Materials Letters 89 (2012) 216218

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Shape memory polymer composite structures with two-way shape memory effects
Zhengdao Wang n, Weibin Song, Liaoliang Ke, Yuesheng Wang
Department of Mechanics, School of Civil Engineering, Beijing Jiao-Tong University, Beijing 100044, China

a r t i c l e i n f o
Article history: Received 22 June 2012 Accepted 24 August 2012 Available online 4 September 2012 Keywords: Shape memory materials Thermal analysis Two-way Buckling

a b s t r a c t
Shape memory polymers (SMPs) usually exhibit one-way shape memory effect. A simple and effective way to obtain two-way shape memory effect by SMP composite structures is proposed. The system consists of a SMP lm with higher glass transition temperature Tg surrounded on another SMP cylindrical core with lower Tg. A special thermomechanical process is performed. During this process the mismatched deformation between the SMP lm and cylindrical core intrigues the structure developing from smooth to buckled conguration, and then recovering its original smooth shape. In this study, we conrmed such two-way transition by the theoretical prediction and experimental observation. The means to produce two-way graded shape memory effect is also proposed. & 2012 Elsevier B.V. All rights reserved.

1. Introduction Smart materials and intelligent structure systems are receiving increasing attention due to their great scientic and technological signicance. Shape memory polymers (SMPs) are a new class of smart materials with the capability of keeping a temporary shape and subsequently recovering its original shape. The potential applications of SMPs cover biomedical engineering [1], space deployable structures [2], micro-electromechanical systems [3], etc. Compared with traditional shape memory alloys and ceramics, SMPs have many advantages such as low density, high xture strain, easy processing, wide shape transition temperature and even biocompatibility. Great work has been performed on the fabrication and mechanism researches of SMPs in the past two decades [48]. It is known that shape memory alloys (SMAs) and liquid crystalline elastomers (LCEs) exhibit two-way shape memory effect that reversibly switches shapes without the need of external mechanical manipulation. Most SMPs, however, are one-way. They can only switch from a temporary shape to the original shape, and the transition is not reversible. Recently, SMPs with two-way and multi-shape memory effects are receiving more interests [911]. This paper aims to present a simple method to realize two-way shape memory effect by using SMPs. The structure changes from a smooth composite cylinder to a gear-like shape and reversibly recovers its smooth shape via a special thermomechanical process. Moreover, how to produce two-way graded shape memory effect is also proposed.

2. Analysis and verication As shown in Fig. 1a, a composite cylinder consists of a SMP lm and another SMP cylindrical core with different Tg. The glass transition temperature of the SMP lm (Tg1) is higher than that of the SMP substrate (Tg2). The thermomechanical process includes the following steps: (1) both the lm and substrate are in the rubbery state at the temperature above Tg1, in which the composite cylinder can have a large deformation under the applied load; (2) keeping that deformation and decreasing the temperature to be lower than Tg2, both the SMP lm and core are xed, and thus the compressed deformation is kept even if removing the applied load; (3) reheating and increasing the temperature to be higher than Tg2 but lower than Tg1, the SMP core has a tendency to recover the original state (radial contraction), while the SMP lm still keeps the frozen state. The mismatched deformation leads to the micro-buckling of the structure; (4) when further increasing the temperature to above Tg1, the SMP lm is also unfrozen, the structure reversely recovers its original state. Similar process is in Fig. 1b. The physical mechanism is by using mismatched deformation between the thin lm and underlying compliant substrate to intrigue micro-buckling. The critical buckling and unbuckling expressions are derived in Appendix A. As an example, two epoxy SMPs prepared by epoxy resin E-51 with varying contents of curing agents of 4,4-methylenedianiline (DDM) are employed as the lm and cylindrical core in this study. The mass ratio of E-51 to DDM in the lm and substrate are 100:19 and 100:15, respectively. Fig. 2 shows experimental results of the shape recovery rate and storage modulus of the SMP lm and cylindrical core as functions of temperatures, where we reasonably use the

Corresponding author. Tel.: 86 10 5168 7257; fax: 86 10 5168 2094. E-mail address: zhdwang@bjtu.edu.cn (Z. Wang).

0167-577X/$ - see front matter & 2012 Elsevier B.V. All rights reserved. http://dx.doi.org/10.1016/j.matlet.2012.08.112

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Fig. 1. Schematic illustration of the process of a two-way shape memory composite structure.

100 80 60 40 20 0 320 340

1E10 Substrate Film substrate Film 1E9

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Fig. 2. Experimental curves of the frozen recovery rate and storage modulus vs. temperatures [8].

storage modulus achieved by Dynamic Mechanical Analysis (DMA) instead of Youngs modulus at different temperatures. More information about the material fabrications and behaviors can be referred in [8]. Fig. 3 shows the theoretical results about the dependence of the buckling amplitude on temperatures during heating, where t 0.5 mm, R 10 mm, epre 20%. It is clear that three stages can be obtained. The buckling amplitude is zero in stage I and III. That means the structure keeps the smooth-surface state. The buckling amplitude, however, is not zero in stage II. That means gear-like buckling shape is developed. Moreover, the buckling amplitude increases at rst, and then keeps decreasing in stage II. Moreover, thermomechanical experiments were preformed. Fig. 4 shows the result. The SMP composite cylinder is compressed with an axial pre-strain of 20% at 393 K, and then keeping that deformation and decreasing to room temperature. After that the load is removed and the structure is xed (Fig. 4a). When we heat the specimen to 378 K at the rate of 10 min/K, the local buckling is developed (Fig. 4b), and the buckling amplitude increases with further heating (Fig. 4c). When the temperature is higher than 393 K, the localized buckling is decreased and nally disappeared at 408 K (Fig. 4f). The structure recovers its initial smooth cylinder. It is noted that the theoretical buckling temperatures in Fig. 3 are in the range of 381409 K and the measured values in Fig. 4 are 378408 K. They are in well agreement. Here we theoretically and experimentally conrmed a simple way to obtain SMP composite structures with two-way shape memory effect. More complicated two-way shape memory proles can be spontaneously formed by this technique. For example, Fig. 1b in the above schematically illustrates how to realize twoway graded shape memory effect by employing a SMP conical substrate/lm system.

0.8

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Amplitude (mm)

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0.0 340 360 380 400 420 440

Temperature (K)
Fig. 3. Buckling amplitude as the function of temperatures: no buckling appears in stage I and III, and buckling happens in stage II.

3. Concluding remarks In summary, we proposed an effective and easy-operating way to realize two-way shape memory effect by a SMP composite structure consisting of a SMP lm surrounded on another SMP cylindrical core. The key point is that the shape transition temperature of the SMP lm must be much higher than that of the SMP cylindrical core. The ideal is conrmed by the theoretical prediction and experimental observation. Moreover, a concept design of two-way graded SMP composite structure is proposed.

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Fig. 4. Two-way shape memory effect of a SMP composite cylinder during heating. Localized buckling structures are developed from (a) to (c), and then slowly disappearing from (d) to (f). (a) 298 K, (b) 378 K, (c) 388 K, (d) 393 K, (e) 398 K, (f) 408 K.

Acknowledgement This work was funded by Natural Science Foundations of China (No. 11272044).

where fs and ff are shape recovery rates of the substrate and lm. Both of them are temperature functions. Naturally, buckling happens on condition of s(T) 4 scr. Therefore, substituting Eq. (1) into Eq. (2) the critical buckling condition is obtained as Ef Es 2R2 2Rt t 2 epre fs ff R2 Es 1 uf Ef 1 us 12us 2Rt t 2 2Es 1u2 f !  1=2 ~ s 1=4 Ef E t Z R 3

Appendix A Considering the elastic strain of SMPs in the rubbery state can be up to 100%, linear elastic buckling theory is used in the following analysis. For an isotropic and linear elastic lm/substrate composite cylinder, the critical stress scr, critical buckling wavelength lcr, and the critical wave number ncr are given by [12] !1=4 !  1=2  1=4 ~ s 1=2 Ef E Ef t R scr , lcr 2pt , ~s R t 3 12E !  3=4 ~ s 1=4 R 12E 1 ncr t Ef ~ where Ef Ef =1u2 f , E s Es =12us 1 us ; Ef and uf are Youngs modulus and Poissons ratio of the lm respectively; Es and us Youngs modulus and Poissons ratio of the cylindrical core; R and t the radius of cylindrical core and thickness of the lm. It is noted that Ef and Es are strongly temperature-dependent in SMPs. For the sake of simplicity, we assume that Poissons ratios of both the lm and core are same during the thermomechanical process, i.e. uf us 0.45. When a SMP composite cylinder with radial pre-frozen strain epre is heated at room temperature, the SMP cylindrical core shrinks more quickly than the lm at rst due to its lower Tgvalue. The mismatched deformation causes the increase of compressive stress in the lm, namely

Similarly, when we further increase the temperature above Tg1, the shape recovery rate of the SMP lm becomes quicker, and the mismatched stress is decreasing. The composite cylinder will elastically recover its original unbuckling state on condition of Ef Es 2R2 2Rt t 2 pre fs ff 2 2Es 1uf R2 Es 1 uf Ef 1 us 12us 2Rt t 2

!  1=2 ~ s 1=4 Ef E t R 3

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sT

Ef Es 2R2 2Rt t 2 epre fs ff R2 Es 1 uf Ef 1 us 12us 2Rt t 2 2Es 1u2 f