Stimuli Responsive Shape Memory Polymer

In Textile Applications
Rafia Iqbal*, Muhammad Faizan Asif*, Unaiza Hassan, Javeria Raheem
[email protected], [email protected]
Department of Polymer and Process Engineering
University of Engineering and Technology, Lahore

Abstract
Smart materials are referred as those materials which show the physical change as
environment has some variation. Among the broad range of smart materials the shape
memory materials are the one which can regain their shape when the internal stress is
removed due to semi-cross linked structure. They changed their physical properties such as
dimensions, and color, when exposed to an external stimuli i.e. temperature, pressure, light,
pH etc. These materials have wide range of application including industrial, medical,
photonics and textile. Now days, textile concept has also modified and the shape memory
polymers are the best answer. Smart features of these materials such as sensing, fast response,
air permeability and elastic capability, they are preferred for textile applications. These SMP
are incorporated in fabrics to improve smart properties. They provide fascinating design,
unique control drug delivery, photochromic textiles, deodorant fabrics, super
hydrophobic/hydrophilic fabrics and many more. The present paper will give a brief review on
history of shape memory polymers, and the recent improvements and ideas. Furthermore,
future advancements in the textile field related to shape memory polymers will be discussed.

Keywords: Smart Polymers, Shape memory polymer Stimuli Responsive, Internal Stress,
Semi-cross-linked, Textile, Photochromic textiles, Deodorant fabrics, Hydrophilic fabrics,
Color design, Drug delivery

Table of Contents
1
Abstract.......................................................................................................................................................1
1. Introduction.............................................................................................................................................3
2. General framework of SMPs....................................................................................................................6
2.1. History..............................................................................................................................................6
2.2. Advantages.......................................................................................................................................7
2.3. Structure and mechanism.................................................................................................................8
2.4. Classification of SMPs.....................................................................................................................10
3. Fundamentals of Shape Memory Switch...............................................................................................11
3.1 Shape memory switches..................................................................................................................11
3.2. Phase level......................................................................................................................................12
3.2.1. Tg-type SMPs...............................................................................................................................12
3.2.2 Ti-type SMPs.................................................................................................................................13
3.2.3 Tm-Type SMPs..............................................................................................................................13
3.2.3a. Polyolefins.................................................................................................................................14
3.2.3b. Polyethers..................................................................................................................................14
3.3. Molecular level...................................................................................................................................14
3.3a. Photo-sensitive units....................................................................................................................14
3.3b. Supramolecular Units...................................................................................................................15
3.3c. Reversible molecular units............................................................................................................15
4. Shape-memory functionalities...............................................................................................................15
4.1. One way shape memory effect (OWSME)......................................................................................17
4.2. Two way shape memory effect (OWSME)......................................................................................17
4.3. Triple shape memory effect (TSME)................................................................................................18
5. Stimuli Responsive SMP.........................................................................................................................19
5.1. Temperature Responsive Polymers................................................................................................19
5.2. Light Responsive Polymers.............................................................................................................20
5.3. Moisture Responsive Polymers.......................................................................................................21
6. Shape memory polymer applications in textiles....................................................................................23
6.1. Functional properties......................................................................................................................23
6.2. Smart fibers....................................................................................................................................23
6.3. Outdoor clothing............................................................................................................................24
6.4. Shape memory fibers......................................................................................................................25

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 6.5. Damping fabrics..............................................................................................................................25
6.6. Deodorant fabrics...........................................................................................................................25
6.7. Photochromic Textile......................................................................................................................25
6.8. Super (hydrophilic/ hydrophobic) fabrics.......................................................................................26
6.9. Shape memory foams.....................................................................................................................26
7. Future directions...................................................................................................................................28
8. Acknowledgment...................................................................................................................................29
References.................................................................................................................................................29

1. Introduction
In the advance researching field, new material are still in developing phase to enhance the

properties of engineering application. In 1980s group of materials discovered which alter their

physical or chemical properties when different stimulus contact with it [1]. Such stimuli include

temperature responsive material, magnetic responsive material, stress or pressure responsive

material, pH change/solvent/moisture responsive material. Technically speaking these all are

stimuli responsive materials (SRM). Stimuli-responsive materials are also known as smart

materials [2] because they sense the change in environment and/or their own state make a

decision and change their functional properties according to purpose. Smart materials notably

change their properties such as optical properties, phase separations, mechanical properties,

shape change, surface etc. [3].

Shape memory polymers (SMP), shape memory alloys (SMA) and shape memory

ceramics (SMC) are one class of smart material that include in shape memory materials [4]. The

material studied first time with shape memory behavior in middle of 20 th century. The first

polymer having the shape memory effect (SME) was recognized by “Mather et al.” in 1940[5].

In spite of recovery, the importance of SMP was not recognized until 1960’s, when the

3
shrinkable PE films, on changing temperature, was discovered ‘Lendlein et al.’ revealed the

biomedical use of SMP as self-tightening suture in 2002[6], that polymer was deformed in

extension form, and tightened by the increase of temperature (reached to human body

temperature). The matrix of polyethylene irradiated with gamma rays as a result it memorize its

initial states. After this research in shape memory polymers has increase due to their low cost,

easy process-ability, softness and their shaping adaptability with simple processing for particular

applications by using different technique such as co-polymerization, blending, addition of fillers

etc. Shape memory effect in polymer due to presence of reversible switching transition and

stable polymer network[7].

The stable network structure in polymer responsible for their shape due to chain

entanglements, chemical crosslinking, network structure and crystalline phase. The reversible

switching transition responsible for temporary shape change due to transition in phases such as

melting temperature transitions, crystallization transitions, glass transitions, anisotropic or

isotropic transitions, reversible cross-linking [8]. Shape memory polymers have amplified during

last twenty years from both industrial sites and academia. Functional textiles, smart fibers, active

biomedical devices and interactive electronic apparatus are some real application of SMP that

have been developed. Smart textile functional materials have been developed since 1990s[9], E-

textiles, in which computing gadgets, digital equipment, and electronics are, used which

provided new features and functionality to fabrics and garments [10].

Novel functions are luminescent textiles, textile display, emotional sensing elements

textile, self-wiping textiles, temperature sensing/controlling textiles have been developed so far.

First SMPs materials were successfully synthesized based on polynorbornene with T g = Ttrans

range in between 35o – 40 oC by the “French Chime company” and commercially available by

4
“Nippon Zeon Co. in Japan” [11]. This temperature window is suitable for developing apparel

functional yarns, textiles, or fibers. Kuraray Company I in japan synthesize poly-isoprene based

SMPs. The temperature range was 67oC [12]. Co-workers and Stylios[12] have described the

consequence of innovation by using SMPs in textile area and the importance of capitalizing on

the fiber appealing, surface treatment and other benefits[13]. Intensive development of yarn,

fabrics is under-research to fulfill the desire of end user and accommodate the essential of

interior and exterior intention in textile. They have also research and produced variety of fiber

composites and yarns with variety of characteristics based on SMPs. To further enhance the

aesthetic intelligence and mechanical strength of SMPs, they produced SMPs composites yarns

with spandex. These all research proposes the potential of shape memory polymer in textile

sector has yet to be completely explored that would lead to distinctive design of textile [12].

Figure 1: Various types of SMMs in world of materials

2. General framework of SMPs

In 1941, L.B. Vernon mentioned ‘shape memory’ effect in polymer 1st time in United States

patent. He professed materials relating dental applications made of elastic memory material

5
(methacrylic acid ester resin). When this material was heating it came to its initial shape[14].

This publication seemed sooner when first shape memory composite appeared (in 1951)[15][16].

Although, SMPs were not gained significant importance till 1960s. In this century, high

temperature shrinkage tubing and films are made by polyethylene which was strongly cross

linked. Many different plastic materials had manufactured which were determined properties of

shape memory materials.

The 1st SMP, was published in 1984 by “CdF-Chimie Company, France” which was made

poly (norbornene) polymer [17]. In that year, SMPs (trade name of Norsorex) were

manufactured by “Nippon Zeon Company of Japan” [18]. The transition temperature was lied

between 35o C to 40o C but limited applications due to its processibility.

The 2 nd SMP (trade name Kurare TP-301) developed by Kurare Cooperation of Japan in

1987. This is based on poly (trans-isoprene) polymer, has Tg of -68 oC but has limitations due to

processibility[19]. The 3rd commercial SMPs, called Asmer, developed by Asahi Company of

Japan. This was based on polystyrene butadiene with Tg range from 60oC -90 oC[19].

In the late 1980s, Mitsubishi Heavy Industries developed Diisocynate shape memory

polymers. Trade names of polyurethane based SMPs were “Diary MM-4510 (polyester polyol

based polyurethane)” & “Diary MM-4520 (polyether polyol based polyurethane)”. Polyurethanes

are thermoplastics with improved processibility[15], [20]. Through the nineties, polyurethane

based SMP attained major concern of the literature because of its ability to control structure and

vary glass transition temperature. Due to thermoplastic nature, polyurethane based SMPs are

easily processed by extrusion, injection molding and blow molding and solution casting.

Polyurethane based SMPs have great chemical and ultraviolent resistance and excellent

biocompatibility[21].

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 In 1997, Liang et. al. [21] proposed utilize SMPs which had low stiffness and strength.

Earlier works in SMPs were predominantly focused on applications[22]. Now a days, these

materials have used for personal applications. Numerous groups have energetically worked on

SMPs which properties can be tuned according to desired applications.

2.2. Advantages

SMPs have wide and more dominant as compared to metals and alloys. SMPs have following

advantages[23]:

 SMPs are used various external stimuli: when heat is applied, SMPs are able to recover

its initial shape and this recovery happened by number of ways. When multi-responsive

materials are used, different responses co-exist.

 SMPs are showed highly elastic programming: through both single and multi-step

processes, this programming is done with multiple stimuli.

 SMPs have diverse range of mechanical designs: there are plenty of techniques for

fabricating switches for different type of SMPs.

 SMPs have ease of processing that’s why their properties are tunable: properties of SMPs

can be tuned according to desired applications.

 SMPs are biodegradable, and have good compatibility with human body. They offers

special chances for remedial (Cardiovascular applications), organic and garment-

integrated devices.

 SMPs are light in weight and occupied large volume (foam). Due to their light weight,

they are used by “NASA and US Air Force Research Laboratory”. They are also vital for

many applications such as aerospace components and devices.

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  SMPs possess much lower thermal conductivities. When thermal insulation is required,

low thermal conductivity is desirable.

 SMPs have recovery strain higher order of magnitude.

2.3. Structure and mechanism

Memorize
Switch Phase
temporary shape
Mechanism of
Two Phases
SMPs
Memorrize
Fix phase
original shape

Figure 2: Shape memory polymer mechanisms

Switch phase has transition temperature which helps in recovery. Glass transition temperature

and melting temperature depend on amorphous and crystalline nature of switch phase[24].

Temporary shapes are formed above the transition temperature, and kept frozen below transition

temperature. Permanent shapes can be obtained by heating again above transition temperature.

While explaining chemical structure, SMPs are phase-segregated linear copolymer which has

both soft and hard segments[25], [26]. Soft segment play role of switch phase and hard segments

act as a fix phase. Following steps describe temperature base mechanical cycle:

1. When SMP is heated above Ttran of hard segment, material is processed.

2. Original shape is memorized by cooling hard segment below Ttran

3. When SMP is cooled, soft segment is deformed resulting in stresses and temporary shape

is fixed.

8
 4. Heating SMPs above Ttran of soft segment and stresses are removed to obtain original

shape.

SMPs are considered as multi block copolymer. The molecular level mechanism of forming

impermanent form “Shape B” and recuperating original foam “Shape A” is described in

following figure:

Figure 3: Molecular mechanism of multi-

Following steps describe mechanism:

1. Shape A is achieved by providing heat to the material above the glass transition

temperature of hard segment, together with external forces applied to material to get

different shapes.

2. Cooling the material below glass transition of soft segment, material retains its shape.

3. Temporary shape B is fixed below the glass transition temperature.

4. Shape A is recovered again when heating above glass transition temperature.

The elasticity change of SMPs is described in following steps:

1. When temperature is above Tg “glass transition temperature”, material goes from glassy

state to rubbery state, where it can easily deformed.

2. Cooling material below its glass transition temperature, deformed shape remains stable.

9
A high value of elastic modulus and long relaxation time helps to keep sharp transition from

glassy to rubbery state.”

2.4. Classification of SMPs

Classification of SMPs[27] has been done on the basis of:

 Structural: chemically crosslinked, and physically crosslinked

 External Stimuli: temperature, pH, light, magnetic and electrical field

Figure 4: integrated approach to SMPs based on structures, stimulus and shape memory functions[11]

10
3. Fundamentals of Shape Memory Switch
3.1 Shape memory switches

SMPs are those polymeric materials which have the aptitude of recovering from a ‘stable’

temporary shape to a ‘memorized’ durable shape in a skillful method on contact with an external

change, generally referred to as ‘stimulus’[28]. SMPs usually has two phases: “fixed state” and

“reversible state” that can be referred as hard segments and soft segments of that material,

respectively [17]. The fixed state is often comprised of long ‘array’ of H-bonds (hydrogen

bonding) sites and that provide physical bonding/cross-links. These cross-link sites hinder

adjacent chains slithering from each other when these are subjected to deformation. The

transformation or switching temperature (Ttrans), allows material to gain its fixed shape, is either

linked with Tg or Tm depend on type of polymer used[30]. In thermally activated SMPs distortion

is stored elastically as macromolecular chain. It is their entropic desire for shape recuperation.

SMPs when subjected to or above Ttrans, they develop large elastic deformation which can then be

fixed by cooling SMPs to or below Tg. The deformation can be regained by reheating the SMP at

Ttrans. This is repeated several times to get shape memory switches[31]

Figure 5: Mechanism of SMPs switching

11
The SMP fabrics can be made to fit in the consumer’s body. This is done by switching between

temporary shapes and permanent shape of the fabric and no outstanding pressure is exerted on

the consumer’s body[12]. Shape memory effect is not an inherent property that means that this

effect is not shown by polymer themselves. This effect is a combination of polymer morphology

and processing which can be understood by functionalization of polymer[32]. SMPs are elastic

polymer networks that are armed with suitable stimuli-responsive switches[33]. Polymer

structure consists of net points and molecular switches. Permanent shape is determined by net

points and net points are generally of chemical (covalent bond) and physical interaction nature.

The molecular mechanism of the SME is demonstrated for the thermally induced shape-memory

effect in Fig.5 Domains of block copolymers act as net interactions (hard segment) and chains

act as molecular switches. Molecular switches have a specific Ttrans. This Ttrans is a switching

segment and its working phenomenon is explained earlier in this topic[34].

3.2. Phase level

Shape memory polymers are constructed through various ways. Like T g in amorphous polymers,

Tm in semi crystalline polymers and Ti in liquid crystals. Ti is isotropic temperature of liquid

crystals where they change their phase to isotropic clear liquid. These T g ,Tm and Ti are

considered as switch phases of these polymers[27], [35].

3.2.1. Tg-type SMPs

This type of Shape memory polymers need a larger recovery stress or stimuli and possess higher

strengths at both high and low temperature limits. Tg-type SMPs show relatively sluggish shape

recovery as compared to Tm- or Ti-type SMPs because of their wider glass transition interim,

which stuck their application where quick shape recovery is required. Thus, Tg-type SMPs have

become more demanding with the current extensive uses. These type of polymers’ properties can

12
also be altered by solvent such as ‘organic solvent and water’[36][33]. This is because of the fact

that the water which is absorbed, weakens the material’s H-bonding and as a result of which

moisture decreases the Tg of the SMP and allows shape recovery at room temperature. T g-type

SMPs are Epoxy, acrylate-type polymers[3], polynorbornene[37], poly(glycerolco-dodecanoate)

etc.

3.2.2 Ti-type SMPs

Ti type SMPs has a notable reversible transformation in polymer chain alignment, allowing the

development of mutable figure variations. Photo-induced shrinkage or twisting, have been done

by using LCEs. For example, film made up of LCEs bends towards the track of light irradiation.

Note that the variation in shape occurs parallel to the course of light divergence after exposing it

to 366 nm wavelength of light. When the bent or distorted film is out to light with a wavelength

larger than 540 nm, it returns back totally to its initial flat shape. The bending–unbending cycle

of such manner can be repeated without any obvious fatigue [38]. The Liquid Crystal phase that

acts as the shape–memory switch can be either a smectic phase or nematic phase. LCEs are being

prepared by introducing Liquid Crystal monomers in side chains or main chain of the

elastomer[39].

3.2.3 Tm-Type SMPs

These types of SMPs have semicrystalline phase as switch phase. Crosslinked Polyethylene is

first synthesized semicrystalline. Polymers having 20-100oC Tm range are used to manufacture

SMPs[40]. Tm type SMPs are categorized in 3 categories based on the type of semicrystalline

segment acting as switch phase.

13
3.2.3a. Polyolefins

Polyolefin-based Shape Memory Polymers have few H-bonds between the switch points and the

fixed points due to the intrinsically non-polar nature of Polyolefins. Thus, they frequently form a

reliable whole micro-phase separation assembly compared with polyether or polyester based

SMPs[41]. Examples of these kind of SMPs are PE, poly(1,4-butadiene) PB, PE-co-1-Octene,

trans-polycyclooctene[42] TPCO.

3.2.3b. Polyethers

SMPs based on polyether have strong molecular interfaces among switches (flexible units) and

the net-points. Hence, in future it will be desired to enhance the micro-phase separation of SMPs,

especially “segmented SMPs” which will subsequently result in optimizing their shape–memory

properties[43][5]. Examples of this kind are polyethylene oxide PEO, poly(tertramethylene ether

glycol) PTMG, poly(ethylene glycol) PEG[44].

3.3. Molecular level

be triggered by ‘intermolecular chain interactions’ or ‘reversible chemical reactions’ occurring

within the structure. So, a molecular switch can be prepared on a molecular level by conducting

reversible reactions under special conditions, and by utilizing reversible units as molecular

switches[45]. There are mainly three types of molecular units which can act as molecular

switches. These molecular units include supramolecular, photosensitive units and mercapto

which have been successfully used to exhibit shape memory effect.

3.3a. Photo-sensitive units

These are the most prevalent molecular units. Light can be accurately monitored because it is a

clean energy. First light sensitive SMP was prepared by Lendlein et al. by adding cinnamic e
14
groups into polymer main chain which are photosensitive. These groups act as molecular

switches. Covalently cross-linked bonds are produced by Cinnamic groups under UV-light of >

260 nm, although these bonds are dropped under UV-light irradiations of < 260 nm[4][37]. High

shape recovery ratio is exhibited by these SMPs but low ‘flexibility ratio’.

3.3b. Supramolecular Units

Supramolecular units have been used since 5 years to shot temporary shape properties in SMPs.

H-bonding in supramolecular relations can detach at higher temperatures which can make

material deformable. Chen et al. prepared a complex H-bond system designed by “pyridine

groups” as H-acceptors [38] to prepare “PU supramolecular networks” by exploiting a pyridine

derivative, Py-SMPUs.

3.3c. Reversible molecular units

Mercapto units are utilized to make reversible molecular units which will act as switch units. In

cellulose acetate products with a cross-linked mercapto group, named as CA-MA. ON-OFF of

system is triggered by redox reaction. The time of recovery of these films is high i.e. 96h[46].”

4. Shape-memory functionalities
Shape-memory-effect (SME) in polymer is inherent property to reminisce the fixed shape even

after several deformations. The shape deforms during phase transformation are known as

martensite and austenite[15], [31]. The shape change when stress or stimuli effect on the

structure of material this process is martensite process and recovery of material to original

position or shape is austenite process. The reverse transformation is due to heating recovery of

inelastic strain; The martensite effect have be reoriented by stress applying on material and

return to austenite produce a large deformation have similar amplitude but with inelastic strain

[47]. Shape memory effects in polymer is normally shown by relaxation and recovery up to
15
400% of polymeric chains due to change in stimuli mostly temperature. In general Polymer

chains consists of two phases fixity phase and switch phase,

Figure 6: Light-induced SMPs (a) permanent shape; (b) temporary shape and (c) recovered permanent shape[17]

Generally SMPs have at least two different segments a stable segment and secondary phase

(which transform in other shape due to external trigger). The stable phase retain their original

shapes with chemically crosslinked networks crystalline phase and interpenetration networks and

secondary phase fixed the temporary shapes by crystallization either by glass transition

temperature or melting temperature. So, secondary phase allows fixative the temporary shape

while the stable phase remembers the original shape of the material [1],[9], [32]. On the basis of

shape that can memorized by a polymer, these are classified as one way shape memory effect

(OWSME), two ways shape memory effect (TWSME) and Triple shape memory effect (TSME).

Figure 7: Illustration of shape-memory functionalities of SMPs

16
4.1. One way shape memory effect (OWSME)

Mostly OWSME prominent in SMPs, it is inherent property of smart polymers. The process

consists of two steps name as programming phase and recovery phase. In programming phase a

temporary shape is induced in fixed phase. In short this process shows reverse transformation

process where the temporary shape is in its martensite phase reverses[10] back to original shape

austenite phase when heat is applied. OWSME characteristics they only remember its original

shape when heat is applied after its temporary shape[48].

Figure 8: Macroscopically mechanism of OWSME

4.2. Two way shape memory effect (OWSME)

Two ways shape memory effect is not an inherent property its thermomechanical cyclic loading

of stress in material produce this effect in material. The material has ability to reminisce both

segments fixity segment and switch segment over cyclic change mechanism either spontaneously

or non-spontaneously[49]. In short TWSME remember both shapes by thermal cycling (both

heating and cooling). When material remember the behavior then it’s possible to alter the shape

of material in both ways spontaneously without applying stress.

17
 Figure 9: macroscopically mechanism of TWSME
At macroscopic level the specimen remember the both shape, large deformation in switch phase

(martensite) cause dislocation introduces so stabilized this phase, this dislocation also present in

fixed phase after reverse back to its parent shape[49].

4.3. Triple shape memory effect (TSME)

Unlike OWSME in polymer triple or multiphase SME is ascribed as multiphase polymer

network which contain two or more than two separate domains which shows the individually

transitions. Triple way shape memory effect has ability to transform into 2 temporary shapes and

reverse back to its first permanent shape; these dual shape changes produced due to physical

cross-linked or chemical cross-linked network structure[28][29].

Figure 10: Illustration of Triple way shape-memory mechanism

18
5. Stimuli Responsive SMP
5.1. Temperature Responsive Polymers

Temperature or thermal responsive SMPs are the most commonly studied and used responsive

polymer among all. In this kind of SMPs, the shape memory mechanism is activated by glass

transition (Tg) or melting temperature (Tm) of polymer depending on its morphology [51].

The thermal stimuli responsive polymer has two shapes

 Shape Reprograming/fixing

 Shape Recovery

Figure 11: Temperature shape memory cycle

detail.

 Below the Ttrans of the switch phase the chain does not show any movements. But when

the temperature increases above from Ttrans, the chain start slipping over another.

 In this state, if force is applied on material, elastic deformation can be observed in the

chains.

 On other hand, when temperature is below Ttrans , the applied stress will be removed and

the switching phase will fix the chains keeping the temporary shape

19
  Finally, on increasing the temperature above Ttrans, the SMPs will regain its shape,

because this original shape is entropically more favorable.

Example:

1. poly( N -isopropylacrylamide) (PNIPAM)

2. poly(oligo ethylene glycol (meth)acrylate)s (POEG(M)A)s

Figure 12: Mechanism step of temperature Responsive SMP. Tg, 1 represent Tg of hard phase and Tg,2 represent
Tg of switching phase

5.2. Light Responsive Polymers

The polymers that show change in their properties due to light stimulus. The light responsive

SMPs shows the shape memory effect by absorbing the light energy and convert it into heat

energy [53]. When light falls on such polymers, the molecular properties change can be observed

i.e. shape change, electrical properties, transmittance, wettability, solubility, compatibility and so

on. The response change in properties depend upon the light intensity, wavelength and

irradiation time[51].

The usefulness and the application capability of such polymers are mostly dictated by following

three parameters

 On light triggering, the magnitude at which property change.

20
  The rate of change occurs.

 The process convertibility to its original shape

Light responsive shape memory polymer mechanism has been described. On the incorporation of

chromophore (a photo response functional group) in polymer chain, the photo-responsive

polymer generated [54]. For shape memory effect reversible chromophores used, that can change

material properties in two photo-stationary states and are used as switches. On the light

excitation of specific wavelength, such polymers undergo a reversible isomerization [17].

Figure
13: Reversible Chromophores Mechanism [54]
The photochromic interconversion between isomeric structures permits exchanging the

properties of the polymeric material by illumination at two distinct wavelengths [54][45].

Examples:

Figure 14: Light Responsive SMP [17]

5.3. Moisture Responsive Polymers

Recently the SME was observed due to change in moisture content or water absorption content

by polymers. A pyridine unit in Polyurethane was introduced by Hu et al to improve moisture

21
absorption [2] and this effect was studied first time in detail by Huand and co-workers [55]. The

change in properties should be thermally reversible. i.e. polyurethane SMP [56]. On the

absorption of water the crystalline segment of PU was dissolved, which results in switch segment

disappearance [55].

The usefulness and the application capability of such a polymer are mainly dictated by [55]

 The immersion time

 Absorption content

Moisture responsive shape memory polymer mechanism has been described. On increasing the

moisture absorption content of SMPs, their glass transition temperature decrease as the hydrogen

bond present in them weakens. Absorbed water can be completely removed on heating by which

polymer chain and water interaction are eliminated. The T g returns to its original value. Two

types of effects usually observed on the absorption of water by SMP, namely bound water and

free water. The glass transition temperature of SMP considerably reduce because of bound water

while free water has negligible effect, as it will totally remove through evaporation [56].

Figure 15: Moisture Responsive SMP Mechanism Steps

22
6. Shape memory polymer applications in textiles
The impressing properties of shape memory polymer make them most interesting candidates for

several applications in recent year. SMPs have been developed mainly for engineering and

biomedical applications which includes orthodontic archwire, muscular stunts, aerospace’s parts

but the use of these materials in textiles also increase in recent years because of its functional

(permeability, wrinkle free fabrics, ironing free, smart textiles) properties[48].

6.1. Functional properties

Functional properties of SMPs play an important role in textile applications which includes

volume expansion or contraction, moisture permeability, refractive index. These properties are -

very significantly prominent above and below Tg/Tm because of difference in kinetic properties

of molecular chains and chains behavior. One of major applications is in sportswear, heat

retaining property and gas barriers properties. Raining coat is also best example in which

material could change their structural properties to keep moisture out and comfortable to carry

and wear, in cold climate it change again to keep the wearer warm[48].

6.2. Smart fibers

SMPs that compatible with body fluids, dual shape memory, high recovery in shape, high fixity

and material have ability to deform instantly temporary shape are used in smart fibers. They

mostly used to fill small or difficult wound where access is limited. The other potential

applications are cardiac valve repair, heart stunt, bones holding screws due to their temperature

adaptive change features. SMPs coated surgical protective garments are used due to their thermo-

physiological properties and comfort, duvet products[2].

23
 Figure 16: Smart vent structure in smart fabrics[2]

6.3. Outdoor clothing

Layers of SMPs are incorporated in multilayer garments, used as protective coatings and high

quality leisure garments. Wide range temperature variation property with adaptable features

makes SMPs most promising garments. United States Army Soldiers Systems Center synthesis

wet or dry suits for their marine force to keep them warm in marine environment and provide

thermal insulations. SMPs are light weighted so they mostly used for such purpose. Other

applications are head caps, shirt neck bands, fishing yarns[11].

Figure 17: Stimuli responsive polymer woven fabrics with time recovery (a) 0 sec (b) 30 sec (c) 60 sec [2]

24
6.4. Shape memory fibers

Shape memory polymer fibers have excellent compatibility with body because of its polymeric

nature; they look similar foam as other normal garments or conventional clothes. Spandex fibers

widely used in market before SMPs fibers but it possess high pressure on wearer due to high

elasticity in fabrics so SMPs fibers replaced spandex because of their comfort sensation, intimate

apparel and low presser exert on wearer. Low pressure socks, cotton garments with SMPs fibers,

they shows wrinkle free effect[8].

6.5. Damping fabrics

SMPs have good impact / damping strength at glass transition temperature (switching

temperature). Secures (block co-polymer polyethylene terephthalate and poly caprolactone)

SMPs fibers are used in seat belts and other safety fabrics. They absorb the impact force or

kinetic force by utilizing the damping properties and expand as cushions for safety of

passenger[48].

6.6. Deodorant fabrics

Polymeric hydrogels such as N-isopropylacrylamide used as deodorant fabrics combine on the

textile surface. They are capable to release the deodorant agents at specific temperature. The

hydrogels are mostly used for this purpose combine on textile with functional groups. These

fabrics are not widely used because of soft handling and high stability issue[48].

6.7. Photochromic Textile

Photochromic fabrics have been widely used in textile as color change material. They absorb the

light change color depend on the wavelength of absorb light. Many organic photochromic

materials discovered mostly azeobenzenes, viologens and spiropyrans mostly used in industry.

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These SMPs materials are widely used in Jacquard fabrics, embroideries and printed garments

for sake of decoration and soft display[38][48].

6.8. Super (hydrophilic/ hydrophobic) fabrics

SMPs fabrics are used as smart surfaces with reversible switching between hydrophobicity and

hydrophilicity and wettability. These materials are used in industrial applications for self-

cleaning surfaces and Tuneable optical fibers. The double structure helps the components

behave in both cases when the temperature is above LCST or below LCST behavior.

Figure 18: Stimuli responsive polymer textile applications[2]

6.9. Shape memory foams

Shape memory polymer foam has been widely used in aerospace industry, weight reducing

agent, as foam in pillows[48]. The pillow filled with SMPs foams remember the neck and

shoulder shape of user body and change their shape at body temperature to provide a body

comfort. SMPs foams used in shoe insoles which effectively enhance the shoe fitting.

26
Figure 19: Shape memory foams applications[2]

Table 1: Overview some example of SMPs[27][33]

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7. Future directions
Due to the fascinating system of SMP, a different potential application has been investigated.

SMP has been widely used for medical application but now commercially available polymers

also have industrial application. This is the drive way of further improvement and the

applications of SMP. There is still room for further growth in the distinct properties of current

SMPs. Recently, different chemical synthesis method are used to develop novel SMP structure.

They provide the deeper understanding of the structure property relationship.

The aspect of designing the novel SMP are the tuning of their switching temperature. The

SMP with low transition temperature are preferred for biological application. However, high

temperature SMP has also got attention due to excellent thermal stability combined with better

mechanical properties. Such SMPs has high elastic modulus which is essential of many potential

applications. Triple and multiple SME can be achieved by tuning of transition temperature.

Tuning can be done by using the monomer of desired temperature or post-synthesis method i.e.

addition of switchable units, solvent vapors, additional stress. Mostly the stimuli used to trigger

SME are thermal and light induced. These stimuli can be easily used in every application. But

stimuli, which can trigger the SME will be extended further. The chances of internal heating of

SMP will be expanded. Recent proposals mostly include IR heating, photo-thermally induced

heating, and inductive heating. Other possible aspect of new SMP regarding to photo induced

SME is tuning of the wavelength. It can be done by tuning of energy transfer way, up conversion

process and by relative photo-switch.

One more possible future aspect regarding to SMP is that without any extra external

involvement (usually heating) required is triggered during material usage. Such SMPs have a

wide range of application in biomedical field, but seem to be far from being reached. Another

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future target in SMP is tuning of required shape transformation. Regarding to this, multiple SME

effect has been investigated. But the improvement in high fixity and recovery is main objective.

Higher fixity and recovery provides higher stability, higher cycle life and better mechanical

properties. The general trend is molecular mechanism base which shows crystallization induced

expansion. A kind of an opposite SMP that provide expansion on heating while cooling induced

contraction could be of interest.

SMPs have many potential applications in many fields but their availability is a crucial

issue. It is due to difficult process-ability and fabrication method. Shape fixity is improved by

crosslinks, which is formed by chemical synthesis. The chemical crosslinking is still an issue for

the industrial application. Whereas physical crosslinked material does not provide improved

mechanical properties as chemical one.

8. Acknowledgment
The final outcome of this project would not have been possible without the guidance, and help of

Dr. Umer Mehmood, assistant professor at department of Polymer and Process Engineering,

UET. The authors are grateful to Department of Polymer and Process engineering for the general

support.

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