This article was downloaded by: [University of Akron] On: 21 April 2009 Access details: Access Details: [subscription

number 789280516] Publisher Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK

Polymer Reviews
Publication details, including instructions for authors and subscription information: http://www.informaworld.com/smpp/title~content=t713597276

New Developments in Elastic Fibers

Jinlian Hu a; Jing Lu a; Yong Zhu a a The Hong Kong Polytechnic University, Hung Hum, Kowloon Online Publication Date: 01 April 2008

To cite this Article Hu, Jinlian, Lu, Jing and Zhu, Yong(2008)'New Developments in Elastic Fibers',Polymer Reviews,48:2,275 301 To link to this Article: DOI: 10.1080/15583720802020186 URL: http://dx.doi.org/10.1080/15583720802020186

PLEASE SCROLL DOWN FOR ARTICLE

Full terms and conditions of use: http://www.informaworld.com/terms-and-conditions-of-access.pdf This article may be used for research, teaching and private study purposes. Any substantial or systematic reproduction, re-distribution, re-selling, loan or sub-licensing, systematic supply or distribution in any form to anyone is expressly forbidden. The publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date. The accuracy of any instructions, formulae and drug doses should be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims, proceedings, demand or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material.

Polymer Reviews, 48:275301, 2008 Copyright # Taylor & Francis Group, LLC ISSN 1558-3724 print/1558-3716 online DOI: 10.1080/15583720802020186

New Developments in Elastic Fibers

JINLIAN HU, JING LU, AND YONG ZHU
The Hong Kong Polytechnic University, Hung Hum, Kowloon
This paper reviews the developments of essential elastic bers. The elastic bers include extensible polymer bers with low or high elasticity and reversibility which consists of the polyurethane elastic ber, polyester-ether elastic ber, polyester elastic ber, olen based elastic ber like XLA, hard elastic ber, bio-component ber, and the shape memory bers. The emphasis of the review is on the development and research process of polymer synthesis, production, characteristics, microstructure, and end-use in industry. It also draws some conclusions about the current problems and future directions. Keywords elastic bers, polyurethane ber, polyester-ether ber, polyester ber, olen based ber, hard elastic ber, bio-component ber, shape memory polymer ber

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Introduction
Elastic bers is a class of ber with elasticity and reversibility, which can be obtained by spinning polymers of specic molecular structure or modied polymers. On the elastic elongation basis, elastic bers can be classied by high elastic ber (elongation of 400 800%), medium elastic ber (150 390%), low elastic ber (20 150%), and micro-elastic bers with elastic elongation below 20%.1 According to the polymer material, elastic bers consist of polyurethane elastic ber, polyester-ether elastic ber, polyester elastic bers, olen based elastic ber like XLA, and others such as hard elastic bers and shape memory bers. The traditional elastic bers such as spandex or lycra have been commercialized for many years. The new products development focuses on the functional bers. The polyester elastic bers of PBT and PTT were discovered in 1940s. However, it was not until the 1990s that petroleum companies developed shorter and more economic process routes to produce these new polymers. The polyester-ether elastic bers are promising bers with wide range uses and lower cost than polyurethane elastic bers. By controlling the molecular structure, different functional polyester-ether bers will be developed. The development of hard elastic ber will emphasize medical applications. The polyolen bers XLA offers performance advantages compared to existing elastic bers. The shape memory ber is a kind of polyurethane based and temperature stimulus bers which makes the textiles with different style and applications.

Received 23 May 2007; Accepted 23 February 2008. Address correspondence to Jinlian Hu, The Hong Kong Polytechnic University, Hung Hum, Kowloon. E-mail: tchujl@inet.polyu.edu.hk

275

276

J. Hu et al.

1.

Polyurethane Elastic Fiber

1.1 Introduction Synthetic elastic bers are generally referred to as elastane or spandex bers in Europe and the United States, respectively. By denition, these bers have an elongation to break more than 200%, usually 400 800%, and on release of the deforming stress, return quickly and almost completely to their original length.1,2 A major advantage of spandex bers over rubber yarns is that they are easily spinnable into thin bers making them suitable for textile applications. Spandex ber, one of the most important thermo-plastic elastomeric bers being commercially produced worldwide, is made with long chain synthetic polymers comprised of mostly segmented polyurethanes. Chemically, it is made up of a longchain polyglycol combined with a short diisocyanate, and contains at least 85% polyurethane.2 It is an elastomer, which means it can be stretched to a certain degree and it recoils when released. These bers are superior to rubber because they are stronger, lighter, and more versatile. In fact, spandex bers can be stretched to almost 500% of their length. The basis for the synthesis of polyurethane elastomeric bers in commercial production at present was the diisocyanate polyaddition process discovered in 1937 by Bayer, H. Rink, and co-workers.3 H. Rinke rst studied the addition reactions of diisocyanates and glycols and he succeeded in spinning bers from the high molecular weight polyurethane resulting from the reaction of butylene glycol and hexamethylene diisocyanate. In 1939, P. Schlack reacted linear polyesters with equivalent amounts of diisocyanates, obtaining high molecular combinations having high elongation and elastic properties. The diisocyanate polyaddition process has been used since 1941 to synthesize designated, high value elastomers having higher tenacities and better end-use properties than the previously-known diene polymers. Reaction spinning was rst investigated by H.A. Pohl in 19424 and was later applied to both linear and cross-linked polyurethane. E. Windemuth in 1949 developed a chemical spinning process in which the chemical synthesis of high molecular weight polyurethane occurred simultaneously with extrusion and ber formation. W. Brenschede succeeded in solution-spinning polyurethane elastomers in 1951. Based on earlier work by M.D. Snyder, J.C. Shivers achieved the rst large-scale technical production of elastane bers by the dry spinning route. The nal development of the bers was worked out independently by scientists at Du Pont and the U.S. Rubber Company. Du Pont used the brand name Lycra and began full-scale manufacture in 1962. They are currently the world leader in the production of spandex bers. All large producers attempted to nd a meltspinning route for elastane yarns. In 1967 Nisshinbo Industries introduced a melt-spun elastane into the Japanese market. This was followed by Kanebo Ltd. in 1977 and Kuraray Co. Ltd. in 1991. A single stage synthesis was next sought, in which the polyurethane raw materials are obtained in the form of granulate, and are subsequently melt spun as reacted polyurethane. A two-stage reaction process is both more modern and provides laments of improved properties. Despite these developments, dry spinning remains the most widely used production process. Table 1 shows the main manufacturers and branding of spandex in the world.3 5 J.C. Shivers described the segmented polyurethane including hard and soft segments. Lyssy gave a schematic structure of polyurethane elastomer, consisting of soft and hard segments, illustrated in Fig. 1.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

New Developments in Elastic Fibers

277

Table 1 Major products and manufacturers of spandex (reprinted from Ref. 3 with permission from Deutscher Fachverlag GmbH) Country USA Company Invista Inc. Dorlastan bers LLC Radici Spandex Corp. Invista (Canada) Co. Fielmex Sade CV Nylon de Mexico SA Invista Ltda. Santista Textil Invista Gomelast, C.A. Petrols Co-Operative Israel Spandex Co. Ltd Asahi Kaser Fibers Corp. Fujibo Kozakai Co. Ltd. Invista Toray Co. Ltd. Kanebo Gosen Ltd. Nisshinbo Industries Inc. Teijin Toyobo Co. Unitika Huvis Corp. Hyosung T&C Co. Kohap Ltd. Tae Kwang Industrial Co. Tongkook Synthetic Fibers Invista Singapore Fibres Anshan Synth. Group Bailu Chemical Fiber Baoding Swan Spandex Corp. Fibre Co. Ltd. Fujian Changle Urethane Fibre Co. Ltd. Haishan Spandex Industry Hangzhou Asahikaser Spandex Co. Invista (china) Co. Ltd. Trademark Lycra Dorlastan Cleerspan, Glospan Lycra Lycra Licra Lycra Plant location Waynesbore; VA Bushy Pak, SC Gastonia, NC; Tuscaloosa, AL Maitland Mexico Monterrey, Nuevo Leon Paulinia Jau, Sao Paulo Mercedes Caracas Naldhari, Gujarat Gamat Gan Moriyama Kozakai Shiga Hofu Tokushima Chuo -ku Tsuruga Suwon Anyang, Kumi Euiwang, Ulsan Busan, Ulsan Kumi Singapore Anshan Xinxiang Baoding Choucun, Shandong Changle, Fujian

Canada Mexico Brazil Argentina Venezuela India Israel Japan

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Spandaven Filabell Spandex Roica Fujibo Spandex Lycra Kanebo Loobell Mobilon Rexe Espa Nexpan Creora Kopadex Acelan Texlon Lycra

South Korea

Singapore P.R. China

Roica Lycra

Hangzhou Qingpu, Shanghai, Foshan (continued )

278

J. Hu et al. Table 1 Continued

Country

Company Jiangsu Haimen Urethane bre Co. Ltd. LDZ Spandex Ltd. Shandong Zibo Urethane Elastic Shaoxing Longshan Spandex Co. Shuanghang Group Tongkook Yantai Spandex Zhejiang Shei Yung Hsin Spandex Acelon chemical Far Eastern Textiles Ltd. FCFC Formosa Asahi Spandex Co. Hualon Corp. Shingkong Synthetic Fibers Shei Heng Hsin Sheiex Industry Co. Tong Hwa Synthetic Fiber Tuntex Distinct Thai Asahi Kasei Spandex Dorlastan bers GmbH Invista (Netherlands) NV Invista (UK) Ltd. Fillatice SpA State Enterprise Chemitex

Trademark

Plant location Nantong, Jiansu Lianyungang, Jiangsu Zibo, Shandong n.a.

Shuka New Star

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Jiangyin, Jiangsu Zhuhai Yantai, Shandong Haining, Zhejiang Fang Yuan, Hsiang

Taiwan

Roica Huastane

Chang Hua

Tao Yuen Sheiex Spandex Roica Dorlastan Lycra Lycra Linel Elaston I-Lan Hsien Chu Pei Hsin Su Bangkok Dormagen Dordrecht Maydown Capriate, Cessalto Volzhsky Jelenia Gora

Thailand Germany Netherlands Great Britain Italy Russia Poland

H. Herlinger, P. Hirt, and H. Hierlemann investigated the mechanical properties of wet spun polyurethane elastic bers by employing liquid crystal chain extenders. This method made the intermolecular covalent bonds stronger and improved the properties slightly relative to other wet spun elastic bers. In order to improve the properties further, F. Hermanutz and P. Hirt synthesized unsaturated elastomers incorporating chain extenders and double bonds. These were wet spun into bers, which were crosslinked by electron or UV irradiation. The tenacity, elongation at break, and residual elongation were improved relative to conventional elastane bers. The methods of liquid crystal chain extenders and crosslinking by irradiation has only been applied in pilot studies. The melt spinning process is becoming important. The elastane polymer

New Developments in Elastic Fibers

279

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Figure 1. Microstructure of spandex (reprinted from Ref. 2 with permission from Deutscher Fachverlag GmbH).

used in melt spinning has to be chemically cross-linked using an excess of isocyanate or polyfunctional isocyanates.

1.2

Production

Polymer Reactions. Two types of prepolymers are reacted to produce the spandex ber polymer back-bone. One is a exible macroglycol while the other is a stiff diisocyanate. The macro-glycol can be polyester, polyether, polycarbonate, polycaprolactone, or some combination of these. These are long chain polymers, which have hydroxyl groups (-OH) on both ends. The important feature of these molecules is that they are long and exible. This part of the spandex ber is responsible for its stretching characteristic. The other prepolymer used to produce spandex is a polymeric diisocyanate. This is a shorter chain polymer, which has an isocyanate (-NCO) group on both ends. The principal characteristic of this molecule is its rigidity. In the ber, this molecule provides strength. Spandex bers are vulnerable to damage from a variety of sources including heat, light, atmospheric contaminants, and chlorine. For this reason, stabilizers are added to protect the bers. Antioxidants are one type of stabilizer. Various antioxidants are added to the bers, including monomeric and polymeric hindered phenols. To protect against light degradation, ultraviolet (UV) screeners such as hydroxybenzotriazoles are added. Another type of stabilizer compounds which inhibit ber discoloration caused by atmospheric pollutants is added. These are typically compounds with tertiary amine functionality, which can interact with the oxides of nitrogen in air pollution. Since spandex is often used for swimwear, anti-mildew additives must also be added. All of the stabilizers that are added to the spandex bers are designed to be resistant to solvent exposure since this could have a damaging effect on the ber.

280

J. Hu et al.

Spinning the Fibers. Spandex bers are produced in four different ways including melt extrusion, reaction spinning, solution dry spinning, and solution wet spinning. Each of these methods involves the initial step of reacting monomers to produce a prepolymer. Then the prepolymer is reacted further, in various ways, and drawn out to produce a long ber. Solution dry spinning is used to produce over 90% of the worlds spandex bres.2 Dry Spinning. The high viscosity elastomer solution, consisting of 20 25% polymer solution in dimethyl formamide or dimethyl acetamide, is extruded through a plurality of spinneret capillary holes vertically down a heated spinning chimney through which heated air ows. Here the laments are solidied by evaporation of the solvent. The spinning conditions, especially the take-up speed, the spinning temperature, and the false twist insertion, have a signicant effect on the mechanical properties of elastane lament yarns.
Downloaded By: [University of Akron] At: 02:19 21 April 2009

Wet Spinning. The elastane solution is spun into an aqueous bath, where the solvent diffuses out and elastic laments are formed by coagulation. After passing through washing baths, the laments are taken up at speeds of up to 100m/min, thereby causing the lament to fuse together. The desired yarn properties are achieved by applying a thermal post-treatment in hot water or hot air, after which the yarns are taken up on winders. Reactive Spinning. This process simultaneously combines the NCO prepolymer chain extension and lament formation in a spinning bath. A uid NCO prepolymer is extruded through a plurality of spinneret capillary holes into a bath containing diamines. Because of the intensity with which some diisocyanates react with diamines, a relatively stable skin of cross-linked polyurea forms on the lament surface. This skin enables the yarn to be taken up. Finally, the hardening of the lament core takes place in hot water, in diamine/alcohol or other solutions. The prepolymer structure is transformed into a covalently cross-linked, segmented elastane lament yarn, which is insoluble in a solvent. Melt Spinning. It is possible to melt spin elastanes from the so-called thermoplastic polyurethanes; these use diols as chain extenders. The melt is extruded through one or more spinneret holes, and the laments formed are cooled by quench air.6 This process permits the production of monolament or multilament yarns. The required yarn properties are achieved by a thermal after-treatment. As the bers exit the spinnerette, a specic amount of the solid strands are bundled together to produce the desired thickness. This is done with a compressed air device that twists the bers together. In reality, each ber of spandex is made up of many smaller individual bers that adhere to one another due to the natural stickiness of their surface. The bers are then treated with a nishing agent. This may be magnesium stearate or another polymer such as poly (dimethylsiloxane).7 These nishing materials prevent the bers from sticking together and aid in textile manufacture. After this treatment, the bers are transferred through a series of rollers onto a spool. When the spools are lled with ber, they are put into nal packaging and shipped to textile manufacturers and other customers. Here, the bers may be woven with other bers such as cotton or

New Developments in Elastic Fibers

281

nylon to produce the fabric that is used in clothing manufacture. This fabric can also be dyed to produce a desired color. 1.3 Microstructure and Properties of Spandex

Microstructure. The unique elastic property of the spandex bers is a direct result of the materials chemical composition. The bers are composed of two types of segments: long, amorphous segments and short, rigid segments of which glass transition temperatures (Tg) are below and above the room temperature, respectively. In their natural state, the amorphous segments have a random molecular structure. They intermingle and make the bers soft. Some of the rigid portions of the polymers bond with each other and give the ber structure. When a force is applied to stretch the bers, the intermolecular bonds between the rigid sections are broken, and the amorphous segments straighten out. This makes the amorphous segments longer, thereby increasing the length of the ber. When the ber is stretched to its maximum length, the rigid segments again bond with each other. The amorphous segments remain in an elongated state. This makes the ber stiffer and stronger. After the force is removed, the amorphous segments recoil and the ber returns to its relaxed state.2,8,9 Due to the thermodynamic incompatibility between the two segments, polyurethanes undergo micro phase separation resulting in the phase-separated heterogeneous structure consisting of hard and soft domains and inter-phases between them. Upon phase separation, the hard segments tend to form the hydrogen bonding between them, which increases the mechanical and thermal stability of the hard domains that act as physical cross-linking sites due to their high Tg, whereas the soft segments form random coil conformations to impart the elastic property to the ber. The various physical properties of the spandex bers such as strength, modulus, mechanical and thermal stability, elasticity, and elastic recovery are closely correlated with the domain structure and interaction between the segments inside the domains (Figure 1). X-ray ber diagrams of unstretched laments show a broad, unoriented, amorphous halo, indicating that the soft segment matrix is amorphous and unoriented.8 In the stretched state (.200%), it is possible to differentiate between polyester and polyether elastanes. In polyester elastanes, stretching causes the amorphous halo to become oriented along the equator without any signs of crystallinity. Stretched polyether elastane shows two oriented crystal reections along the equator. The soft segment matrix has been three dimensionally crystallized by the stretching (Figure 1). Characteristics. Spandex has better physical properties than rubber ber in tenacity, modulus, anti-aging, minimum linear density and dyeability. Table 2 shows the performance comparison. The longitudinal surface is smooth. The cross-sectional views are variable. Dry spun elastane yarns show round, oval, or dumbbell shaped lament cross-sections, while wet spun elastanes have mainly strongly lobed, irregular lament proles. In some elastane yarns the lament fusion can be so strong that they merge into one another. This is particularly so in the case of wet spun yarns, where higher decitex yarns show lament tale geometry. Melt spun elastanes are produced as mono-or multilaments of predominantly round cross-section. The thermal behavior of elastanes at low temperatures is governed by the soft segments. At high temperatures, the thermal behavior depends on the hard segment matrix, the molecular weight, and the type of chain extension and the orientation of the

Downloaded By: [University of Akron] At: 02:19 21 April 2009

282

J. Hu et al. Table 2 Performance compare of rubber ber and spandex

Performance Tenacity (cN/tex) Elongation (%) Elastic modulus (cN/tex) Anti-aging Lag elongation (%) Dyeability Minimum linear density (dtex)

Rubber ber 3 600 700 0.2 Bad 3 No 100

Spandex 9 13 500 600 0.5 Good 20 Yes 11

Downloaded By: [University of Akron] At: 02:19 21 April 2009

hard segment. At temperatures above 1708C, there is a noticeable thermal degradation of the ber, which manifests itself as yellowing and as a deterioration of the elastic properties.9 11 Elastane bers are soluble in highly polar solvents, such as DMF and dimethylacetamide. While elastanes containing polyether soft segment are less subject to hydrolysis, polyester elastanes are more resistant to oxidation. Under mild conditions, elastane is resistant to acids, alkalis, oxidizing agents and reducing agents. Treatment with highly concentrated acids and caustics for an extended times; however, this results in a loss of elastic properties, and the loss increases with increasing temperature.10 Elastane is insensitive to hydrolytic effects during normal washing and handling, and is unaffected by the use of normal solvents. Elastane bers have good resistance to oxygen and ozone. Nitrogen oxides cause a color change to yellow or yellow brown, the intensity depending on the concentration, ambient temperature and relative humidity. Elastane are more resistant to ageing and abrasion than rubber yarns. Long exposure, particularly to UV radiation leads to a change in color of the ber and to photochemical degradation. Polyester urethane has higher resistance to photo-oxidation than polyether urethane.11 1.4 New Products of Spandex Highly Hydroscopic and Moisture Liberating Spandex. Asahi Kasei was rst to develop the high hydroscopic and moisture liberating spandex (Roica BZ).11 15 This ber has high hydroscopic property like cotton, but also has quick moisture liberation property. It can absorb water in a high humidity environment and release it under low humidity environment. Highly Soft Spandex. Spandex has a high elongation. If tensile modulus is high, the constrictive force is big. So it is uncomfortable when wearing especially for children and elders. Grafting alkyl side chain on polyether dihydric alcohol of the soft segment is a general method to reduce tensile modulus of the ber. But it is difcult to do in industry. Asahi Kasei invented a catalyst making this process possible. This high soft spandex named Rioca HS17 has come into the market. Invista has developed a similar product naming it Lycra soft. Easy Setting Spandex. Spandex woven under tensile state resists shrinkage deformation. It is necessary to release the deformation under certain thermal condition. Thermal setting

New Developments in Elastic Fibers

283

of spandex with polyester soft segment is good because of the good thermal plastic property but that of spandex with polyether soft segment is poor. However, thermal stability of polyester spandex is poor, so it cannot be interwoven with polyester ber.16 Asahi Kasei has developed a low temperature setting spandex named Roica BX, which not only have good setting effort but can interweave with polyester ber and set under high temperature. Other high setting spandex includes T560, T562 B of Invista and Espa M of Toyobo and Mobilon P of Nisshinbo. Other Functional Spandex. Some new products of specic functions were developed such as the chemical or chlorine resistant spandex, anti-bacterial spandex, high tenacity spandex, easy dyeing spandex. The primary use for spandex bers is in fabric. They are useful for a number of reasons. First, they can be stretched repeatedly, and will return almost exactly back to original size and shape. Secondly, they are lightweight, soft, and smooth. They are also resilient, since they are resistant to abrasion and the deleterious effects of body oils, perspiration, and detergents. They are compatible with other materials, and can be spun with other types of bers to produce unique fabrics, which have characteristics of both bers. Spandex is used in a variety of different clothing types.11 Since it is lightweight and does not restrict movement, it is most often used in athletic wear. This includes such garments as swimsuits, bicycle pants, and exercise wear. The form-tting properties of spandex make it a good for use in under-garments. Hence, it is used in waist bands, support hose, bras, and briefs.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

2. Polyester Elastic Fiber

Recently polyester based elastic ber has been developed rapidly. The main class includes PBT poly(butylene terephthalate) ber and PTT (polytrimethylene terephthalate) ber. PBT18 was included in the polyester patent issued by Whineld and Dickson, two scientists of the Calico Printers Association. Production of PBT ber for textile use rst started between the end of the 70s and the mid 80s in Japan and in the USA. In Japan producers were Toray (Sumola), Teijin (Finecell), Kuraray (Artlon), Unitika (Wonderon), Kanebo. In the USA, the company was Celanese. PTT ber19 was rst patented in 1941 but it was not until the 1990s, when Shell Chemicals developed a low cost production method. Poly(butylene terephthalate) was carefully studied in the mid of 1970s when two distinct a and b crystalline phases were identied. About ten year later Lu and Spruiell21 followed the work of Boye and Overton21a and Jakeways et al.22 to show that the b form can be obtained in the unstrained state and indicated drawing conditions which favor the production of this crystalline phase. High-resolution, solid-state 13C NMR studies of the a and b polymorphs have revealed several important features concerning the conformations and motions of PBT chains in both crystalline phases.22 It appears the glycol residues are in the nearly extended trans conformations in both crystalline forms, while different orientations of the ester groups and phenyl rings probably account for the 10% difference in the ber repeats of a and b structures. In both crystals the methylene carbons are sampling rapid motions, which are signicantly faster than the motions experienced by the carbons of the terephthaloyl residues. Recently, Tonelli21c proved by 13C NMR studies that in the a polymorphs, the ester groups are rotated  408 out of the phenyl planes to which they are attached.

284

J. Hu et al.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

PTT is a semicrystalline polymer synthesized by the condensation of 1,3-propanediol (PDO) with either terephthalic acid or dimethyl terephthalate, followed by polymerization. Studies of PTT had never gone beyond academic interest until recent years because one of its raw materials, PDO, was very expensive and available only in small volume. PTT received less attention when compared with PET and PBT. However, recent breakthroughs in PDO synthesis made PTT available in industrial quantities, thus offering new opportunities in carpet, textile, lm, packing, and engineering thermoplastics markets.23,24 Numerous studies on the crystal structure and mechanical properties of PTT have been reported.25 31 Analysis of the crystalline structure of PTT shows that the aliphatic part of PTT takes a highly coiled structure of gauche-gauche conformation. PTT has a triclinic crystalline structure, each cell of which contains two chemical repeat units. Thermal behavior and crystallization kinetics of PTT have also been extensively investigated.32,33 In general, the glass-transition temperature is in the range of 42758C, depending on the thermal history; the melting temperature is about 2288C, which is almost equal to that of PBT (about 2258C) and is much lower than that of PET (about 2658C). The well-known Avrami equation and secondary nucleation theory could well describe the crystallization kinetics of the polymers. Pyda et al.32 investigated the heat capacity of PTT and estimated the heat of fusion for a 100% crystalline PTT to be 30 kJ/mol. Chung33 studied the bulk isothermal crystallization kinetics and compared the crystallization rate of PTT with that of PBT and PET, using DSC. Based on the analysis of crystal growth rate, the Avrami rate constant K and crystallization half-time were determined. It was found that PTTs crystallization rate is between that of PBT and PET when compared at the same undercooling degree, contrary to the widely believed concept that aromatic polyesters with odd numbers of methylene units are more difcult to crystallize than the even-numbered polyesters. PTT does not follow the odd even effect. Among the three polyesters, PBT has the highest crystallization rate, about an order of magnitude faster than PTT, which in turn is an order of magnitude faster than that of PET. The crystallization rate for a semicrystalline polymer is important in practical applications. The key advantage is that it combines the desirable physical properties of PET (strength, stiffness, toughness, and heat resistance), while retaining basic polyester benets of dimensional stability, electrical insulation, and chemical resistance. 2.1 PBT and PTT Elastic Fiber Polymer Production. The polymer production is similar to the PET synthesis and involves direct esterication and ester interchange polymerization (Figure 2).

Figure 2. Molecular formula of PET, PBT, and PTT.

New Developments in Elastic Fibers

285

In fact, PBT is polyester in which, during the condensation reaction of the dihydric alcohol with terephthalic acid, ethylene glycol is replaced by butanediol with four methylene groups. For PTT, Shell chemicals developed the low cost method of producing the high quality PDO, the starting raw material of the PTT. There are two routes to synthesize PTT namely, the transesterication of dimethyl terephthalate (DMT) with PDO and esterication route with TPA (terephthalic acid) and PDO. In the rst stage of polymer synthesis, TPA or DMT is mixed with PDO to produce oligomers having 1-6 repeat units with the help of a catalyst. In the second stage this oligomer is polycondensed to a polymer with 60 100 repeat units. The catalyst used in the rst step also accelerates the polycondesation reaction (Table 3). Generally, this objective can be fullled by two methods. The rst is the use of a lower process temperature, which reduces the processing time in the melt phase to a minimum and keeps oxygen out completely. The second way might be selecting a sufcient amount of a catalyst and adding stabilizers like phosphorus compounds or sterically hindered phenols.37 39
Downloaded By: [University of Akron] At: 02:19 21 April 2009

Fiber Spinning. PTT and PBT are melt spun and like PET are sensitive to hydrolytic degradation. This means that a drying process is necessary before extrusion. The temperature must be below 1508C, otherwise oxidative degradation will occur. When considering the use of the spinning and winding process from PET to PTT, one has to take three properties into account:20,33,34,36,40
. . .

Melt temperature Glass transition temperature Intrinsic elasticity

The lower melt temperature means that there is a shorter length of time until the spun lament in the yarn line is cooled down and the quench air adjustment and the cooling Table 3 Physical properties of polyester spandex and polyether spandex Performance Tenacity (cN/tex) Elongation (%) Recovery elongation (%) Elastic modulus (cN/tex) Tg(8C) Specic weight Moisture regain Heat resistance Polyether type 6.18  7.94 480  550 95 (elongation 500%) 1.1 270  508C 1.21 1.3 Yellowing at 1508C, stickiness at 1758C Acid resistance, yellowing in H2SO4 and HCl Tenacity loss after long exposure to sunlight Polyester type 4.85  5.47 650  700 98 (elongation 600%) 25  458C 1.20 0.3 Thermal plasticity improving at 1508C; tenacity loss at 1908C Dilute acid resistant, hot alkali labile Tenacity loss and color change after long exposure to sunlight

Acid and alkali resistance Atmospheric resistance

286

J. Hu et al.

length dimensions are different from the PET spinning process. Another important difference with PET is the lower glass transition temperature, which affects much faster cold crystallization. This has a signicant impact on the development of the ber morphology during solidication and cooling down. The spinning conditions are more comparable to PA6 than to those of PET.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Characteristics and Microstructure. The diacid group affects the mechanical property of polyester and its processability depends on the type of the diol group. In particular, poly(trimethylene terephthalate) (PTT) is a highly crystalline polymer. Its melting temperature is lower than that of PET by 20 308C. Therefore, the processability of PTT is superior to that of PET. The highly exible PTT bers are obtained as a result of its low initial modulus. The elasticity and dyeability of PTT are better than those of PET or poly(butylene terephthalate) (PBT). It is well known that the number of methylene unit inuences the physical properties of many polycondensation polymers such as polyamides and polyesters, which is called the odd-even effect. PET molecules are fully extended with two carboxyl groups of each terephthaloyl group in opposite directions, and all open chained bonds are trans with successive phenylene groups at the same inclination along the chain. PTT has a conformation with bonds of the -OO(CH2)3OO- unit having the sequence of trans gauche gauche trans, leading to a concentration of the repeating unit. The opposite inclinations of successive phenylene groups along the chain force the molecular chains to take on an extended zigzag shape. Because of the molecular characteristic differences, the theoretical maximum elongations (c-axis that is parallel to the ber axis) of PET and PBT reach about 98 and 86%, respectively, whereas that of PTT is only 76%. On the contrary, PTT has a helical structure of an angle of 608 (gauche) for its oddnumbered carbons, resulting in the 75% gain of fully extended chain length. For this reason, to enhance the physical properties of PTT brous materials, the PTT chain should be extended with the change in distortion angles in crystalline as the spring extension.36,38 Table 4 gives a rough comparison between PTT, PBT, PET, nylon, and spandex.37
. . . .

PTT have slightly more power stretch and recovery than PBT and more than PA6/ 66 and PET PBT remove extra pressure and give more comfort than spandex PTT have the best soft hand of all, as PBT will be close to PET Both are easily dyed at 1008C and can be mixed with other ber and offer stain resistance, chlorine resistance, and a good resilience.

The outstanding features of PTT bers can be summarized as:35 40

.

. .

Very good elongation and recovery under low load creating a wearing comfort. The ber recovers 100% from 120% strain. For textured yarns, the ber offers up to 145% stretch with 100% recovery. Dyeable at low temperature: PTT can be dyed at 1008C with the same or slightly deeper shades than PET at 1308C. Disperse dyed PTT shows excellent colorfastness to laundering, crocking test, and UV light and ozone. Soft handle, good dry-ability, and stylish drape (low Youngs Modulus). Better abrasion resistance and dimensional stability.

New Developments in Elastic Fibers Table 4 Fiber properties comparison chart37 Property Melting temperature (8C) Glass transition (Tg) Density (gcm23) Initial modulus (cN/dtex) Elastic elongation (%) Softness Recovery Bulk Heat-set capability Abrasion Chlorine resistance Dyeability Stain resistance Light fastness Wash fastness Color intensity Static resistance Cost PTT 228 45 65 1.33 2.6 28 33 2 1 2 1 2 2 2 2 2 PBT 221 20 40 1.35 2.4 24 29 1 1 2 22 1 2 2 2 2 2 PET 260 70 80 1.38 9.15 20 27 21 21 21 1 21 22 1 1 2 21 2 2 PA6/66 223 80 90 1.14 2.1 27 32 1 2 2 2 21 1 21 21 21 1 21 Spandex

287

Downloaded By: [University of Akron] At: 02:19 21 April 2009

230 290 270 50/25 45 1.21 0.11 0.45 400 800 22 2 22 21 22 22 22 22 22 22 22 22 22

2 best, average, 22 worst.

Able to retain heat set pleats and creases. The ber heat sets at lower temperatures than PET.

The performance of the PBT bers can be summarized as follows:37,40

.

. . .

High extensibility even under low loads and quick recovery from deformation once the strain has been relieved (in practice, an elasticity in between the height of spandex yarns and the lower level of nylon textured yarns) Processability, in texturing, under gentler operating conditions than in the case of PET Dyeability at the boil Good color fastness, dimensional stability also in the wet state, and fastness to chlorine.

Applications. The applications of PTT in the textile industry include lament yarns, staple bers and BCF yarns for carpets. In blends with other synthetic bers such as Lycra or natural bers such as cotton, PTT enables a variety of end products that have a soft feel, good drape, and stretch and recovery qualities.37 40
.

. .

Sewing thread: one of the most recent application elds is sewing thread which will endow clothing products with added value by appropriate extensibility, recovery and dimensional stability. Sportswear and leisurewear: the extraordinary properties of PTT are very much useful for sports and leisurewear plus elastic interlinings and shirting fabrics Spunbonded fabrics

288
. . .

J. Hu et al. Carpets: wear performance is equal to or better than nylon without the staining or cleaning problem. Upholstery: good stretch recovery, dye and print capability, stain resistance, and resiliency. Apparel: softness, stretch and brilliant lasting colors in both knit and woven fabrics, in hosiery and intimate apparel, linings, denim, swimwear etc.

For PBT ber, in addition to traditional end-use, such as stretch jeans, bathing suits, sportswear and hosiery, a particularly promising application trend is that of apparel stretch yarns, produced by twisting a textured PBT yarn with a natural staple ber yarn.40

2.2 Bicomponent Self-crimp Elastic Fiber Self-crimp bers behave like natural wool with a textured appearance. The crimps are formed from a composite of two parallel but attached bers with differing shrinkage or expansion properties. Since the crimp is naturally formed, the false twist or airtexturing involved in typical ber processing for synthetic bers becomes unnecessary and can be eliminated. Another important characteristic of the self-crimp yarn is that the crimp is not imposed on the ber from the outside, but rather results from the rearrangement of the internal molecular structure of the ber material. Usually, the crimp generated by either false twist or air-texturing is imposed on the ber via mechanical deformation of the ber as a 2D zig-zag crimp. In some applications the crimped ber must be extremely resilient, for example, in ber lling for pillows, furniture, and so on. In such cases a mechanical 2D crimp is insufcient, and instead, a latent helical self crimping of the ber is necessary. A combination of various polyester materials can be used, for example, PET (polyethylene terephthalate), CD (Cation Dyeable PET), PTT (polytrimethylene terephthalate), and PBT (poly(butylene terephthalate)). The basic driver of self-crimping is a shrinkage differential within the ber. Early theories to study the crimp mechanism were based on mechanical models of bimetallic strips. During the early 1980s, Denton41 developed an advanced equation that used a geometrical and mechanical approach to describe this effect. The equation has been proven practical when applied to most bers with regular cross-sections. Denton41 reached three important conclusions based on his equation: 1. Fibers with a single interface exhibit the best crimp potential; 2. The crimp potential is maximized in a skein with a straight interface passing through the center of the cross-sectional area of a conjugated ber; and 3. The crimp potential is zero for any cross-section with a center of symmetry (such as centric core/sheath). To obtain sufcient crimp the differential shrinkage must exceed a certain value. The differential shrinkage can be obtained in different ways and thermal shrinkage without. A theoretical model proposed by Denton41 proved to be very useful for predicting crimp potential. Maintaining identical or very similar melt viscosities of the two components was demonstrated to be very critical for obtaining a straight interface and eliminating the dog-legging problem during melt spinning. Regarding the thermal treatment following melt spinning, a temperature range of 20  308 higher than the Tg of the harder side in the ber is the optimum condition. The crimp tests illustrate that the triangular shapes are found to be superior to the round cross section.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

New Developments in Elastic Fibers Spinning of conjugated ber has some technical difculties:40
. . .

289

The melt instability between the two ingredients; The need to instantly adjust the throughput ratio; The complex design of the conjugated spinnerets.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Du Pont de Nemours (Wilmington, DE) started to study the rst self-crimp yarn (PP) in the early 1960s. Recently, the newly commercialized self-crimp products of DuPont, polyester T-400 and nylon T-800, have become very popular in the market. Unitica (Hyogo, Japan) also commercialized the self-crimp yarns, Z-10 and S-10. Furthermore, a nylon/polyurethane bicomponent lament, Sideria, developed by Kanebo (Japan), can adapt heat treatment to self-crimp itself to an appropriate degree. Some research shows that the crimp of triangular shapes is superior to the round cross section. The optimum volume ratio for making a self-crimp bicomponent skein is 50/50. Finally, the study found that the combination of PET/PTT outperformed that of PET/PBT and PET/CD in terms of crimp potential, crimp stability, and elastic recovery. This phenomenon is primarily attributed to the markedly different thermal shrinkages of PET and PTT (Figure 3).

3. Polyether-ester Elastic Fiber

Polyether ester ber was developed early as a thermoplastic elastomer in the 1970s and industrialized in plastics trade. Recently some research center and factories have done some research about the polyether ester, but dont produce volume.43 Fiber of polyether-ester was obtained by melt spinning from the polyester and polyether block copolymer.44 It was a medium elastic ber with breaking elongation of 600% and the elastic recovery is above 85% at the elongation of 100%. It has good dyeability and anti-chemical properties. There are many similar properties of polyether ester ber and spandex. In chemical structure, both bers have long chain polyether and the elasticity root from the entropy change. The advantages of polyether-ester ber are the cheap raw materials and nontoxic and spinning on PET conventional machines. So the polyether-ester ber may replace spandex in some applications. There are no chemical crosslinking points and hydrogen bonds between the long molecular chains.45 The intermolecular linking of the crystallites offers the elasticity.

Figure 3. Cross section of bicomponent self crimp bers a) PTT/PBT bicomponent ber, b) T400 ber (reprinted from Refs. 40,42 with permission from John Wiley & Sons Inc.).

290

J. Hu et al. Table 5 Characteristics of polyether-ester General tenacity Medium tenacity 2.67 3.56 800 1000 95 97 High tenacity 7.12 8.01 7.0 10.0

Tenacity (cN/dtex) Elongation (%) Recovery elongation (elongation of 50%) Density (g . cm23) Melting point (8C)

0.45 0.89 300 800 80 90 1.0 1.3 200 220

200 220

.230

For common polyether-ester, the crosslinking between molecules is weak. In order to enhance the elasticity, appropriate tie points will be formed, which do not only relate to the chemical structure but also the spinning and post treatments. Polyether-ester also includes the hard segments of crystalline regions and soft segment of amorphous regions.46,47 An elastomer can be described as a continuous amorphous phase dotted with microcrystalline structure. When stretched, stress is applied to the crystalline phase through joint and microcrystalline phase orients, then nally the stress is applied to the net structure of the polymer. So the soft segment deforms. When unloaded, the soft segment will release energy and recover to the original state (Table 5). Polyether-ester elastomer is a linear block copolymer. The typical chemical structure is shown in Fig. 4. The most suitable materials are terephthalic acid, 1,4 butylene glycol, ethylene glycol and polydihydric alcohol ether. The polymerization process includes the esterication, prepolymerization, and post polymerization as for the conventional polyester polymerization method. Du Pons patent adopted branched dicarboxylic acid and dihydric alcohol as amorphous soft segments to avoid the frozen crystallization during drawing. This method improved the tear strength and exibility properties.43 In order to improve the elasticity stability, a Japanese patent48 reported a method to add an unsaturated compound of high temperature stability to the copolymer. Improving the phase separation is another method to increase the stability. A patent49 reported that adding some crystalline nucleation agents such as calcium stearate or magnesium stearate can accelerate phase separation and microcrystalline formation and improve the elasticity nally.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Figure 4. Polyether-ester molecular formula.42,44

New Developments in Elastic Fibers

291

Polyether-ester ber can be gained by melt spinning as polyester does. The chips of polyether ester dry in vacuum tumble dryer for half an hour at 1208C at 40Pa. The spinning temperature is controlled 208C higher than the melting point.

4. Hard Elastic Fiber

Hard elastic material is characterized by its special morphology and mechanical properties. These materials are usually prepared from the melt in the form of extruded lms and bers under specic condition of crystallization. For common elastic materials, while under tension, the molecule of the high elastic state polymer material is extended; when unloaded, the molecule tries to come back the coiled shape. From the point of view of thermodynamics, this elasticity root is the change of entropy, so it is called entropy elasticity. According to this mechanism, the polymers with high crystallinity do not have high elasticity. But PP, PE, etc bers present high elongation like rubber and have good reversion under specic melt spinning condition. Because of the higher modulus than rubbers, so they were called the hard elastic bers.49,50 The essential morphological feature of the elastic materials, as revealed by X-ray diffraction and electron microscopy,51 is the presence of stacked crystalline lamellae. Their lamellar surfaces are aligned normal to the extrusion direction of the bers. The generalized properties of these row structure materials include high elastic recovery from very high strains such as 50 95% recovery from 100% extension, a reversible reduction of density with an enormous increase of pore volume upon stretching, and high deformability with good recovery at liquid nitrogen temperature. Polymers that can be used for the formation of such elastic materials include semicrystalline polymers as polyoxymethylene (POM), poly (propylene) (PP), poly-(4-methyl-1-pentene) (PMP) (TPX), polyethylene (PE), etc.52,53 The mechanism of elasticity is based on splaying apart of their lamellae, and their reversible bending and torsional deformation during macroscopic deformation of the materials. Additional work on PP hard elastic bers showed that the ber exhibited a porosity of a peculiar nature when it was stretched signicantly. The formation of microvoid is due to the stacked lamellar crystal structure normal to the ber axis within the material. When the ber is stretched, the crystal lamellae are separated with a large amount of voids that are interconnected. That is why hard elastic polymers can be prepared into hollow ber membranes through melting spinning-stretching (MS) process. Hollow ber membranes such as i-PP, PE made by the MS process have been commercialized and widely applied in water treatments. The deformation mechanism of hard elastic bers results in special elastic properties. At least four basic structural models have been proposed to explain their elastic properties. These consist of a. a leaf-spring model involving the elastic bending of lamellae; b. reversible shear of lamellae between xed tie points; c. a general model based on a change in entropy in the intermolecular layer and an increase in surface energy during extension of a hard elastic ber, and d. a combined structural model that attributes the stress for extension to the pulling of brils from lamellae and the retractive force resulting in the particular elastic properties to surface energy and entropy effects in the brils. These four models indicate different mechanical properties and structures in the strained state.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

292

J. Hu et al.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Figure 5. Deformation models of hard elastic PVDF bers (reprinted from Ref. 54 with permission from John Wiley & Sons Inc.).

The model in Fig. 5 shows the deformation process. From 5 to 40% extension, the oriented crystal lamellae separate gradually and undergo an elastic process, the amorphous region undergoes crystal rotation and plastic deformation processes. Further increase of stress leads to increasing competition from elastic and plastic deformation processes and these results correspond to the second yield point in the stress-strain curve. Above 40% extension, the plastic deformation process becomes increasingly dominant. The whole process can be divided into three parts: crystal rotation, lamellar separation, and plastic deformation. The hard elastic bers can be interwoven with other common ber to produce elastic fabric such as sock, kneecap, and swimwear. It can replace spandex partly; can be used to produce carpet, which have good recovery property; and produce elastic threads, elastic safe nets, and shnets.

5.

XLA Fibers

XLATM is olen-based stretch ber that is naturally resistant to harsh chemicals, high heat, and UV light. Incorporating XLA ber into fabrics offers unmatched opportunities for developing easy-to-handle, durable garments with improved shape retention. In USA Lastol ber is the new generic name for this polyolen based elastic ber.55 58

5.1 Microstructure The special microstructure of XLA combines long, exible chains with crystallites and covalent bonds or cross-links, forming an intricate network (Fig. 6). Using Dow proprietary technology, the length of the chains and number of crystallites are specically controlled to give XLA ber a unique elastic prole. High stretch is achieved with low

New Developments in Elastic Fibers

293

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Figure 6. Microstructure of XLA bers (reprinted from Ref. 59 with permission from the Dow Chemical Co.).

levels of force, allowing garments to stretch and ex effortlessly and still return to their original shape.

5.2

Characteristics

5.2.1 Heat Resistance. The cross-links formed in the bers molecular structure are the key to superior heat resistance. As the temperature increases, crystallites will gradually disappear and cross-links take over, keeping the network intact. After cooling to room temperature, crystallites will reform. This makes XLA very different from conventional melt-spun bers, which rely on crystallites for both recovery and heat resistance. Figure 7 shows bers at room temperature and after three minutes at 2208C. When the slide cover was slightly pressed, the degraded spandex ber came apart, while the XLA ber maintained its integrity. Because XLA ber can survive intense heat, it enables a greater range of processing for stretch fabrics and garments. High temperature thermosol dyeing, high pressure and high temperature jet dyeing of polyester (1308C), and high temperature or extended

Figure 7. Hot- stage photomicrographs of 40-denier XLA ber and spandex (reprinted from Ref. 60 with permission from the Dow Chemical Co.).

294

J. Hu et al.

time-curing processes for functional nishes are now possible. Stretch fabrics enhanced with XLA can also withstand high temperature steam press (Hoffman Press), tumble drying, and medium or high ironing temperatures. 5.2.2 Chemical and UV Resistance. XLA ber technology is based on olen chemistry and just like other olen-based plastics, which can be used to make bottles for bleach and cleaners. The bers are inherently resistant to chemical degradation. Fiber test exposures were carried out in conditions closely simulating or even more severe than industrial processes such as no-iron nishing, mercerizing, and industrial laundering. Under the stress of these harsh conditions, the ber strength did not noticeably change. Because olens have an afnity to hydrocarbon solvents and mineral oils, XLA ber should not be exposed to these classes of chemicals for extended periods of time. Just as it wards off the effects of chemicals, XLA resists degradation caused by UV light. The chemical and UV light resistance of XLA ber technology enable valuable processing advantages and offer excellent durability. Resistance to chemicals allows for optimum processing conditions and enables the application of a wide variety of functional nishes. Chemical resistance enables aggressive garment processing like denim washes, noiron garment dipping, and refurbishment via commercial laundering and dry-cleaning even industrial laundering and the high-heat tunnel drying of uniforms. UV/Xenon resistance makes the bers to deliver stretch in end-use applications demanding top-notch performance such as active wear, industrial, and automotive.60 The unique ber technology of XLA combines that soft feeling, smooth performance and uid motion into familiar base fabrics like cotton, wool, and linen, so fabrics stay fresh, exible, and durable for the futures endless, exciting opportunities. 5.2.3 Application. XLA elastic ber is being used in a number of different fabrics and concept garments suitable:59 62
.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

. .

Wool: suits, suit separates tailored sportswear, formal wear, and career wear made from pure worsted wool and worsted wool blends can be enhanced with XLA elastic ber. These stretch wools and wool blends offer improved recovery over natural stretch and improved drape and hand over spandex yarn alternatives. Swimwear: for performance swimwear, XLA elastic ber offers stretch that stays continuous exposure to chlorine and UV light will not compromise the lasting stretch performance of XLA. Intimates: XLA elastic ber for intimates can offer a new standard in t, color matching, comfort, and drape. No-wrinkle stretch cotton: easy care can be achieved through performance and functional nishes such as stain and wrinkle resistance and permanent crease without loss of elasticity.

6.

Shape Memory Fibers

6.1 One Way Shape Memory Fiber Presently, the study about shape memory polymer (SMPU) materials has been widely conducted since it was introduced in 1984 in Japan.63 Based on the research result, the mechanism of the thermally induced shape-memory effect of these materials has been

New Developments in Elastic Fibers

295

established on the base of the formation of phase segregated morphology. In shape memory polymer such as shape memory polyurethane, in one of the phases, there is a transition temperature (Ttrans) in usage temperature range such as melting point or glass transition temperature of soft segments domain. The obvious characteristic of shape memory polymer is the elastic modulus, which can be changed at least two orders of magnitude times at the temperature between lower and higher than the transition temperature (Ttrans). In addition, the formation of stable hard segment domains acting as physical crosslink above the permanent transition point (Tperm) is responsible for memorizing the permanent shape. Tperm may be melting temperature of hard segment (Tmh) or glass transition temperature of hard segment (Tgh) according to different molecular structure, such as hard segment content and the molecular regularity of the hard segment. Above this temperature, the polymer melting occurs and will not be different from the conventional elastomer. The transition temperature Ttrans is either a melting temperature(Tms)64 or a glass transition temperature(Tgs).65,66 In the case of Tms, a relatively sharp transition can be observed in most cases while Tgs (glass transitions temperature of soft segment) always is located in a broad temperature range. Mixed glass transitions temperature Tg mix between the glass transition of the hard segment and the soft segment may occur in the cases where there is no sufcient phase separation between the hard segment and soft segment. Mixed glass transition temperature can also act as switching transitions for the thermally induced shape-memory effect.67,68 As for the application of shape memory polymer used in ber spinning to impart the smart function into fabric, there are only few literatures references about the study of shape memory polyurethane ber. Nevertheless, the sparse application and production of these kinds of functional bers has aroused much attention. In the patent, Hayashi et al.67 reported that a woven fabric of shape memory polymer which is formed by weaving yarns of shape memory polymer bers along or by weaving said yarns or ordinary natural or synthetic bers wherein the shape memory polymer bers are made of a polyurethane elastomer having a shaped memory property. Chun et al.69,70 studied the shape memory polyurethane composed of PTMG, BDO, MDI, with the switching temperature range from 2 158C to 1.58C. The shape memory ber made of their shape memory polyurethane can be prepared with electrospinning with the use of the mixed solvent of DMF (N,Ndimethylformamide) and THF (tetrahydrofuran)71 (Figure 8). The electrospun polyurethane nonwovens with hard segment concentration of 40 and 50 wt% were found to have a shape recovery of more than 80%. Hu et al.72,73 have studied the shape memory effect of shape memory polyurethane ber composed of PBA (poly (butylene adipate)) or PEA (poly (ethylene adipate)), MDI (4,40 -methylene-bis-phenyl isocyanate), BDO (1,4-butanediol) with the transition temperature at around room temperature (29  648C). Moreover, with the usage of various processing technology, the shape memory polymer has been successfully engineered into the series of bers and yarns with tailor-made shape memory function, applicable tenacity (6  14cN/tex) and maximum strain (35  204%). The shape memory function of the bers can be demonstrated by the applicable xing ability (70  100%) for stretching at room temperature and the admirable recovery ability after heating the stretched ber beyond the transition temperature. 6.2 Comparison between Shape Memory Fiber and Traditional Elastic Fiber

Downloaded By: [University of Akron] At: 02:19 21 April 2009

In the study of shape memory polyurethane ber, not only the shape memory function was worthy of being investigated systematically, but the comparison between shape memory ber and traditional man made ber need to be made as well, so as to obtain an overall understanding for such kinds of functional bers.

296

J. Hu et al.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

Figure 8. Stress-strain behaviour of various man-made bers (reprinted from Ref. 72 with permission from John Wiley & Sons Inc.). (a) is the whole X scale from 10% to 700%. (b) is the enlargement X scale from 10% to 150%.

It is easy to notice that the man made laments approximately might be attributed to two features: one is of high tensile strength (tenacity: 5  7 g/den for Nylon 6) and modulus, but low elongation at break (25  40% for Nylon 6) and high elastic recovery with only minor deformation such as Nylon 673; the other one is of a very low initial modulus, very high elongation ratio at break (500  600%) and nearly complete instant elastic recovery after stretching (90  100%) such as Lycra.74 In the study for shape memory polyurethane lament, the heating responsive shape memory effect was expected to be introduced into the multi-laments, namely to cause the deformation to be recovered with stimulus of heating above the transition temperature. The glassy or crystallizable soft segment at the temperature below transition temperature (Tg or Tm) can impart the ber with relative high initial modulus, applicable elongation ratio and strength at break, in which the last factor is usually considered mostly for kitting process.71 73 As shown in Figure 8, the stress-strain

New Developments in Elastic Fibers

297

Downloaded By: [University of Akron] At: 02:19 21 April 2009

curve of SMPU bres (PU56-90, PU56-120, PU66-90, PU66-120) is located between the high modulus ber such as nylon and the high elasticity bre such as Lycra; for stress-strain behavior, the inuence of thermal setting is found to be greater than the hard segment content in the range of hard segments content used in this study; the thermal setting with higher temperature will give rise to the lower modulus and tenacity and the higher maximum elongation ratio in these two series of shape memory polyurethane bers. Furthermore, the yield points of shape memory polyurethane ber can be observed at the strain at around 5% and the higher the hard segment content in SMPU bre, the higher the yield strength will be. Using dynamic mechanical analysis (DMA), the elastic modulus (E 0 ) in the normal using temperature range about a variety of man-made bers was demonstrated in Fig. 9. The resultant data show that the main difference between SMPU ber and conventional man-made bers is the variation of E 0 in normal using temperature range. For SMPU bers such as PU56 120 and PU66 120, the variation of E 0 is very signicant. Namely, when the temperature was increased above the transition temperature, the E 0 will sharply decrease and the rubbery state platform will appear and be extended to above 1808C. However, for other types of man-made bers such as polyester and Lycra, though in the entire heating scan range, there are some transition areas of E 0 , such as 2408C for Lycra,74 100  1058C for polyester bers and yarns,75 the elastic modulus is almost the constant and change little with the increase of temperature in room temperature range. Therefore, this point imparts the heating responsive shape memory properties to the SMPU bre in normal using temperature. For common elastic bers, might be the elasticity should be dened as the instant recoverability of the length on release of the deforming stress. The recoverability in shape memory bers should be the recovery ability of deformed bers with external stimulus such as heat or chemicals. In this case, the external stimulus is a must.

Figure 9. Comparison of elastic modulus between SMPU bre and various man-made bers.

298 6.3 Two Way Shape Memory Fiber

J. Hu et al.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

So far, most of the research on shape memory polymer was focused on shape memory effect based on the programming comprising deforming with external force and automatically recovering from deformed status with the external stimulus, which were usually called one-way shape memory effect in the study of shape memory materials.75 77 Recently, Terentjev et al. developed new thermoplastic liquid-crystalline elastomers synthesized by using the telechelic principle of microphase separation in triblock copolymers, in which the large central block is made of a main-chain nematic polymer renowned for its large spontaneous elongation along the nematic director and the crosslinking is established by small terminal blocks formed of terphenyl moieties.78 The thin wellaligned ber, spun from the melt under heating condition at the temperature above the nematic-isotropic transition, shows signicant two-way shape memory effect, which is characterized by the thermal actuator behaviorreversible contraction of heating and elongation on cooling caused by the nematic director. In the spinning process, the nematic ordering and the telechelic crosslinking were formed simultaneously. The amplitude of actuation strain within the studied temperature range (408C  1108C) even can reach 500%. The transition point located at around 1008C depends on the nematic-isotropic transitions temperature. Presently, although the transition point is quite high for ordinary apparel application, this two way shape memory ber can help inspire some novel practice of shape memory ber in smart and functional textile design.

Conclusions
The new developments of spandex focus on the functional bers such as highly hydroscopic and moisture liberating spandex, highly soft spandex, heat setting spandex, chemically or chlorine resistant spandex, anti-bacterial spandex, high tenacity spandex, easy dyeing spandex. The polyester-ether elastic bers are promising bers with a wide range of uses and lower cost than polyurethane elastic ber. By controlling their molecular structure, different functional polyester-ether bers will be developed. The developments of hard elastic ber will emphasize on the production of hollow ber and lter materials in medical application. The polyolen bers XLA overcomes limitations of traditional polyolen and offers performance advantages compared to existing elastic bers. It offers processing benets to textiles mills, and enhances durability of stretch garments. The shape memory bers make the textiles with different style and applications. The future aim is to investigate two-way multi-stimulus, multi-function bionic shape memory polymer, which can be activated by thermal, humidity, chemical, magnetism, and electricity or optical stimulus and has anti-bacterial, antistatic, anti-mildew, or ultraviolet resistant functions and to establish a systematic, comprehensive, and an integrated theory of the shape memory polymer and apply the shape memory polymer in textiles.

References
1. Xinyuan, Song. Structure and elasticity of elastic ber and its dyeing and nishing (I), Printing and Dyeing 2006, 8, 44 46. 2. Fabricius, M.; Wulfhorst, B. Elastane bers (spandex), Chemical Fibres International 1995, 45 (10), 400.

New Developments in Elastic Fibers

299

3. Elastane yarns lower capacity utilization in 2006, Chemical Fibers International 2006, 1, 10. 4. Hicks, E. M. Lycra spandex ber I structure and properties, American Dyestuff Reporter 1963, Jan. 7, 33 35. 5. Ibrahim, S. M. Fibers, elastomeric, Encyclopedia of Polymer Science and Technology 1967, 6, 573 593. 6. Meckel, W.; Goyert. Thermoplastic Elastomers, Carl Hanser Verlag: Munich Vienna, New York, 1987. 7. Iyer. Recent development in polyurethanes XI, Man-made Textiles in India 1988, 31, 269 271. 8. Bonart, H. X-ray investigations concerning the physical structure of cross-linking in segmented urethane elastomers, J. Macromol. Sci. Phys. 1968, B2 (1), 115 138. 9. LEE, Han sup; Ko, Jung Hwan; Song, Ki Suk; Choi, Kyung Hee. Segmental and chain orientational behavior of spandex bers, Journal of Polymer Science Part B Polymer Physics 1997, 1882 1832. 10. Richeson, G. C.; Spruiell, J. E. Preparation, structure, and properties of copolyester-ether elastic laments, J. Appl. Polym. Sci. 1990, 41, 845. 11. Zhou Liang; Wang Wenke; Song Dongyan. Development of high performance polyurethane Elastic Fiber, Polyester Industry 2001, 14 (2), 12 16. 12. Japan Patent, J11-229277. 1999-08-24. 13. Japan Patent, J9-278144. 1997-09-02. 14. Japan Patent, WO97-46748. 1997-12-11. 15. Japan Patent, J9-78348. 1977-03-25. 16. As read on line on February 22, 2008 at http://www.lycra.com.cn/products/. 17. As read on line on February 22, 2008 http:/ /www.lycra.com.cn/products/softcomfort.html. 18. Tao Jie. New type elastic ber PBT, Overseas Textile Technology 1987, 1, 1 4. 19. Hoe, H Corterra. A new polyester bre, Textiles Magazine 1998, 2 (1), 12 14. 20. Tomasini, M. PBT A very special polyester, Chemical Fibers International 1997, 47 (1), 30 31. 21. (a) Fu-Min Lu; Spruiell, J. E. Inuence of processing conditions on structure development and mechanical properties of poly(butylene terephthalate) lament, Journal of Applied Polymer Science 1986, 31 (6), 1595 1607; (b) Boye, C. A.; Overton, A. Bull. Am. Phys. Soc. 1974 (19), 352; (c) Jakeways, R.; Ward, I. M.; Wilding, M. A.; Hall, I. H.; Desborough, I. J.; Pass, M. G. J. Polym. Sci. Polym. Phys. Ed. 1975 (13), 799; (d) Tonelli, A. E. Polymer 2002, 43, 6069 6072. 22. Gomez, M. A.; Cozine, M. H.; Tonelli, A. E. High-resolution solid-state 13C NMR study of the alpha and beta crystalline forms of poly(buty1ene terephthalate), Macromolecules 1988, 21, 388 392. 23. Davies, G. R.; Smith, T.; Ward, I. M. Dynamic mechanical behavior of oriented poly (tetramethylene terephthalate) as a function of static extension, Polymer 1980, 21, 221. 24. Tashiro, K. Solid-state transition of Poly (butylene terephthalate) Induced by mechanical deformation, Macromolecules 1980, 13, 137 145. 25. Desborough, I. J.; Hall, I. H.; Neisser, J. Z. The structure of poly (trimethylene terephthalate), Polymer 1979, 20, 545. 26. Jang, S. S.; Jo, W. H. Phase transformation of poly(trimethylene terephthalate) in crystalline state: an atomistic modeling approach, Fibers Polymer 2000, 1, 18 24. 27. Ho, R. M.; Ke, K. Z.; Chen, M. Crystal structure and banded spherulite of poly (trimethylene terephthalate), Macromolecules 2000, 33, 7529 7537. 28. Chuah, H. H. Orientation and structure development in poly(trimethylene terephthalate) tensile drawing, Macromolecules 2001, 34, 6985 6993. 29. Wang, B.; Li, C. Y.; Hanzlicek, J.; Cheng, S. Z. D.; Geil, P. H.; Grebowicz, J.; Ho, R.-M. Poly (trimethylene terephthalate) crystal structure and morphology in different length scales, Polymer 2001, 42, 7171 7180.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

300

J. Hu et al.

30. Yang, J.; Sidoti, G.; Liu, J.; Geil, P. H.; Li, C. Y.; Cheng, S. Z.D. Morphology and crystal structure of CTFMP and bulk polymerized poly (trimethylene terephthalate), Polymer 2001, 42, 7181. 31. Hong, P.-D.; Chung, W.-T.; Hsu, C.-F. Crystallization kinetics and morphology of poly (trimethylene terephthalate), Polymer 2002, 43, 3335 3343. 32. Pyda, M.; Boller, A.; Grebowicz, J.; Chuah, H.; Lebedev, B. V.; Wunderlich, B. Heat capacity of poly(trimethylene terephthalate), J. Polym. Sci. Part B: Polym. Phys. 1998, 36, 2499 2511. 33. Chung, W. T.; Yeh, W. J.; Hong, P. D. Melting behaviour of poly(trimethylene terephthalate), J. Appl. Polym. Sci. 2002, 83, 2426 2433. 34. Jakeways, R.; Smith, T.; Ward, I. M.; Wilding, M. A. Reversible crystal deformation and conformational changes in poly (tetramethylene terephthalate), Journal of Polymer Science, Polymer Letters Edition 1976, 14 (1), 41 46. 35. Hwo, C.; Brown, H. Opportunities of corterra PTT bers in textiles, Chemical Fibers International 2000, 50 (2), 53 55. 36. Chen Kequan. Structure and properties of PTT bers, Synthetic Fiber Industry 2001, 24 (6), 37 40. 37. Dupeuble, J. C. Technologies for the PBT, PTT and PET supply chain, Chemical Fibers International 2001, 51 (1), 43 44. 38. Kathiervelu, S. Polytrimethylene terephthalate (PTT) bres, Synthetic Fibres 2002, 31 (4), 11 12. 39. Yonenaga, A. PTT bre a new textile mass product, International Textile Bulletin 2000, 46 (5), 35 36. 40. Carr, P. L.; Jakeways, R.; Klein, J. L.; Ward, I. M. Tensile drawing, morphology, and mechanical properties of poly (butylene terephthalate), Journal of Polymer Science: Part B: Polymer Physics 1997, 35, 2465 2481. 41. Denton, M. J. Crimp curvature of bicomponent bres, Journal of the Textile Institute 1982, 73, 253 63. 42. Rwei, S. P.; Lin, Y. T.; Su, Y. Y. Study of self-crimp polyester bers, Polymer Engineering and Science 2005, 838 849. 43. As read on line on February 22, 2008 at http:/ /www.lycra.com.cn/products/t_400.html. 44. Zhao, Qingzhang; Xia, He. Study on the polyether ester elastic ber I, Textile Research 1994 (1), 18 22. 45. Zhao Qingzhang; Xia, He. Study on the polyether ester elastic ber II, Textile Research 1994 (2), 1 4. 46. Zhao Qingzhang; Xia, He. Study on the polyether ester elastic ber III, Textile Research 1995 (1), 36 39. 47. Yang Cheng; Liu, Xiaoya; Li, Ruxia; Wu, Dacheng. Crystallinity amechanical properties of poly (ester- ether) liquid crystalline elastic ber, Synthetic Fiber 2000, 9, 26 28. 48. Wu Shengli; Li, Guang; Jiang, Jianming. Development of thermoplastic polyether-ester elastic ber, Synthetic Technology and Application 2000, 15 (3), 32 35. 49. Japan Patent, 61-57850, 1986. 50. Japan Patent, 45350, 1984. 51. Du Guoqiang; Xu Guofeng; Yu Tongren. Hard elastic polymer material, Polymer Materials Science and Engineering 1986 (2), 1 6. 52. Sprague, B. S. Hard elastic ber, J. Macromolecular Science Physics 1971 (19), 427 432. 53. Xu Youyi; Xu Changhui; Xie Baiming. Research development of crystalline hard elastic polymer material, Functional Material 1996, 27 (1), 12 31. 54. Chun-Hui Du; Bao-Ku Zhu; You-Yi Xu. A Study on the relationship between the crystal structure and hard elasticity of PVDF bers, Macromolecular Material and Engineering 2005, 290, 786791. 55. Dow Chemical: New Lastol Dow XLA Fiber Plant in Spain, Chemical Fibers International 2003, 53, 425. 56. First Lastol Elastic Fiber Plant in Spain, Chemical Fibers International 2004, 54, 354.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

New Developments in Elastic Fibers

57. 58. 59. 60. 61. 62. 63. 64.

301

65. 66. 67. 68.

Downloaded By: [University of Akron] At: 02:19 21 April 2009

69. 70. 71. 72. 73. 74. 75. 76. 77.

78.

New Generic Fiber Nams, Fibers International 2005, 55, 141. Elastic ber Dow XLA CP for swimwear textiles, Fibers International 2005, 55, 270. As read on line on February 22, 2008 at http://www.dow.com/xla/prod/. As read on line on February 22, 2008 at http://www.dow.com/xla/prod/comfort.htm. As read on line on February 22, 2008 at http://www.dow.com/xla/prod/durability.htm. As read on line on February 22, 2008 at http://www.dow.com/xla/prod/care.htm. As read on line on February 22, 2008 at http://www.dow.com/xla/prod/design.htm. Liang, C.; Rogers, C. A.; Malafeew, E. Investigation of shape memory polymers and their hybrid composites, Journal of Intelligent Material Systems and Structures 1997, 8 (4), 380 386. Kim, B. K., et al. Polyurethane ionomers having shape memory effects, Polymer 1998, 39 (13), 2803 2808. Jeong, H. M., et al. Water vapor permeability of shape memory polyurethane with amorphous reversible phase, Journal of Polymer Science: Part B: Polymer Physics 2000, 38, 3009 3017. Takahashi, T.; Hayashi, N.; Hayashi, S. Structure and properties of shape-memory polyurethane block copolymers, Journal of Applied Polymer Science 1996, 60, 1061 1069. Lendlein, A.; Kelch, S. Shape-memory polymer, Angewandte Chemie-International Edition 2002, 41, 2034 2057. Kobayashi, et al. Woven fabric made of shape memory polymer 1992, Mitsubishi Jukogyo Kabushiki Kaisha (Tokyo, JP): United States Patent 5. 128, 197. Lee, B. S., et al. Structure and thermo-mechanical properties of polyurethane block copolymers with shape memory effect, Macromolecules 2001, 34, 6431 6437. Cha, D. I., et al. Electrospun nonwovens of shape-memory polyurethane block copolymers, Journal of Applied Polymer Science 2005, 96, 460 465. Zhu, Y., et al. Development of shape memory polyurethane ber with complete shape recoverability, Smart Materials & Structures 2006, 15, 1385 1394. Ji, F. L., et al. Smart polymer bers with shape memory effects, Smart Materials and Structures 2006, 15 (6), 1547 1554. Mark, H. F.; Atlas, S. M.; Cernia, E. Man-made bers, Polymer Engineering and Technology 1968, 2, 277. Meyer, R. V.; Haug, E.; Spilgies, G. Sources of stretch, Textile Asia 1994, 40 45. Manich, A. M., et al. Thermal analysis and differential solubility of polyester ber and yarns, Textile Research Journal 2003, 73 (4), 333 338. Moore, C. L.; Bruck, H. A. A fundamental investigation into large strain recovery of one-way shape memory alloy wires embedded in exible polyurethane, Smart Materials & Structures 2002, 11, 130 139. Ahir, S. V.; Tajbakhsh, A. R.; Terentjev, E. M. Self-assembled shape-memory bers of triblock liquid-crystal polymer, Advanced Functional Materials 2006, 16, 556 560.