NTC Project: M05-GT14

Shape Memory Polymer Fibers for Comfort Wear

Fred L. Cook1, Karl I. Jacob1, Malcolm Polk1, Behnam Pourdeyhimi2 1 Polymer, Textile & Fiber Engineering, Georgia Institute of Technology 2 College of Textiles, N. C. State University Goals The four primary goals of the project are: to understand shape memory effects in polymers by experimental and theoretical investigations; to utilize shape memory effects in developing fibers to enhance comfort in apparel by chemical modifications to lower the switching temperature; to seek other applications for shape memory polymers; and to design novel, two-way shape memory fibers. Abstract Although the commodity fiber market is stagnant in the U.S., value-added specialty markets provide a competitive edge for the fiber/apparel industries. Specialty products like Gore-Tex have always kept a steady and substantial market share since their introductions in the latter quarter of the 20th century. By making use of the latest basic science of shape memory polymers, we will design, develop and produce fibers that when formed into fabrics will exhibit superior comfort behavior. As the future U. S. market share is substantial for these niche products, aiding the transformation of the cutting edge research knowledge base to value-added products in shape memory polymers is the primary focus of this work. We are seeking to synthesize polymeric materials with one and two switching temperatures as shape memory polymers. Our initial plans for the syntheses of the shape memory polymers are well defined, and computational simulations will be directed towards enhancing our understanding of the polymeric behavior of these unique materials. Status As the approval to commence fund charging for this Year 1 project just arrived, we are in the process of identifying a student to be recruited for this project from the group entering GIT for the Fall Semester/05. We will have a PHD student identified and working on this project for his/her thesis research within the next month. The initial work strategy is already complete and we expect to make rapid progress once the student has been assigned to the project. Our initial strategies and experimental protocols, both from the chemistry and computational approaches, are already well defined. Objective

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Our objective is to design, engineer and produce fibers with shape memory polymers or shape memory systems for comfort wear. Shape memory metal-alloys that remember the parent shape and return to the parent shape from a temporary shape by the application of heat have been know for sometime. However, the concept of shape memory polymers is a relatively recent invention. Our objective in this work is to use the basic science and developed knowledge base of shape memory materials and structures to design and produce novel fibers for fabrics with substantially improved comfort characteristics. Controlling the changes in fiber cross-sectional shape based on temperature, thereby resulting in desirable thermal and moisture transport characteristics of the resulting fabric, is the focus of this work. Our objectives will be addressed in three steps: first by developing one-way shape memory fibers, then expanding into variable two-way shape memory fibers using bi-component technology, and finally developing fully two-way shape memory fibers by engineering the polymer. Background Shape memory polymers have the capability of changing their shape in response to external stimulus [1]. One of these external stimuli is temperature. Thermoresponsive shape memory polymers consist of two polymer components and resulting two phases, one with a higher melting temperature than the other [1-8]. An excellent review of the shape memory effects in polymers was provided by Lendlein and Steffen [1]. The shape-memory effect is not related to a specific material property of single polymers, but instead is realized from a combination of the polymer structures and the polymer morphologies [1]. The shape memory behavior can be produced with the appropriate structure/morphology combination with significantly different chemical compositions. Shape memory polymer systems, after processing into a form, assume a permanent shape which can be deformed to produce other shapes. First, the polymer system is conventionally processed to receive its permanent shape. Deforming the polymer system to its temporary shape is called programming, which could include cold drawing, deforming, and/or heating [1]. A permanent shape can therefore be stored in the system while it takes the induced temporary shape. Having one permanent shape and many temporary shapes can be defined as a one-way shape memory effect. Of course the temporary shapes can be again realized by mechanical deformation. Most of the shape-memory polymers found in the literature have at least two separate phases, particularly polyurethanes [1]. The phase responsible for the highest thermal transition, such as highest melting point among all the phases, is the basis for the permanent shape. Above this temperature the polymer is completely in the melt state. The glass transition temperature can be also used as a molecular switch for a temporary shape. Entropy elasticity is used to regain the permanent shape [9-22]. Metallic alloys, ceramics and gels can exhibit thermally-induced, shape-memory properties [1]. Transformation from martensitic phase to austenitic phase by change of temperature can serve as the basis for shape memory alloys. Polymer gels can also be used as shape memory polymers, based on their ability to respond to external stimuli (pH, moisture intake, electric field, etc.). Layered gels can be used for two-way shape memory effects. Some of these layered gels show more complex behavior. Most of the shape memory effects are based on the existence of separate phases that will go back to the coiled polymer structure, cross-links, hydrogen bonding, etc. Chains want to go back National Textile Center Annual Report: November 2005

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to the random coiled configuration, while they are constrained in a phase or with permanent or temporary cross-links and partial bonding. The shape-memory transformation depends on the mechanism by which polymer molecules transpose between the constrained formation to random coiled formation. By making use of this change, the shape memory effects can be appropriately engineered. Shape memory polymers are processed by conventional methods to have a permanent parent shape in the molding (or spinning) process. Subsequently these fibers can be deformed to take different temporary shapes at a temperature below that at which the parent shape was formed. For shape memory polymers, the permanent parent shape is stored in the system while the polymer assumes different temporary shapes, and by heating the polymer to a transition temperature the permanent shape can be restored. The phase corresponding to the higher melting polymer component acts as the physical cross-link responsible for the permanent shape. The second component acts as a molecular switch and helps to freeze temporary shapes below the transition temperature, with either the glass transition temperature or the melting temperature serving as the transition/switching temperature. Chemical cross-links can be used as elastomeric shape memory polymers, instead of physical cross-links. Temporary shapes can thus be formed above the switching temperature and can be frozen by keeping the material below the switching temperature, while the permanent shape can be obtained again by heating above the switching temperature. Design of such shape memory polymers are advanced to a level that it is now possible to design and produce specific combinations of properties required for specific applications by slightly varying the chemical composition of the system [1]. Some of the shape memory polymers are biocompatible and biodegradable. Currently, the main applications of shape memory polymers are in the medical field. However, since shape memory polymers are not expensive to produce, their applications could be easily broadened to other areas, e.g., niche textiles, to take advantage of their unique properties. Most of the thermally induced shape memory polymers (SMPs) have a one-way shape memory effect: they remember one permanent shape formed at the higher temperature, while many temporary shapes are possible at lower temperatures for which the systems do not have any memory. A two-way thermally induced SMP will A remember two permanent shapes, one formed at higher B temperature and one formed at lower temperature. By thermally cycling the system, these types of polymeric materials will take two different shapes depending on the temperature. These shape memory systems are engineered at the molecular level for the required behavior. Bi-component fibers with substantially different

Fiber Cross Section: A & B are two polymers coefficients of thermal expansion (CTE) can also (outer and inner components) in a hollow bi produce thermally-induced shape memory effects via component fiber.

one structurally engineering the fiber rather than engineering the polymer. Bi-component fibers also have National Textile Center Annual Report: November 2005

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two distinct phases or layers in this case (the outer and inner component A & B as shown in a hollow fiber in the figure), one with the high CTE component and one with the low CTE phase. The net thermal and elasticity effects on the fiber, resulting from the competition of thermallyinduced expansions, result in the system remembering all of the temperature dependent permanent shapes, and thus providing a multitude of permanent shapes or two-way variable memory effects. Approaches Coolmax and Thermax are two very successful specialty fibers produced by the DuPont Company. These fibers are designed to take advantage of the cross-sectional shapes of fibers for providing comfort at high and low temperatures. While Coolmax has a crescent cross-section capable of better wicking ability, Thermax uses the reduced thermal conductivity of the entrapped air in the fiber for protection from cold weather. The disadvantage of such weatherspecific fabrics make it necessary to have two separate sets of apparel designed specifically for cold or hot weather. Using SMPs, it is possible to design fibers to maximize comfort for all weather conditions. The basic idea is to design a fiber with a crescent cross-section (as in the figure above) such that at higher temperatures the crescent cross-section opens up to form a channel in the fiber as the permanent shape, which closes at lower temperatures to mimic a closed hollow fiber. The fiber thus resembles a hollow fiber at lower temperatures while it opens up to form a channel in the fiber at higher temperatures. By selecting polymers with significantly different thermal expansion coefficients and coupling them with polymers with higher thermal expansion coefficients comprising the inner section, a fiber system very sensitive to temperature changes will be formed. Our calculations and preliminary experiments with polymers support our hypothesis that such systems will be highly thermally sensitive. By perfecting this technology, the same fiber and fiber assembly could retain properties to maximize comfort at high or low temperatures, mimicking the properties of Coolmax and Thermax in a single fiber-garment system. With this approach, the shape memory effect is not restricted to one permanent parent shape that the system remembers, but the geometry and shape for the cross-section of the fiber will be adjusted continuously corresponding to the temperature. These systems will also behave with consistency in repeated thermal cycles, i.e., even after subjecting them to various temperature changes. Our first attempts will be focused on one-way shape memory effects with one permanent shape for fibers retained at higher temperatures. When the temperature is lower, the polymer molecules thus collectively change the existing shape to a new temporary shape, which can be removed by subjecting the fiber assembly to a higher temperature, e.g., by ironing the garment at an elevated setting. We will also attempt to induce a full, two-way shape memory effect with a three phase (three component) material system, in which the cross-sectional geometry required at the high and low temperature ranges will be frozen in a permanent shape. However, before producing two-way shape memory fibers, we will first use bi-component fibers to incorporate one-way and two-way shape memory effects by adjusting the chemistry of the polymer molecules.

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Systems with block polymers of polyethyleneterephthalate (PET)/polyethylene oxide (PEO) and Nylon 6 or 66/ polyethylene are good candidates for shape memory polymers by engineering the chemistry. For our initial work, we will use a block polyester copolymer with PET/poly(oxy1,3-propyleneoxyadipate, POPA). According to Martin in "Synthetic Methods in Step-Growth Polymers," POPA has a melting point of 45C which may be lowered by copolymerization to form a random block system [23]. Block copolymers will be synthesized by two techniques: (1) acyl chloride end capped PET blocks and POPA blocks will be coupled with adipoyl chloride, and (2) acyl chloride-end capped PET blocks will be reacted with hydroxy-end capped POPA. A switching temperature of 45C is ideal for very hot weather; however, by lowering the transition temperature to 40C, the applicability of this polymer system can be extended to ordinary hot weather conditions. By modifying the chemistry, we will thus reduce the transition temperature to 40C for this system. By lowering the switching temperature closer to that of standard room temperature (25C), we can create a polymer fiber system capable of altering the cross-sectional shape and geometry at the switching temperature. A bi-component fiber appropriately designed with a crescent cross-section can produce the desired two-way shape memory effect for producing fibers for comfort apparel. The polymer component with the higher thermal expansion coefficient will be the inner component of the fiber cross section (B in the figure above, equivalent to the core in a solid bicomponent fiber), and the polymer with the lower thermal expansion coefficient will be the outer component of the fiber. The resulting fiber will have a specific geometry at a specific temperature, with a memory of temperature dependent shapes. Such fibers are relatively easy to produce, and the extended memory effects make them very useful in a great variety of weather conditions. This system will form a channel cross section at higher temperatures and approach a closed hollow fiber at lower temperatures. A fabric system with such bi-component fibers will have superior comfort properties at all weather conditions. Humidity can also be used as a factor in determining the temperature, by making use of its plasticity effect. The fiber must be spun such that the crescent cross-section is almost closed when the fiber is formed. When the temperature is increased, the cross-section opens up as the inner component of the fiber expands more, and subsequently closes up as the temperature is decreased. Bicomponent fiber spinning facilities at Georgia Tech will be used for producing fibers with specific shape memory effects and different cross-sectional geometries. As a final step in the project, we will also thoroughly investigate and design a fully two-way shape memory fiber system by engineering the polymer with a three-phase system. This step is more involved as we are seeking a polymer system that can be spun to form shape memory fibers. However, development of fully two-way shape memory fibers will have significant commercial interest. Although substantial progress has been made in synthesizing SMPs, a thorough theoretical foundation is still lacking in the literature on these materials. SMPs are are relatively recent developments, and the nature of structural and morphological interplay between the various phases in the SMP at various temperatures is a complex molecular phenomenon. Relations between crosssectional shape and polymer morphology will be addressed using both continuum and molecular models. Design of the shape and cross section of necessary polymer components to develop a twoNational Textile Center Annual Report: November 2005

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way shape memory fiber system will be theoretically conducted. Design of the appropriate crosssectional geometry of bi-component fiber requires demanding numerical simulations, mainly using Finite Element Analyses. Simulations to study variations of cross-sectional shape with temperature require very involved numerical simulations. We have the computational and software capabilities to conduct such simulations, and they promise to provide basic, fundamental understanding of the material/structural shape memory effects, leading to novel, value-added fibers. In addition to comfort applications, SMPs have direct applications in the military and homeland security. Current use of electroactive materials for parafoils to drop heavy cargo (food, ammunition, heavy equipment, etc.) from planes in regions of combat can potentially also be replaced with SMP fibers. Military applications from this work will be explored particularly to contribute to the efforts in homeland security. Summary We have a well defined work plan to investigate (1) shape memory fibers, and (2) shape memory polymers. We expect to make sufficient progress in the experimental research once a PHD student is identified and assigned to the project over the next month. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] (14) [15] A. Lendlein, S. Kelch, Shape memory polymers, Angew. Chem. Int. Ed., 41, 20342057, 2002. T. Harai, H. Maruyama, T. Suzuki, S. Hayashi, J. Appl. Poly. Sci ., 45, 1449-1451, 1992. T. Harai, H. Maruyama, T. Suzuki, S. Hayashi, J. Appl. Poly. Sci ., 45, 1849-1855. M. Uchida, M. Kurosawa, Y. Osada, Macromolecules, 28, 4583-4586, 1995. X. He, Y. Oishi, A. Takahara, Poly. J., 28, 452-457, 1996. Y. M. Lee, S. H. Kim, C. S. Chao, J. Appl. Poly. Sci ., 62, 310-311, 1996. A. Lendlein, R. Langer, Science, 296, 1673-1676, 2002. M. Brennam, Chem. Eng. News, 79, 5, 2001. K. Nakayama, Int. Polym. Sci. Technol. 1991, 18, T43-48. H. Tobushi, S. Hayashi, S. Kojima, JSME Int. J. Ser. I 1992, 35, 296-302. S. Hayashi, S. Kondo, C. Giordano, Conference Proceedings of the Annual Technical Conference and Exhibition of Plastic Engineers, 1994, 1998-2001. T. Takahashi, N. Hayashi, S. Hayashi, J. Appl. Poly. Sci. 1996, 60, 1061-1069 H. Tobushi, S. Hayashi, A. Ikai, H. Hara, J. Phys. IV 1996, 6, 377-384. B. K. Kim, S. Y. Lee, M. Xu, Polymer 1996, 37(26), 5781-5793. F. Li, X. Zhang, J. Hou, M. Xu, X. Luo, D. Ma, B. K. Kim, J. Appl. Poly. Sci. 1997, 64, 1511-1516. National Textile Center Annual Report: November 2005

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[16] [17] [18] [19] [20] [21] [22] [23]

M. Wang, X. Luo, X. Zhang, D. Ma, Polym. Adv. Technol. 1997, 8, 136-139. X. Luo, X. Zhang, M. Wang, D. Ma, M. Xu, F. Li, J. Appl. Polym. Sci. 1997, 64, 24332440. B. K. Kim, S. Y. Lee, J. S. Lee, S. H. Baek, Y. J. Choi, J. O. Lee, M. Xu, Polymer 1998, 39, 2803-2808. J. R. Lin, L. W. Chen, J. Appl. Polym. Sci. 1998, 69, 1563-1574. J. R. Lin, L. W. Chen, J. Appl. Polym. Sci. 1998, 69, 1575-1586. L. C. Chang, T. A. Read, Trans. AIME 1951, 189, 47.

W. J. Bhler, J. W. Gilfrich, R. C. Wiley, J. Appl. Phys. 1963, 34, 1475. M.E. Rogers and T.E. Long eds., Synthetic Methods in Step-Growth Polymers'', Wiley and Sons, Hoboken, N.J., p.34, 2003. Web page http://www.tfe.gatech.edu/faculty/jacob/ntc/

National Textile Center Annual Report: November 2005