider an SMP with constant elastic compliances Ma and Mf , respectively, in the active and frozen phases, as well as zero thermal strains. Suppose that the material is loaded to a prescribed stress S at the initial temperature (in active phase), followed by cooling to the frozen phase while holding the stress constant at S. We then have, during cooling, Z t ~ 0 t dt Et 1 fytMa S fytMf S fMa S Mf Sgf0 yty
0

Ca S.

(12)

That is, the strain remains constant during cooling. This is the expected result when the material is being frozen under constant stress. Without the term Mf S in the integrand of Eq. (12), the strain during cooling would be Ma S fytMf S, implying that the mechanical strain would increase during cooling under constant stress. Liu et al. (2006) conducted uniaxial tension tests of an epoxy SMP and collected a wealth of experimental data. We can determine the constitutive functions of the present model using part of their experimental data, and compare the model predictions with the remaining data. To this end, we shall consider isotropic materials under uniaxial tension in the next section. It is noted that the linear model for isotropic SMPs can be obtained in an alternative way by rst deriving from Eq. (1) a nonlinear model for isotropic SMPs, and then linearizing it for small deformations.

3. Isotropic SMPs, uniaxial tension For an isotropic linear elastic SMP, the elastic compliance tensors Ma y and Mf y are given by Ma yS 1 f1 na yS na ytr SIg, E a y 1 f1 nf yS nf ytr SIg; Mf yS E f y

(13)

where E a and E f are Youngs moduli of the active and frozen phases, respectively, and na and nf Poissons ratios. They are all assumed to depend on temperature. Moreover, the thermal strains of an isotropic SMP are given by
t Et a y a yI; t Et f y f yI,

(14)

t t a y and f y are the scalar thermal strain functions for the active and frozen phases, respectively. Substituting Eqs. (13) and (14) into Eq. (7), we nd that

Et 1 fytft a ytI

1 1 na ytSt na yttr StIg E a yt 1 1 nf ytSt nf yttr StIg fytft f ytI E f yt

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Z
0

t t ft a yt f ytI

1 1 na ytSt na yttr StI E a yt (15)

1 ~ 0 t dt. 1 nf ytSt nf yttr StIgf0 yty E f yt

In a uniaxial tension experiment, the stress tensor has the following component form: 0 1 st 0 0 B C 0 0 A, St @ 0 0 0 0 where st is the axial stress at time t. The corresponding strain tensor has the component form 0 1 t 0 0 B 0 C Et @ 0 l t A, 0 0 l t where t is the axial strain at time t, and l t the lateral strain at t. Substitution of Eqs. (16) and (17) into Eq. (15) yields     st st t t t 1 fyt a yt fyt f yt E a yt E f yt   Z t s t s t t ~ 0 t d t, t f0 yty a yt f yt E a yt E f yt 0     n y tst nf ytst a t t l t 1 fyt a yt fyt f yt E a yt E f yt   Z t n y t s t n y t s t a f t ~ 0 t dt. t f0 yty a yt f yt E a yt E f yt 0

(16)

(17)

(18)

(19)

Eqs. (18) and (19) can be used, among other things, to determine the constitutive functions from uniaxial tension experiments, or to predict the material behavior in a uniaxial tension test once the constitutive functions have been determined. We now turn our attention to this matter. 4. Experimental determination of the constitutive functions. Model prediction Liu et al. (2006) carried out a careful experimental program to calibrate the constitutive model that they developed. In the process, they have made a number of assumptions on the constitutive functions: they assumed that Youngs modulus of the frozen phase is constant, and that Youngs modulus of the active phase is a linear function of absolute temperature. Moreover, they chose an empirical formula for the frozen volume fraction. These assumptions require a prior knowledge of the constitutive behavior of the material and greatly reduce the need of the experimental data, as all the constitutive functions are characterized by a few material constants. In particular, they were able to determine these material constants through curve tting by using the strain recovery data. The stress measurements during cooling were not used at all. Here we attempt to calibrate the present model by using the experimental data obtained by Liu et al. (2006), with a somewhat different methodology. Specically, we do not use the above-mentioned assumptions, and attempt to determine the constitutive functions with full use of the available experimental data. In particular, we used both the stress measurements during cooling and the strain measurements during heating. Also, these measurements in the whole temperature range are fully utilized, since we make no assumption on the form of the constitutive functions. In fact, it is possible to use the current approach to assess the reasonableness of the assumptions made in Liu et al. (2006). For example, by assuming that Youngs modulus of the frozen phase is constant, we can examine to what extent Youngs modulus of the active phase can be approximated as a linear function of absolute temperature, and examine the accuracy of the empirical formula proposed by Liu et al.

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Since no measurements of lateral deformation were made in the experiments of Liu et al., no information on Poissons ratios can be obtained. We thus focus on Eq. (18) which relates the axial stress to the axial strain. t There are ve constitutive functions in Eq. (18), namely, fy; t a y; f y; E a y, and E f y. However, it is found that for the uniaxial tension experiment not all ve functions are independent, in the sense that not all of them can be determined by the experiment, and that not all of them are needed to describe the material behavior in such an experiment. Precisely, three combinations of these ve functions constitute all the information accessible and amenable to the experiment. A possible choice of these combinations is given by the following three constitutive functions:

Overall thermal strain function

t t y 1 fyt a y fyf y

y 0 t t a z f zf z dz.

(20)

y0

Instant elastic compliance function C y 1 fy fy . E a y E f y (21)

Distributed elastic compliance function   1 1 Dy f0 y. E a y E f y

(22)

For an arbitrary temperature history yt with y0 y0 , we have Z t Z y t 0 0 t t ~ 0 t dt t y t  y t f y t y t a f a z f zf z dz.

0 y0

(23)

In virtue of Eqs. (20)(23), we can rewrite Eq. (18) as Z t ~ 0 t dt. t t yt C ytst Dytsty
0

(24)

Eq. (24) indicates that the material behavior of an SMP under uniaxial tension is completely described by the three constitutive functions dened in Eqs. (20)(22). From a practical point of view, it then sufces to determine these constitutive functions in an experimental program. It is obvious from Eq. (24) that the overall thermal strain function t y can be readily obtained by measuring the strain as a function of temperature with zero stress in a cooling or heating process. Fig. 1 shows the experimental measurements of the thermal strain in the temperature range of 273358 K, which is reproduced from Liu et al. (2006, Fig. 4). They measured strains for both cooling and heating, and reported slight difference between the two sets of data. Only the data points for cooling are shown in Fig. 1 with a curve tting to remove obvious experimental scattering. Here and henceforth, we use the smooth tted curves in the calibration of the model. A typical shape memory cycle has been described in Part I Section 5. Relevant measurements in such a cycle were made by Liu et al. (2006). We now discuss determination of the constitutive functions by using their measurements. The rst step of the cycle is loading from zero strain to a prescribed strain pre at the initial temperature y0 358 K. The overall thermal strain is zero. Eq. (24) then becomes t C y0 st. (25)

Fig. 2 shows the stress and strain measurements by Liu et al. (2006, Fig. 3) and a straight line tting to the data points. The linear relation between the stress and strain as indicated in Eq. (25) is seen to hold well. Since

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Fig. 1. Overall thermal strain function.

Fig. 2. Stressstrain relation during initial loading at high temperature y0 358 K.

fy0 0, C y0 is the elastic compliance of the active phase at the initial temperature, and is found to be approximately 8:8 MPa1 . The second step is cooling while the strain is held at pre . It follows from Eq. (24) that Z t t Dytsty0 t dt. (26) pre  yt C ytst
0

Since the temperature is a monotone decreasing function of time in this step, we can rewrite Eq. (26) with temperature being the independent variable: Z y  y  z d z, pre t y C ys Dzs (27)
y0

 is such that where s  yt. st s (28)  y was measured by Liu The temperature reaches y2 273 K at the end of the second step. The function s et al. (2006, Fig. 5), and is shown in Fig. 3.

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Fig. 3. Stresstemperature relation during cooling with constant strain pre 9:1%.

The third step is unloading while temperature is being held at y2 273 K. It follows from Eq. (24) that Z y2 t  z dz. t  y2 C y2 st Dzs (29)
y0

Eq. (29) corresponds to a straight line on the stressstrain diagram, which was measured by Liu et al. (2006). The elastic compliance C y2 of the frozen phase can be found from the slope of this line, and is reported to be approximately 750 MPa1 . The fourth and the last step of the cycle is heating at zero stress. As discussed in Part I Section 5, we again dene st such that stot and that yst yt. Eq. (24) then leads to Z st t t yt Dytsty0 t dt. (30)
0

 such that Dene   yt. t  By using Eq. (28), we can rewrite Eq. (30) as Z y  y t y  z dz.  Dzs
y0

(31)

(32)

y, as measured by Liu et al. (2006, Fig. 6) is shown in Fig. 4. Function  Combining Eqs. (27) and (32), we nd the instant elastic compliance function and the distributed elastic compliance function as C y  y pre  ,  y s 1 d y t y.   y dy s (33)

Dy

(34)

By using Eqs. (33), (34), and the experimental data presented in Figs. 1, 3, and 4, we nd functions C y and Dy. We leave these function as computed without tting them into empirical formulas. Upon substituting them into Eq. (24), we can then predict the thermomechanical behavior of the material in any temperatureloading path. In the next section, we present a few predictions and compare them with the experimental measurements of Liu et al. (2006). Among other things, this provides validation of the linear model.

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Fig. 4. Straintemperature relation during heating with zero stress.

5. Theoretical predictions. Validation of the model The rst set of predictions is for the same types of temperature-loading paths as described above, with different pre-strain levels. In addition to the experiment with pre 9:1%, which is used to calibrate the model, experiments with pre 0 and 9:1% were also carried out by Liu et al. (2006). In particular, for pre 0, the initial loading is absent, and the sample is cooled while being held in its initial length. It is subsequently unloaded at the low temperature, and nally heated at zero stress. For pre 9:1%, the initial loading is compressive, although the stress during cooling changes from compressive to tensile.  y as functions of temperature during cooling for these values of pre-strain are found by The stresses s solving the integral Eq. (27) and using the functions C y and Dy obtained above. They are plotted in Fig. 5 as model predictions, together with the experimental data. Since no approximation is used here, the model prediction for pre 9:1% is exactly the same as the smooth curve obtained from the experimental data through curve tting. Other two curves, on the other hand, provide true comparison of the theory and the experiment. It is observed the theoretical predictions are in reasonable agreement with the experimental measurements.  y After cooling, the sample is unloaded at the low temperature, and then heated at zero stress. The strain   y as previously obtained. The resulting predictions during heating is computed by using Eq. (32), Dy and s y are plotted in Fig. 6. Good agreements with the experimental data are observed. of  Liu et al. (2006) also carried out experiments of different temperature-loading paths than those described above. One such experiment involves the same initial loading and cooling processes, but followed with heating at the pre-strain without unloading. Since the present model asserts full recovery when the material returns to the active phase, the nal heating process will be simply the reverse of the previous cooling process. Indeed, the predicted stresstemperature relations are exactly the same as those presented in Fig. 5. We plot these curves in Fig. 7, along with the experimental data during heating. While the model predictions in Figs. 5 and 7 are the same, the experimental data are slightly different since the material exhibited small hysteresis effects, as commented by Liu et al. (2006). Yet another set of experiments involves the same initial loading, followed by cooling at the xed pre-strain, and unloading at the low temperature. Then instead of heating at zero stress, the specimen is heated at the  y the stress as a function of constant strain fix that has occurred in the end of unloading. Denoting by s  y again the stress as a function of temperature during initial heating, we temperature during heating, and by s nd, using the same arguments leading to Eqs. (27) and (32), that  y fix t y C ys Z
y

 z dz. Dzs
y0

(35)

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Fig. 5. Predictions of the stresstemperature relations during cooling at various pre-strain levels.

Fig. 6. Predictions of the straintemperature relations during heating at various pre-strain levels.

Fig. 7. Predictions of the stresstemperature relations during heating immediately after cooling at various pre-strain levels.

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Fig. 8. Predictions of the stresstemperature relations during heating at constant strain levels after unloading.

 y, we can solve Eq. (35) for s  y. It is expected Using measured t y and previously determined C y, Dy and s that during heating, a compressive thermal stress will rst be developed due to the strain constraint. As the temperature approaches the transition temperature, the level of this compressive stress will decrease as the material becomes more compliant. For the case where the pre-strain is tensile, the stress eventually should turn to tensile from compressive. Such behaviors were observed in both experiments and model predictions, as shown in Fig. 8. However, the agreement between the experimental measurements and model predications is not as good as those in the previous comparisons. Similar discrepancies were also observed by Liu et al. (2006, Fig. 16). This discrepancy could be caused by either the inaccuracy of the model or the inaccuracy of the measurements. We wish to examine the assumptions that Liu et al. (2006) made on the constitutive functions, which greatly simplify the task of calibrating the model. Specically, they assumed that E f y const:; E a y 3Nky, fy 1 1 , 1 cy0 yn (36) (37) (38)

where N is the cross-link density, k Boltzmanns constant k 1:38 1023 N m=K, and c and n are material constants to be determined by experiment. Eq. (38) is an empirical formula, and Eq. (37) follows from a classical theory of rubber elasticity for network polymers. Since the material is much stiffer in the frozen phase, the assumption (36) of Youngs modulus in frozen phase being constant is likely to have a negligible effect on the overall accuracy of the model. As discussed above, these three constitutive functions, when being left in general form, cannot be individually determined by the uniaxial tension experiment. However, if we assume the function form for one of these three constitutive functions, the remaining two can be determined from the experimental data. Here, we take assumption (36), and examine to what extent the constitutive functions E a y and fy as determined by the experiment can be approximated by the functions on the right-hand sides of Eqs. (37) and (38). It follows from Eq. (21) that E f y2 1 , C y2 (39)

where y2 273 K is the temperature at which the entire material is in the frozen phase. We shall take E f y2 as the constant value for E f . We can then solve Eqs. (21) and (22), arriving at Ry 1 Dz=C zC y2 dz fy 1 e yo ; E a y . (40) Ry Dz=C zC y2 dz C y2 C y C y2 e yo

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The constitutive functions fy and E a y are computed from (40), with use of C y and Dy previously determined from the experimental data. It is found that the predicted frozen volume fraction fy can be approximately expressed by the empirical formula (38) with reasonable accuracy. However, the predicted Youngs modulus for the active phase is qualitatively inconsistent with the classical result (37). A number of factors could attribute to this inconsistency, including the accuracy of Eq. (37) itself, reasonableness of the assumption of constant Youngs modulus for frozen phase, accuracy of the experimental data, and accuracy of the model. In concluding this paper, we have developed a nonlinear constitutive theory for SMPs, with a primary goal to describe the large deformations of such materials. A linear model is derived from the nonlinear theory and is examined by using the existing experimental data. The experiments for large deformations of SMPs are being currently conducted. Such experiments can be used to calibrate and validate the nonlinear constitutive models. Also under investigation are the models that incorporate the rate dependent and time dependent behaviors of the material. Acknowledgments We would like to thank Dr. Ken Gall for helpful discussions on an earlier version of this work. The numerical and graphic assistances provided by Liang Li and Joao Paulo Poupard are acknowledged. We also acknowledge the supports of the Texas Institute for Intelligent Bio-Nano Materials and Structures for Aerospace Vehicles, funded by NASA Cooperative Agreement No. NCC-1-02038. Chen wishes to acknowledge the support of ARO Grant 46828-MS-ISP.

Reference
Liu, Y., Gall, K., Dunn, M.L., Greenberg, A.R., Diani, J., 2006. Thermomechanics of shape memory polymers: uniaxial experiments and constitutive modeling. Int. J. Plasticity 22, 279313.

Further reading
Behl, M., Lendlein, A., 2007. Shape-memory polymers. Mater. Today 10, 2028. Bhattacharyya, A., Tobushi, H., 2000. Analysis of the isothermal mechanical response of a shape memory polymer rheological model. Polymer Eng. Sci. 2000, 24982510. Bueche, F., 1954. The viscoelastic properties of plastics. J. Chem. Phys. 22, 603609. Chen, Y.C., Hoger, A., 2000. Constitutive functions of elastic materials in nite growth and deformation. J. Elasticity 59, 175193. Dupaix, R.B., Boyce, M.C., 2007. Constitutive modeling of the nite strain behavior of amorphous polymers in and above the glass transition. Mech. Mater. 39, 3952. Gall, K., Dunn, M.L., Liu, Y., 2004. Internal stress storage in shape memory polymer nanocomposites. Appl. Phys. Lett. 85, 290292. Gurtin, M.E., 1970. An Introduction to Continuum Mechanics. Academic Press, New York. Lendlein, A., Kelch, S., 2002. Shape-memory polymers. Angew. Chem. Int. Ed. 41, 20342057. Liu, Y., Gall, K., Dunn, M.L., McCluskey, P., 2003. Thermomechanical recovery couplings of shape memory polymers in exure. Smart Mater. Struct. 12, 947954. Liu, Y., Gall, K., Dunn, M.L., McCluskey, P., 2004. Thermomechanics of shape memory polymer nanocomposites. Mech. Mater. 36, 929940. Pokrovskii, V.N., 2000. The Mesoscopic Theory of Polymer Dynamics. Kluwer Academic Publishers, Dordrecht. Rao, I.J., 2002. Constitutive modeling of crystallizable shape memory polymers. ANTEC Proceedings 2002, 19361940. Rouse, P.E., 1953. A theory of the linear viscoelastic properties of dilute solutions of coiling polymers. J. Chem. Phys. 21, 12721280. Shaw, M.T., MacKnight, W.J., 2005. Introduction to Polymer Viscoelasticity. Wiley-Interscience, New York. Tobushi, H., Hara, H., Yamada, E., Hayashi, S., 1996. Thermomechanical properties in a thin lm of shape memory polymer of polyurethane series. Smart Mater. Struct. 5, 483491. Tobushi, H., Hashimoto, T., Hayashi, S., Yamada, E., 1997. Thermomechanical constitutive modeling in shape memory polymer of polyurethane series. J. Intell. Mater. Syst. Struct. 8, 711718. Tobushi, H., Hashimoto, T., Ito, N., Hayashi, S., Yamada, E., 1998. Shape xity and shape recovery in a lm of shape memory polymer of polyurethane series. J. Intell. Mater. Syst. Struct. 9, 127136.

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1778 Y.-C. Chen, D.C. Lagoudas / J. Mech. Phys. Solids 56 (2008) 17661778 Tobushi, H., Matsui, R., Hayashi, S., Shimada, D., 2004. The inuence of shape-holding conditions on shape recovery of polyurethane shape memory polymer foams. Smart Mater. Struct. 13, 881887. Truesdell, C., Noll, W., 1992. The Non-Linear Field Theories of Mechanics, second ed.. Springer, Berlin. Zimm, B.H., 1956. Dynamics of polymer molecules in dilute solution: viscoelasticity, ow birefringence and dielectric loss. J. Chem. Phys. 24, 269278.