SHAPE MEMORY POLYURETHANE FOR SMART GARMENT

Subrata Mondal*, Jinlian Hu*, Zhuohong Yang+, Yan Liu* and Yau-shan Szeto* * Institute of Textiles and Clothing,The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong + Wuhan Institute of Science and Technology, China ABSTRACT Thermal-responsive shape-memory polyurethane consists of two phases, a thermally reversible phase for maintaining a transient shape and fixed phase structure for recovering the original shape. The use of shape memory polyurethane in clothing is a novel concept. The aim of this paper is to introduce the application of shape memory polyurethane to smart clothing, whose thermal insulation value could be change depending on the change of temperature of the external environment to give comfort regardless of weather change. Thus a review on the shape memory polyurethane is introduced: the mechanism of the shape memory polyurethane is described; the difference between ordinary polyurethane and shape memory polyurethane, the research on shape memory polyurethane and its potential application to smart garment are summarized; the work being carried out in the Hong Kong Polytechnic University are also introduced. Keywords: Shape memory polymer, Shape memory polyurethane (SMPUs), Smart Textile 1. INTRODUCTION

Shape memory is the ability of a material to remember its original shape, the material deformed into a temporary shape and returns to its original shape by external stimuli. The first material known to have these properties were shape memory metal alloys (SMAs) which have been developed in 1960s 1. Shape Memory Polymers (SMPs) are one type of shape memory materials defined as polymeric materials with the ability to sense and respond to external stimuli in a predetermined shape, which were firstly developed in France and commercialized in Japan in 1984. Polymers such as polynorbornene, trans-polyisorprene, styrene-butadiene copolymer, crystalline polyethylene, some block copolymer, ethylene-vinyl acetate copolymer and segmented polyurethane 2-13, 54-56 etc., have been discovered with shape memory effect. Compared with shape memory alloys, SMPs have better potentiality for textile and clothing, and related products: in case of SMAs, mechanical properties can be adjusted only within a limited range and the maximum deformation that can undergo is about 8%. On the other hand, shape memory polymers (SMPs) have easy shaping, high shape stability, and adjustable transition temperature. Shape memory polyurethane (SMPU) is a class of polyurethane that is different from conventional polyurethane in that these have segmented structure and a wide range of glass transition temperature (Tg). If a SMPU is cooled from above Tg to a temperature below Tg, in presence of a mechanical load, and afterremoval of load, significant deformations anywhere in the range of 10-200% get locked into the polymer. These deformations, and the original shape are all recoverable when the

* Corresponding author. Jinlian HU, Email: tchujl@polyu.edu.hk Tel. /Fax No: +852-2766 6437/2773 1432
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polymer is heated back beyond Tg. Both the shape memory effect and the elasticity memory system effect of shape memory polymers make them a useful candidate for todays intelligent material systems and structures 30-31. 2. THE MECHANISM OF SMPU

Shape memory may be triggered by heat, light, electricity and other stimuli. The shape memory polyurethanes to be discussed in this paper are thermo-sensitive SMPUs. SMPUs are composed of incompatible hard and soft segments that demix on a molecular level to form a micro phase separated structure 12-28. The hard micro phase is a hard segment-rich micro domain, which is generally semi-crystalline and imparts stiffness and reinforces to the material. The soft-segment-rich micro phase, which is responsible for the elastic behaviour of polyurethanes, is usually amorphous with a glass transition temperature (Tg) below room temperature. A large, reversible change in elastic modulus across the Tg makes shape change and shape retention possibility.
elastic modulus

Glassy state

Glass transition

Rubbery state

Melting state

Low

Tg

High

Fig. 1. Temperature dependence of elasticity of SMPU

At temperature above the glass transition temperature (Tg), the polymer achieves a rubbery elastic state where it can be easily deformed without stress relaxation by applying external forces over a time-frame t<<, where is a characteristic relaxation time. When the material is cooled below its Tg, the deformation is fixed and the deformed shape remains stable. The pre deformation shape can be easily recovered by reheating the material to a temperature higher than the Tg 55. Therefore; admirable shape-memory behavior requires a sharp transition from glassy state to rubbery state, a long relaxation time, and a high ratio of glassy modulus to rubbery modulus. The micro morphology of SMPU strongly affects its mechanical properties. There are many factors, which can influence this morphology SMPUs: chemical structure, composition, and sequence-length distribution of the hard segments, overall molecular weight and its distribution. 3. THE ORDINARY PU AND SMPU

The properties of ordinary polyurethane (e.g., from 1,6-hexane diisocyanate and 1,4-butane diol) are similar to polyamides. It is composed of two starting material 33, such as, a) diisocyanate and b) either short chain glycol or long chain polyethers or polyester glycol. The PU made by short chain glycol and diisocyanate has multiple hydrogen bonding 35 between NH- and OC- groups, which result in high hardness and strength and low degree of solubility. On the other hand PU obtained by reaction of long chain, non-crystalline,
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unbranched, OH-functional polyethers or polyesters (which do not contain free or low molecular weight glycols) with stoichiometric amounts of diisocyanates contain about 4 to 7 % urethane groups 34. The intermolecular forces for polyethers and polyesters PU are weak van der Waals force, as result, hardness and strength are comparatively low and the product exhibit rubber-like properties. Both types of products have only one phase. The technical importance of ordinary PU is cross linked hard products (PU rigid foams, non-textile coatings). Segmented polyurethanes can show shape-memory properties. Shape memory PU are composed of at three basic starting materials, these are a) long chain polyether or polyester polyol, b) diisocyanate and c) glycol or diamine (chain extender). Diisocyanate and chain extender are hard segment, on the other hand long chain polyol is soft segment. These types of polyurethane are characterized by a segmented structure (block copolymer structure) and the morphology depends on chemical composition and the length of the segment (block). The shape memory polyurethane has micro phase separated structure due to the thermodynamic incompatibility between the hard and soft segment. Hard segments can bind themselves via hydrogen bonding and crystallization, making the PU very solid below melting temperature. Reversible phase transformation of soft segment is reported to be responsible for the shape memory effect. The shape memory effect can be controlled via molecular weight of soft segment, mole ration between hard and soft segment, and polymerisation process 24. The typical textile applications of shape memory polymers are as fibre and coating etc. ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~---------------~~~~~~~~ soft segment hard segment Figure 2: Segmented Polyurethane 4. THE PROPERTIES OF SMPU ~~~~~~~ = long chain diol, = short chain diol, ----- = diisocyanate, = urethane group.

Shape memory effect Ordinary polyurethane cannot completely restore their residual inelastic deformation upon heating. In contrast, SMPUs can recover all the residual plastic deformation up to 400% through a micro-Brownian movement triggered by heating them 10-20C above their glass transition temperatures (Tg). Furthermore mechanisms of shape memory effect, structure, and properties of such polymers have been studied. The shape memory effect of segmented polyurethane is due to the network structure formed by hard and soft block. The hard blocks are formed by the reaction of diisocyanate with low molecular weight glycol, or diamine (chain extender). The hard blocks constitute about 30-50% by weight of the total polymer. On the other hand, soft segments are formed by polyol (oligomer). The microphase separation of these two dissimilar blocks produces regions of hard blocks concentration (domains) which act as cross-link points for the soft blocks. The network structure can be easily deformed above glass transition temperature (Tg) to give a temporary shape, the original shape can be recover when the material heat above the glass transition temperature.

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Permeability Temperature dependency of water vapour permeability is an important factor to be considered for the effective utilization of this type of smart materials. The shape memory effect can be applied to the areas like smart fabrics that can control moisture permeability. The fabrics coated or laminated with SMPU should have higher water vapour permeability at higher temperature and low water vapour permeability at lower temperature 29-32. Other properties When SMPU changed from glassy state to rubbery state, Youngs modulus, tensile and elastic properties would vary greatly, which would be useful for garments. For example, when the SMPU based garments would washed at higher temperature or worn at body temperature, it could recover to the original state (wrinkle free). Other properties, such as wrinkle free, permeability and absorbability can also be considered with SMPU. 5. THE RESEARCH PROGRESS ON SMPU

The shape memory polyurethane can hold more than one shape in memory. Suitable compositions are segmented structure. Shape memory behavior depends on NCO/OH ratio. It has found that the glass transition temperature (Tg) of soft segment slightly increased as the NCO/OH ratio varied from 1 to 1.2, but decreased at 1.3. The enhancement of shape memory properties was not found at NCO/OH = 1.3 43. Lee, et. al 57 have seen that the shape memory effect also depends on the amount of hard segment content. They found that the hard segments get more aggregated to form domains in the PU block copolymer as hard segment increases. 80-95% of shape recovery was obtained at 30-45 wt % of hard segment content, and the control of hard segment content in PU block copolymers is very important in determined their physical properties. Tobushi, H., et. al (Aichi Institute of Technology, Japan) and Hayashi, S., (Mitsubishi Heavy Industries, Ltd., Japan) 44-53 have been studied the SMPU for a long times. They have applied patents 36 about the preparation of SMPU and their application as shape memory foam. They already commercialized shape memory polyurethane (SMPUs) for consumer products such as intravenous canola, spoon and toothbrush handles for handicaps. Polyurethane based on diol-terminated polycaprolactone (PCL diol)/MDI/HDI/chain extender based polyurethanes 7,24-26, 37-42 have effective shape memory effect. The shape memory effect was manifested at reversible phase (PCL phase) rich composition. Polyol with molecular
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weight 500 gm/mole and above resulted in two phase mixed structure of the PU. The extent of phase mixing depended on the cross linking density and hard segment content, as well as the type of polyol. The modification of shape memory polyurethane by hydrophilic segments, diol terminated poly(ethylene oxide) or dimethylol propionic acid (DMPA) enhance different properties. Fatigue 25 in shape memory effect was minimized introducing some amount of DMPA units into the polyurethane chains. The hydrophilic segments increased the hysterisis 38 in shape memory effect by reducing the crystallinity of the hard segment. The neutralize DMPA unit enhanced the sensitivity of the thermo responsive water vapour permeability (WVP) by amplifying the increase of WVP at the temperature range above the glass transition temperature. Chen, et. al 58-61 found that the morphology of soft segment in ester-type polyurethane with different molecular weight of polyol, was in an amorphous state and no crystalline domain was found. By increasing the crosslinked density (varying the content of trimethylol propane, TMP) or decreasing the length of soft segment {MW of poly(butylene adipate)}, the glass transition temperature of studied sample increased. By introducing the chemical crosslinked structure, the deformed samples completely recovered their original shape and rendered shape-memory behavior under the complex deformation. In the Hong Kong Polytechnic University, (Hu, et. al 62-65) carries out the study of the SMPU and their application to textiles. Till date, we have synthesized several kinds of SMPUs and trial for shape memory fabrics. The characteristics of SMPU especially the water vapour permeability have been investigated. Thin films by casting from solutions of polymers where the film thickness is controlled by the solution concentration. The polymer is sticky to the glass plate, so we coat the glass plate with an inactive liquid, for example glycerol or silicone oil. The rollers or doctor knife are pressed into the film and drawn apart. There is no control over the draw ratio or the draw rate. After casting, placed the casting plate inside the oven in order to evaporate the solvent. During the evaporation of solvent, concentration gradient in the film will be produced. Solvent evaporation causes localized cooling at the top that can result in thermocapillary instability within the film solution, and thereby driving convective flows that may result in non-uniform films. The entire system is initially isothermal but is subjected to evaporation-driven cooling at the free surface of the gradually thinning fluid. In this case according to the hydrodynamic stability theory, the free surface of the film will be subjected to disturbances. The disturbances will disappear with time, if the film is stable (below critical condition). They will be amplified with time and will create periodic patterns connected with deformations of the film, if the film is unstable. By controlling the solvent evaporation rate and thickness of the liquid films, the pattern formation in the films, can be controlled. Surface roughness created by thermocapillary instability when the solvent is rapidly evaporating. In contrast, no instability is seen for slowly evaporating solvents, and hence, the surface of the resulting films are always smooth. The films of controlled roughness can thus be obtained simply by varying the solvent evaporation rate. The direct slowly evaporation of the casting polymer solution produced film with a fairly dense and smooth structure. Cast films exhibit a range of morphologies due to the effect of solvents, substrates, orientation, temperature and time. The choice of solvent is quite important for final structure. Spherulites, a common textural structure observed in crystalline polymers. In true thin films, the spherulitic texture is two dimensional, whereas in these thicker films materials the spherulites are three-dimensional. Membrane casting temperature can attribute the shape memory behavior. Sample cast at higher temperature have higher crystallinity and higher
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phase separation than a sample cast at lower temperature. The difference of mechanical properties and shape memory effects due to the difference in casting temperatures is related to the different microstructure 63-64. The clothing and fabrics finished with SMPU showed good shape memory effect and had good wrinkle recovery angle, crease resistance etc. 6. SOME APPLICATION OF SHAPE MEMORY POLYURETHANE (SMPU) IN TEXTILE

Brownian motion occurs when the temperature rises above a predetermined activation point. As a result of this motion, micro-pores are created in the SMPU membrane, which allows water vapour and body heat to escape. Because permeability increases as the temperature rises, the membrane is able to respond intelligently to changes in the wearers body and environment temperature. When the temperature is low, the membrane acts to reduce permeability and prevent the heat and sweat to pass through it. This helps to retain body heat. This flexible barrier function enables the garment to intelligently adjust its insulating properties in response to temperature changes, assuring excellent moisture management properties and increases comfort. So when the shape memory polyurethane is activated in garments, confers greater versatility in the protection the garment provides against extremes of heat or cold. For clothing applications, the reversible temperatures for the shape memory effect to be triggered should be near body temperature. The SMPU can be used with textiles. They can be laminated, coated, filmed, foamed and even straight converted to fibres. The following are the several applications that were reported in the literature: When shape memory polyurethane laminated to a fabric, a smart fabric (waterproof, windproof, and breathable, trademark DiAPLEX,) is formed. It is also possible to coat SMPU on a fabric such that its permeability changes as the wearer's environment and body temperature change to form an ideal combination of thermal insulation and vapor permeability for army clothing. When the body temperature is low, the fabric remains less permeable and keeps the body heat. When the body is in a sweat condition, it allows the water vapour to escape into the air because its moisture permeability becomes very high with increasing body temperature. This releases heat from the apparel. Since the fabric is waterproof, the apparel made with coated or laminated SMPU fabric can be used regardless of weather. Some application of shape memory polyurethane in textile including the followings 65-69: Thermal Protective Clothing Sportswear Leisurewear Under wear Outer wear Gloves Socks
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 7.

Shape memory fibres Smart fabric etc. CONCLUSION

A review about the study of SMPU and their application to textiles were summarized in this review paper. There are many reports about shape memory polymers, although these polymers have been proposed for a number of uses, their textile applications have been limited; due the reversible temperatures for the shape memory effect to be triggered is higher than body temperature. Polyurethane-based shape memory polymers with a wide range of glass transition temperatures drawn interest in the textile field. The study of SMPU is still limited. Their shape memory mechanism, the relation between structure and effect, especially their application to textiles and garments still have potentiality to develop. Considering these factors, we think the study of the following will be interesting and challenging: To develop new shape memory polyurethane. Study on the relationship between SMPU structure, ingredients and properties in function and processing. Develop smart textiles with shape memory functions using SMPU. Establish the method to evaluate the properties and performance of SMPU and smart textiles. REFERENCES 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11. 12. 13. 14. 15. 16. Bardhan, M.K. and Sule, A.D., 2001, Man Made Tex. in India, 44 (3), p.81. Bonart, R. , Morbitzer, L. and Hentze, G., 1969, J. Macromol. Sci. : Phys., B3 (2), p.337. Bonart, R., Morbitzer, L. and Muller, E.H., 1974, J. Macromol. Sci. : Phys., B9 (3), p.447. Chen, L.W. and Lin, J.R., J. Appl. Polym. Sci., 69 (8), (22, Aug., 1998) 1563. Chen, L.W. and Lin, J.R., J. Appl. Polym. Sci., 69 (8), (22, Aug., 1998) 1575. Chen, W., Zhu, C. and Gu, X., 2002, J. Appl. Polym. Sci., 84, 1504. Ding, X.M., Hu, J.L., Tao, X.M. and Hayashi, S., 2001, The 6th Asia Textile Conference, Hong Kong. Funakuba, H., 1987, Shape Memory Alloys, Vol. 1, Gordon and Breach Publisher, New York, Chap. 3. Hayashi, S., 1993, Int. Prog. Urethane, 6, p.90. Hayashi, S., Conference: US- Japan Workshop on Smart Materials and Structures, Seattle, W.A., USA (3-4 Dec., 1995). Hayashi, S., 1992, U. S. Pat., No 5,145, 935. Hidenori, O. and Takao, M., 1993, U. S. Pat., No 5270388. Hirai, T., Maruyama H., Suzuki, T. and Hayashi, S., 1992, J. Appl. Polym. Sci., 45, p.1849. Hu, J.L., Ding, X., Tao, X. and Yu, J., 2001, Textile Asia, 32 (12), p.42. Hu, J.L., Zeng, Y.M. and Yan, H.J., Textile Res. J., in Press. Ikematu, T., Kishimoto, Y. and Miyamoto, K., U. S. Pat., No 5,189,110 (23, Feb., 1993).
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