Shape-Memory Polymer Device Design

encouragement.

Chapter One

Introduction to Shape-Memory Polymers

David L. Safranski,    MedShape, Inc., Atlanta, GA, United States

Abstract

This chapter serves as an introduction to the basics of shape-memory polymers. It details their history and development from radiation cross-linking during the mid-20th century. The key thermo-mechanical properties and how those properties determine the classification of shape-memory polymers are discussed. The stages of the shape-memory cycle and its underlying fundamental mechanism are highlighted as well. A brief summary is given of the four main recovery methods to activate a shape-memory polymer. For clarity and consistency throughout this work, the terminology used in the field of shape-memory polymers is defined. Limitations of shape-memory polymers regarding the activation methods, recovery time, recovery force, and work capacity are also discussed.

Keywords

Shape-memory polymer; shape-memory effect; shape-memory cycle; activation methods; recovery force; shape-memory polymer terminology

Contents

1.1 Introduction 1

1.2 History of Shape-Memory Polymers 3

1.3 Cross-linking, Thermal Transitions, and Shape-Memory Polymer Classification 5

1.3.1 Cross-linking 5

1.3.2 Thermal transitions 6

1.3.3 Classification of shape-memory polymers 8

1.4 Mechanism of the Shape-Memory Effect 8

1.5 Recovery Methods 11

1.6 Shape-Memory Polymer Terminology 13

1.7 Limitations of Shape-Memory Polymers 16

1.7.1 Recovery time and activation methods 16

1.7.2 Recovery force and work capacity 17

1.8 Overview of This Work 19

References 20

1.1 Introduction

Shape-memory polymers are a class of mechanically active polymers that are able to change shape in response to a stimulus. They memorize a permanent or original shape, undergo deformation to store a temporary shape, and then return to their original memorized shape upon exposure to a stimulus. A variety of stimuli may be used for actuation, such as heat, infrared or visible light, solvents, magnetic fields, current, and mechanical force [1–7]. The classic one-way shape-memory cycle has three parts: (1) programming, which is the stage when the shape-memory polymer is deformed from its original state into its temporary shape using a mechanical force often at an elevated temperature; (2) storage, which is the stage when the temporary shape is locked by cooling below the activation temperature and removal of the mechanical force; and (3) recovery, which is the stage when the shape-memory polymer recovers or attempts to recover its original shape. Fig. 1.1 shows the classic one-way shape-memory cycle. An object is heated above an activation temperature, the object is deformed in some manner at this elevated temperature, constrained at this elevated temperature in this new temporary shape, then cooled to store the temporary shape. If released from constraint, then heated, it will recover back to its original shape. If constrained when heated, it will apply a force instead of recovering its original shape. The majority of shape-memory polymers undergo so-called one-way activation, when once the shape-memory polymer is exposed to its stimulus, it returns to its original shape and remains in it. It does not change back to its temporary shape upon cooling, it stays in its permanent shape after recovery and any subsequent cooling.

Figure 1.1 One-way shape-memory cycle with three steps: (1) Programming, (2) storage, (3a) unconstrained recovery or (3b) constrained recovery. Adapted with permission from RSC, Ortega, A.M., et al., Effect of cross-linking and long-term storage on the shape-memory behavior of (meth)acrylate-based shape-memory polymers. Soft Matter 2012;8(28): 7381.

Most current applications of shape-memory polymers use the one-way activation between the temporary and original shapes. There are more advanced chemistries and programming methods that allow for multi-shape recovery and two-way shape-memory cycle, which will be discussed later in Chapters 4 and 5, Programming of Shape Memory Polymers: The Temperature Memory Effect and Triple/Multiple-Shape Memory Effect in Polymers and Activation Mechanisms of Shape-Memory Polymers. While the shape-memory cycle may sound relatively straightforward, there are many factors that can play a role in the performance of shape-memory polymers. Not only will we cover the major concepts of shape-memory polymers, including terminology, polymer structure, and the fundamental mechanism, but we will also focus on engineering design, material selection, and current applications of shape-memory polymers.

1.2 History of Shape-Memory Polymers

The shape-memory effect in polymers is not a modern discovery. In Flory’s Principles of Polymer Chemistry, he introduces the thermodynamics of rubber elasticity with a historical description of John Gough’s third experiment from 1805 [9,10]:

If a thong of Caoutchouc be stretched, in water warmer than itself, it retains its elasticity unimpaired; on contrary, if the experiment be made in water colder than itself, it loses part of its retractile power, being unable to recover its former figure; but let the thong be placed in hot water, while it remains extended for want of spring, and the heat will immediately make it contract briskly…

This experiment shows the fundamentals of the shape-memory effect as we currently understand it. With the introduction of vulcanization by Goodyear in 1844, vulcanized rubber was now heat stable due to the sulfur cross-links and became a staple of everyday use. The first three decades of the 20th century were an important time for polymers. In 1907, Leo Baekeland invented the first synthetic polymer, a thermoset called Bakelite. Then in the early 1920s, Hermann Staudinger proposed that polymers were macromolecules formed from long chains of covalently bonded atoms, not colloidal aggregations of small molecules. Throughout the 1930s, Wallace Carothers and colleagues at the DuPont Experimental Station developed neoprene, polyesters, and nylon, which allowed for numerous products to be made from synthetic polymers. During and after World War II, synthetic polymers with elastic memory came into practical use [11]. Acrylic plastics with elastic memory were used in the construction of aircraft cockpits to replace glass and make waterproof joints [12,13]. The acrylics were heated until soft, shaped around a dome, inserted for placement, and then reheated to secure the seal. Plastic rivets with elastic memory were also patented at this time that would allow for blind riveting [14]. While not termed shape-memory polymers, the same thermo-mechanical cycle was being utilized. Meanwhile, the mechanics and thermodynamic principles behind rubber elasticity were being developed in the mid-20th century by Guth, Treloar, and Flory [15–17].

With the development of polymer cross-linking via irradiation, Charlesby described the memory phenomenon as an interesting and often amusing property of lightly irradiated polyethylene [18]. The first major application of shape-memory polymers was heat-shrink tubing by Paul Cook at RayChem Company in the late 1950s [19,20]. RayChem initially started with cross-linking polyethylene, but now many polymers, such as polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), and polyvinylidene fluoride (PVDF) are available as heat-shrink tubing. At the same time, George Odian and colleagues at Radiation Applications, Inc. developed deployable space structures from cross-linked polyethylene in the early 1960s for NASA [21,22]. While the terminology in their studies may have been different, they explored some of the critical aspects of the shape-memory cycle. At that time, the term elastic memory or memory effect was used to describe the recovery process along with a crystalline clutch mechanism was used to describe shape fixity, but the inherent process was the same as today [21,23]. A polymer, lightly cross-linked semi-crystalline polyethylene, was deformed above the melting temperature of the polyethylene crystals. The deformed part was cooled into a new stable configuration because of recrystallization locking the new shape, and the part could return to its original geometry upon heating. Fig. 1.2 shows the effect of radiation dosage and recovery temperature on the recovery of cross-linked polyethylene that was programmed with a 180° bend at 80°C [21]. At the time, it was known that cross-links and melting/recrystallization transition were involved in this ability to hold a temporary shape and recover the original shape.

Figure 1.2 Effect of cross-linking radiation dose on shape-recovery (as measured from a 180° bend) of cross-linked polyethylene. Adapted with permission from Odian, G. and B.S. Bernstein, The Use of Radiation-Induced Plastic Memory to Develop New Space Erectable Structures. 1963, NASA: NY.

Over the course of the next several decades, the elastic memory term from the field of radiation cross-linked polymers was still being used to describe this phenomenon. Unfortunately, few research studies were performed in this area after the initial studies in the 1960s, but industrial applications were being explored as evidenced by the patent literature on heat-shrinkable or heat-recoverable products and methods of joining plastics. During the 1960s, NiTi, also known as Nitinol from Nickel Titanium Naval Ordnance Laboratory, was gaining in popularity as well as the term shape-memory effect to describe the behavior of NiTi and similar mechanically active alloys [24]. In the late 1980s and early 1990s, researchers in Japan, especially at Zeon, Co., Asahi, Co., and Mitsubishi Heavy Industries, Ltd. explored shape-memory polymers for a variety of commercial applications using polynorbornenes and polyurethanes [25–28]. It was during this time that the use of the term shape-memory was used to describe polymers with elastic memory, even though the inherent mechanisms of shape change are distinctly different between shape-memory alloys and shape-memory polymers. Starting in the mid-1990s, academic interest in this field dramatically grew, and started to focus on the underlying mechanics primarily for both biomedical and aerospace applications.

1.3 Cross-linking, Thermal Transitions, and Shape-Memory Polymer Classification

1.3.1 Cross-linking

Polymers have a variety of structures, including linear, branched, and network, depending upon the types of monomers that make up its composition (Fig. 1.3). Polymer networks are formed when the polymer chains are either physically or covalently linked together, preventing permanent chain displacement. This restricts the mobility of the chains, forms permanent netpoints, and sets an original shape for the shape-memory polymer. Cross-linking is most readily achieved through exposure to heat and a cross-linking molecule or exposure to a radiation source (UV light, gamma, electron beam) [1,21,29–32]. The cross-linking is termed chemical cross-linking when covalent bonds form the links between the molecules (e.g., epoxies or methacrylate networks). The cross-linking is termed physical cross-linking when physical interactions such as phase separation, hydrogen bonding, or physical entanglements form the links between the molecules (e.g., thermoplastic polyurethanes). Cross-linking is typically quantified by the cross-linking density. The cross-linking density is determined from the modulus in the rubbery regime from classic rubber elastic theory, Eq. (1.1) [33]

(1.1)

where E is the elastic modulus, R is the universal gas constant, T is the temperature in Kelvin, and ν is the cross-link density.

Figure 1.3 Schematic of polymer structures. (A) Linear, (B) branched, (C) lightly cross-linked, (D) highly cross-linked.

1.3.2 Thermal transitions

The glass transition is not considered a first-order phase transition, but a kinetic phenomenon or a second-order transition. The glass transition is a temperature range over which the amorphous regions change from a brittle glassy state to a flexible rubbery state as they are heated. Below the glass transition temperature, the polymer structure is glassy and rigid with limited molecular motion. Above the glass transition temperature, the polymer structure is mobile and large-scale molecular motion is possible. The glass transition is often measured with three techniques: Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and thermomechanical analysis (TMA). For DSC, a step change occurs in the heat capacity of the polymer during the glass transition. For DMA, a dramatic decrease in storage modulus signifies the onset of the glass transition or the peak of the tan delta is often used to represent the glass transition temperature, even though the glass transition occurs over a temperature range. For TMA, a change in volume or a change in the coefficient of thermal expansion occurs when heating through the glass transition. For shape-memory polymers, this rapid increase in viscosity (~10¹² Pa·s) and modulus during cooling through the glass transition serves to lock in the temporary shape. The glass transition temperature for shape-memory polymers can vary widely depending upon chemical structure and compositions, where the glass transition of (meth)acrylates ranges from −23°C to 112°C [34]. Further discussion of the theory of the glass transition can be found elsewhere