SHAPE MEMORY POLYMER

1. INTRODUCTION: Materials that respond dynamically to environmental stimuli can be called intelligent or smart materials. They have significant potential applications in various fields. Whether smart materials are responding in an adaptive way is questionable A very smart adaptive response is exhibited if the materials/material systems are able to respond dynamically to a number of input stimuli and if this response is repeatable. The term very smart also refers to materials that can (1) Respond reversibly to the changes in the surrounding environment and (2) Contribute an optimal or useful response by either changing its physical properties, geometry, mechanical properties, or electromagnetic properties Shape memory materials (SMM) are able to sense a change in temperature and react by changing into a prescribed shape [1]. SMM have additional properties, which include pseudo elasticity or recoverable stroke (strain), high damping capacity and adaptive properties, which are due to the ability to reverse the transformation during phase transitions. The materials deform into a temporary shape and returns to its original shape by external environmental stimuli such as chemicals, temperature, or pH. Shape memory materials are stimuli-responsive materials. Shape memory materials (SMM) are able to sense a change in temperature and react by changing into a prescribed shape. There are a variety of physical changes that SMM can sense in their environment, including thermal, mechanical, magnetic or electric. These physical factors are able to simulate the shape memory effect (SME) enabling them to respond and transform into a prescribed shape, position, strain, stiffness, natural frequency, damping, friction and other static and dynamic characteristics of material systems.

1.1 FEATURES OF THE SHAPE MEMORY POLYMER: A sharp transition that can be used to promptly fix the secondary shape low temperatures and trigger shape recovery at high temperature. Super elasticity (high deformability) above the transition temperature to avoid residual Strain (permanent deformation). Rapid fixing of temporary shape by immobilizing the polymeric chains without creep. SMPs possess two material phases. The glass and the rubber phases. In the glass phase, the material is rigid and cannot be easily deformed. When the temperature is greater than "Glass transition temperature", the material enters the soft rubber phase and becomes easily definable

1.3 CLASSIFICATION OF THE MATERIALS SHOWING SHAPE MEMORY EFFECT SMM can be seen in a variety of materials such as alloys, ceramics, polymers and gels. These have been explored and developed as they demonstrate SME behavior [1-3]. These materials have also been commercially developed as they are a part of some consumer products [4]. 1.3.1 1.3.2 1.3.3 1.3.4 Shape memory alloys (SMA) Shape memory Ceramics Shape memory polymers Shape memory gels

1.3.1 Shape memory alloys (SMA) : The most prominent and widely used shape-memory materials currently are shape-memory alloys (SMAs). Their shape-memory effect stems from the existence in such materials of two stable crystal structures: a high temperature favored austenitic phase and a low temperature-favored (and yield-able) martensitic phase. Deformations of the low temperature phase, occurring above a critical stress, are recovered completely during the solidsolid transformation to the high temperature phase. This shape-memory effect witnessed by SMAs is considered to have been first observed in a AuCd alloy by Chang and Read in 1951[5]. The discovery of the shape memory effect in the equi atomic nickel titanium alloy (NiTi, Nitinol1) in 1963 led to greatly enhanced interest towards commercial applications due to the combination of a desirable transition temperature close to body temperature, super elasticity, biocompatibility, and a so-called two-way shape-memory capability.[6-9] 1.3.2 Shape memory Ceramics:
Certain Zro2 ceramics undergo a transition from tetragonal to monoclinic structure like a martensitic transition thermally off by the application of stresses. These ceramics are called Martensitic Ceramics.

1.3.3 Shape memory polymers (SMPs): The polymers which exhibit shape memory effect is called shape memory polymers. The mechanism of shape memory polymers is entirely different from that of shape memory alloys. The shape memory polymers depend largely on the glass transition temperature for the shape memory effect. They can be stimulated by temperature, pH, chemicals, and light, and are defined as polymer materials with the ability to sense and respond to external stimuli in a predetermined way. [10] 1.3.4 Shape memory gels: Another class of polymers possessing shape-memory properties are shape-memory gels. These materials are usually more flexible than shape-memory rubber and are best represented by y. Osadas work from hokkaido university in japan.[1114] Analogous to shape memory rubber, a typical shape-memory gel is a cross-linked material having a hydrophilic fraction that can be swelled in water and hydrophobic sections with reversible orderdisorder structures controlled by temperature. While cross-linking sets the permanent (high temperature) shape, the ordered structure that forms at temperatures, T , Tcritical, can be used to fix secondary shapes established by deformations at higher temperature, T . Tcritical. Heating above Tcritical then triggers quite complete shape recovery

1.4

ADVANTAGES OF SHAPE-MEMORY POLYMERS:

Compared with shape-memory alloys, polymeric shape memory materials possess the advantages of high elastic deformation (strain up to more than 200% for most of the materials), low cost, low density, and potential biocompatibility and biodegradability. They also have a broad range of application temperatures that can be tailored, tunable stiffness, and are easily processed. These two materials (polymers and metal alloys) also possess distinct applications due to their intrinsic differences in mechanical, viscoelastic, and optical properties. A comparison of the different characteristics of SMPs and SMAs is summarized in Table 1

Table no 1: Properties of SMP and SMA Property Density in g/cm3 Extent of the deformation (%) Youngs modulus at T< T(tran.)/GPa Youngs modulus at T> T(trans) GPa Biocompatibility ad biodegradability Shape memory polymer 0.9-1.1 Up to 800% .01-3 (0.1-10) 10-3 Can be biocompatible/ biodegradable Shape memory Alloy 6-8 <8% 83(NiTi) 28.41 Some are bio compatible not biodegradable

2. SHAPE MEMORY POLYMER

2.1 PRINCIPLE OF SHAPE MEMORY POLYMER: The polymer materials have various elasticity from hard one like a glass to soft one like a rubber. The shape memory polymers, however, have the characteristics of both of them, and its elasticity modulus shows reversible change with the glass transition temperature (here after called tg) as the border. The dependence of the elasticity modulus to the temperature is shown in figure1. The shape memory polymers, when heated above Tg, get as soft as rubber and are easy to change the shape, and when cooled below Tg, it retains the shape intact (shape fixing characteristic). When heated up again above Tg, the material autonomously returns to the original shape (shape recovery characteristic). The material property which is repeatedly returning back to the original shape is called shape memory." [16]

Fig. 1 Principle of shape memory polymer

2.2 WAYS OF ACTIVATING SHAPE MEMORY POLYMER: 2.2.1 Thermo responsive shape memory polymers 2.2.2 Electrical heating induced shape memory effect 2.2.3 Light induced shape memory polymers 2.2.4 Magnetically induced shape memory effect 2.2.5 Water activated shape memory effect

2.2.1 Thermo responsive shape memory polymers The shape memory polymers which change in shape with the change of temperature are called thermo responsive shape memory polymers. By far these are the most common shape memory polymers. [17]

2.2.2 Electrical heating induced shape memory effect The shape memory polymers are generally not conducting. So they are made Conductive by blending with carbon Nano powders. The electric current is converted into heat. They recover the original shape when an electric current is passed through the shape memory polymers.[17]

2.2.3 Light induced shape memory polymers The shape memory polymers which are to be activated by light should have some photo sensitive groups which act as molecular switches. The shape memory polymers are stretched and illuminated by a light of wavelength greater than a fixed wavelength and the photosensitive groups form cross links .The polymer is locked in the new shape and retains the temporary shape even when the stress is released. When this is illuminated by a light of lower frequency, the cross linking cleaves allowing the material to go back to its original state [18]

2.2.4 Magnetically induced shape memory effect Non-contact triggering of shape changes in polymers has been realized by incorporating magnetic nanoparticles in shape memory polymers and inductive heating of these compounds in alternating magnetic fields. Magnetic nanoparticles having an iron (III) oxide core in silica matrix could be incorporated into the shapememory polymers. [17-18]

Fig. 2: Sequence of photographs showing the shapememory polymer (black strip) changing to its permanent shape in the presence of an alternating magnetic field

2.2.5 Water activated shape memory effect The Actuation of the polymer can be achieved by immersion in water. A shape memory polymer which has the permanent shape of a straight rod is programmed into a Z shape . The left part of the polymer is dipped into water and the right part is not dipped . There is a reduction of the glass transition temperature for the left part and it gets actuated ie gets back to its original form with the help of the room temperature water itself. [19]

Fig.3 Recovery of functionally gradient SMP actuated by water in a sequence

Fig.4 Appearance recovery in magic mirrors (the appearance of an old woman recovers to her young appearance in a magic mirror)

2.3 Structure and mechanism of SMPs The common conventional SMP systems include cross-linked PE [20] and PE/nylon6 graft copolymers [21], trans-polyisoprene (TPI) [22], cross-linked ethylenevinyl acetate copolymer [23], styrene-based polymers [24,25], acrylate-based polymers [26], polynorbornene [27], cross-linked polycyclooctene [28], epoxy-based polymers [29], thio-ene-based polymers [30], segmented polyurethane (PU) [31], and segmented PU ionomers Additionally, some new biopolymers, such as poly(3-hydroxyalkanoate)s (PHAs) copolymers composed of dodecanedioic acid or sebacic acid monomers[5557] and bile acid-based polyesters [58], have been developed to exhibit SME, but their shapememory or mechanical properties are not highly desirable and require further optimization.

Fig.5 The molecular models of thermally induced SMEs for cross-linked PE and different systems.[20] Fig.5 demonstrates the progress of representative models developed for thermal-sensitive SMPs. For example, in chemically cross-linked semi crystalline PE, the crystalline phase with a crystal melting temperature (Tm) is used as a switch unit to provide the shape fixity capacity [20]. The chemically cross-linked PE network memorizes the permanent shape after deformation upon heating. Subsequently, the general molecular mechanism of thermally induced SMPs was proposed (Fig. 5b) in which the network structure is either chemically or physically cross-linked and the switch units are made from a semi crystalline or amorphous soft phase. If the increase in temperature is higher than Ttrans of the switching segments, these segments are flexible

(shown in red) and the polymer can be deformed elastically. The temporary shape is fixed by cooling down below Ttrans (shown in blue). If the polymer is heated up again, the permanent shape is recovered. An elastomer /polymer will exhibit shape-memory functionality if the material can be stabilized in the deformed state in a temperature range that is relevant for the particular application. This can be reached by using the network chains as a kind of molecular switch. For this purpose the flexibility of the segments should be a function of the temperature. One possibility for a switch function is a thermal transition ( Ttrans) of the network chains in the temperature range of interest for the particular application. At temperatures above Ttrans the chain segments are flexible, whereas the flexibility of the chains below this thermal transition is at least partly limited. In the case of a transition from the rubber -elastic or viscous state of the glassy state, the flexibility of the entire segment is limited. If the thermal transition chosen for the fixation of the temporary shape is a melting point, strain -induced crystallization of the switching segment can be initiated by cooling the material which has been stretched above the Ttrans value. The crystallization achieved is always incomplete, which means that a certain amount of the chains remains amorphous. The crystallites formed to prevent the segments from immediately reforming the coil -like structure and from spontaneously recovering the permanent shape that is defined by the net points. The permanent shape of shape -memory networks is stabilized by covalent net points, whereas the permanent shape of shape -memory thermoplasts is fixed by the phase with the highest thermal transition at Tperm. The molecular mechanism of programming the temporary form and recovering the permanent shape is demonstrated schematically in Figure 4 for a linear multi block copolymer, as an example of a thermoplastic Shape-memory polymer, as well as for two covalently cross -linked polymer networks. This expression describes the property of an elastomer one would not expect in an amorphous polymer chain. The memory effect represents a problem in the processing of non vulcanized natural rubber. In the case of a quick deformation of the amorphous material of a sudden subsequent decrease or removal ( or reduction) of the external force, the polymer re -forms its original shape. Such polymers will also exhibit a shape -memory effect if a suitable programming technique is applied. In this case, temporary entanglements of the polymer chains which act as physical net points can be used for the fixation of the permanent shape. This thermal transition can be used as a switching transition if the glass transition of the amorphous material is in the temperature range that is relevant for a specific application.

2.4 Draw backs of shape memory polymers: A significant drawback of shape memory polymer is because of the relatively low stiffness values.A low stiffness value indicates a relatively small value of the recovery force under constraint. But adding reinforcements help in overcoming the drawbacks . They allow us to tailor the material stiffness. Fiberglass and Kevlar reinforcements increased the stiffness of the SMP resins and reduced recoverable strain levels. Moreover, discontinuous fiber reinforced composites showed shape recovery in all directions, while continuous fiber reinforced composites only showed recoverability under transverse tension or bending The addition of Nano particulate SiC reinforcements increases both the hardness and elastic modulus of the base resin material. The increase in both of these material properties is a direct consequence of the relatively high hardness/modulus of the SiC particles relative to the polymer matrix. The hardness and modulus increases are directly proportional to the weight fraction of SiC. The hardness and modulus of the composite material can be tailored for a given application by altering the weight fraction of the SiC, or using alternative reinforcement materials/architectures

3. APPLICATIONS OF SMPS Shape memory polymers find its application in various fields due to its special and unique properties 3.1 Shape Memory Fabric : The shirt with long sleeve could be programmed so that the sleeves shorten as room temperature becomes hotter. The fabric can be rolled up, pleated, creased and returned to its former shape by applying heat. Ex: blowing air through hair dryer. 3.2 Ergonomic: The violin is made from the combination of shape memory polymer and carbon fibers. The shape memory polymer used here is "Veriflex". It's designed to help reduce the neck and shoulder pain of the player, as it can be reshaped as desired by the player. 3.3 SI Suits: The suit was developed to help the sailors on the oceans and sea. It adapts to the temperature variations and maintains a person's body temperature constant. The membrane gives optimal breathability in any given atmospheric condition. 3.4 Morphing aircrafts: Developing and demonstrating morphing materials and technologies that are necessary to construct deployable Morphing aircrafts and other innovative adaptive structures critical to air force are taking place. 3.5 For selfTightening sutures Shape memory polymers are very useful as self tightening sutures . In general the sutures are to be stitched very carefully. They may damage the cells of the skin if the threads are stitched very tight .on the other hand , if the threads are too loose , it does not do the required function .The shape memory polymers if used , the threads can stitched loosely and when the threads come into contact with the body , because of the body temperature , it contracts to tighten it to the just required force

Fig.6 the suture are getting tightened as the temperature reaches the body temperature

3.6 Bard backs smart fibers for surgery: Shape-memory polymers have the potential to completely revolutionize medical surgery, as well as having a broad range of other applications, and the first product developed by the name Science was smart suture that ties itself into the perfect knot. This means that potentially, surgeons will be able to seal hard -to-reach wounds with the aid of a shape -shifting thread that knows how to tie itself and never needs to be removed. The new smart biodegradable plastic fiber cannot itself when heated to a few degrees above body temperature. Researchers believe the same material could be made to last much longer and one day be used for self-repairing medical devices and also to shrink otherwise bulky implants such as screws that hold bones together.

3.7 APPLICATION OF THE SHAPE MEMORY POLYMER IN THE TEXTILE SMPs can be made in the form of fibers (macro, micro and Nano fibers) [3235], solutions [36,37] films [38,39] and foams [40,41] for further textile and apparel applications, such as non-woven materials coatings finishing lamination weaving and knitting The following provides the current status of SMP applications to textiles. 3.7.1 SMP macro fibers Significant progress has been made in the manufacture of textile fibers from shapememory polymers through common spinning methods. It is easy to make a polymer fiber, as long as the polymer has adequate molecular weight, sufficient viscosity or a suitable melting point, but it is difficult to make a fiber for textiles. The durability, elongation, tactile properties and process ability of fibers are the main factors that influence their final end uses. SMP fibers include micro fibers, Nano fibers and non-woven. [42-45] 3.7.1.1 Properties of SMFs: Macro scale SMFs can be made by wet, melt and dry spinning Compared with other traditional chemical fibers, particularly elastic fibers, shapememory fibers (SMFs) are unique because their elastic modulus changes within a specified utilization temperature range, and they exhibit a recovery ability with an external stimulus Their molecular orientation, recovery stress, hard-segment micro domains and post-treatments were also studied Fig. 7 compares the change in modulus under increasing temperature, which shows that the SMF is superior, with better temperature response performance than spandex, nylon, XLA (olefin-based fiber product of Dow company), etc. Fig. 8 compares the stressstrain curves of shapememory fibers and other fibers, and the curves of shapememory fibers are between those of spandex and nylon fibers.[46]

Fig 7 Comparison of the elastic modulus between SMPU fiber and existing man-made fibers.

Fig.8 Stressstrain curve comparison of different fibers Up to now, a series of shapememory fibers have been developed with variable mechanical property range, shapememory fixity, recovery and switch temperature range, which allow for diversified textile designs. Because textile processing includes dying, finishing, and heat-setting, shapememory fibers should have antioxidant, anti-thermal, chlorine-resistant and anti-aging properties, which present challenges for the production of commercially viable SMFs. 3.7.1.2 Novel and functional SMFs Melt spinning also provides an efficient method to prepare fibers with various profiles and functionalities. A new SMPU hollow filament with a thermal-sensitive internal diameter via melt spinning, as shown in Fig.9 [47]. Additionally, another electro-active SMFs by incorporating MWCNTs [48] and Temperature-regulating fibers made of PEG-based smart copolymers [49].

Fig.9 Thermally adjustable internal cavities of hollow SMFs (deformed by transverse pressing, a original shape; b deformed shape; c recovered shape).

3.7.1.3 SMF yarns, fabrics and garment design: The appeal of the application of SMFs to textiles is their shape fixity and lengthwise recovery along the fiber, accompanied by changes in their stress. SMFs have been made into yarns by ring and friction spinning techniques, and the yarns have been applied to the knitting and weaving of fabrics. [50]

3.7.2 SMP solutions for finishing fabrics Alternatively, an SMP solution has been directly used as a finishing agent to obtain valuable properties in different types of textile fabrics, such as cotton or wool. Another method for producing shapememory fabrics is shapememory finishing, which is a process that transfers the shapememory properties from polymers to fabrics. Compared with the shapememory fabrics knitted or woven with SMFs, a small content of SMP is sufficient to transfer the SME to the fabric during shapememory finishing. This process is highly efficient.[4547]

Fig.10 Wrinkle recovery mechanism of shape memory fabric finished with SMPs

In Fig.10, wrinkles and damaged creases of a fabric treated through shapememory finishing recover back to their original flat and creased form when the temperature is raised to or above the transition temperature of the SMP. The typical shapememory effects of a fabric are shown in Fig.11.

Fig11 Typical shape memory recovery effects of shape memory finished fabrics

3.7.3 Smart Fabrics Based on NiTi SMA: Figure12(a) illustrates the shape memory recovery of smart textile having the trained two - way NiTi SMA Spring varied with temperature. The shape of the smart fabric will vary as the trained SMA is deformed and spring back to the original shape.

Fig.12 Shape Memory Recovery of Smart Textile Having a Trained SMA spring with a thermo mechanical
training process

In this case, the smart fabrics can display two-way shape memory effect when the spring is trained for two -way SME with a thermo mechanical training process shown in Figure (b). The effect of annealing temperature on SME is related to the change of internal stress fields and the anisotropic distribution of dislocation, as well as the states of parent phase due to shape and disperses degree of Ti3Ni4 precipitates. This dislocation structure creates an anisotropic stress field in the matrix, which guides the formation of marten site phases into variants of preferential orientations in relation to the deformation adopted in the training procedure, thus resulting in a macroscopic shape change during subsequent thermal transformation cycles.

Fig.13: Examples of shape memory fabrics after shape memory training

Figure13 illustrates some complex examples of the trained shape memory texture structure of SMA, by a set of designed clamping devices. For SME training of the SMA fabric, initially SMA woven samples, covered with these clamp devices, are heated in an oven for an appropriate thermo mechanical training process when kept with the binder, and then quenched in water. The shape of the SMA woven fabric could be transformed from an initial predestined state at a low temperature, into a trained coil state at a high temperature, with a high rate of shape recovery rate. 3.7.4 SMP films, foams and laminated textiles Shapememory films and foams have a number of applications in laminated smart fabrics [51]. The functions of SMP films applied to textiles include waterproofing, WVP, seam sewing, crease recoverability and crease fixing. To optimize these effects, various properties of SMP films have been investigated, such as their thermomechanical properties, the effects of different structural factors on their physical and water vapor transport properties [39,51-52], their molecular weights [53] the effects of crystal melting and the influence of different processing temperatures. 3.7.4.1 Water vapor permeability of SMP films WVP is one of the significant adaptive parameters of thermal-induced SMP films, which enables broad applications that include textiles. SMPUs have become good candidates for breathable laminated nonporous fabrics due to the sensitivity of their WVP to temperature and humidity. The WVP properties of SMPUs with an amorphous reversible phase, and water vapor permeable fabrics were prepared by coating the SMPU membranes on a fabric substrate.

3.7.4.2 Applications in breathable textiles: A higher comfort level can be achieved using shape memory polymer coated garments. By coating with shape memory polymers like shape memory poly urethanes, we can control the permeability to a large extent. we can have a high water vapour permeability at a higher temperature and a lower water vapour permeability at a lower temperature, thus making it useful to be used in both the conditions .This allows it to be used for breathable textiles. The polymer forms a thin layer of non porous surface on the fibres .so the water vapour permeability would be a three step mechanism of sorptiondiffusiondesorption mechanism. The water vapour molecules would be absorbed onto the polymer surface and then the diffusion takes place, finally the water molecules are desorbed out of the surface because of the concentration differences with the environment. At the crystal melting point of the soft phase, the micro Brownian motion of the soft phase would occur. This leads to discontinues changes in the density and provide enough gaps for the water vapor molecules to pass through. 4. FUTURE OUTLOOK SMPs represent a class of smart polymeric materials with a variety of chemical compositions, mechanisms and mechanical responses. SMPs has Accelerated growth in research activities and New SMPs with novel structures and diversified functionality. No of significant progress in enabling SMP technologies, such as materials, processes, and techniques; however, these application successes remain limited. Innovating the integration of all or major functions in practice is worth our concerted effort. As for the distinctive weak points, such as low recovery stress, we must look for new technologies to produce more powerful materials. While we cannot be unreasonable in our expectations for the near future, the existing problems can be overcome by finding more innovative applications that exploit the existing features and capacity of SMPs. This goal requires tremendous creativity and sharp vision as well as investment

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