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A review of actively moving polymers in textile applications

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DOI: 10.1039/b922872a

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APPLICATION www.rsc.org/materials | Journal of Materials Chemistry

A review of actively moving polymers in textile applications†

Jinlian Hu* and Shaojun Chen
Received 3rd November 2009, Accepted 27th January 2010
First published as an Advance Article on the web 10th March 2010
DOI: 10.1039/b922872a

Actively moving polymers being developed rapidly have drawn wide attention. A review is presented to
highlight the most important areas and directions in textile applications. The molecular structure of
actively moving polymers is introduced firstly. The textile applications of actively moving polymers are
then summarized from the fibre spinning (including wet spinning, melt spinning and electro-spinning),
fabric manufacturing, shape memory finishing technologies and water vapor permeability
Published on 10 March 2010 on http://pubs.rsc.org | doi:10.1039/B922872A

investigation. Additionally, the challenges of actively moving polymers in textile applications are
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pointed out and some research directions are suggested.

1. Introduction
Actively moving polymers (AMPs) are one class of stimuli-
sensitive polymeric materials which have the capability to
respond to specific changes in their environment (e.g. tempera-
ture, light and pH) by adopting certain macroscopic shapes.1–5
According to their moving behavior, they are classified as shape
memory polymers (SMPs) and shape changing polymers (SCPs)
by Behl and Lendlein.1 As for the SMPs, they can be deformed
and fixed in a temporary shape. Moreover, the temporary shape
can be recovered to its original predefined shape by exposure to
external stimulus.6–9 However, the SCPs change their shapes as
long as they are exposed to a suitable stimulus. Alternatively, the
original shape is recovered when the stimulation is termi-
nated.10,11 Compared with SMPs, the geometry of SCPs can not
be varied. Instead, the temporary shape of SMPs can be easily
changed by tailor-made programming from one to another. The
typical actively moving behaviors of SMPs and SCPs are pre-
sented in Fig. 1.
Institute of Textiles and Clothing, the Hong Kong Polytechnic University,
Hung Hom, Kowloon, Hong Kong, China. E-mail: tchujl@inet.polyu.edu.hk;
Fax: +00852 27731432; Tel: +0085227666437
† This paper is part of a Journal of Materials Chemistry themed issue on
Actively Moving Polymers. Guest editor: Andreas Lendlein.
At the molecular level, AMPs including SMPs and SCPs are
elastic polymer networks which consist of switches and netpoints
as shown in Fig. 2. The netpoints determine the permanent shape
of polymer network and can be of a chemical (covalent bonds) or
physical (non-covalent bond) nature. Physical cross-linking is
formed through the crystals, amorphous hard domains or other
forms of entangled chains.1,2,4,5,12 The supramolecular complexes
based on cyclodextrin (CD) inclusions are also reported to be
physical netpoints recently.13–15 The switches are the major
constituents and responsible for strain fixation and partial strain
recovery. Either the amorphous phase with a low glass transition
temperature (Tg),16–18 or semi-crystalline phase with a low
melting temperature (Tm),11,19–21 or liquid crystalline (LC) phase
with a low isotropization temperature (Ti) can serve as the
switches in the thermally-induced AMPs.22–25 So far, the amor-
phous phase, the semi-crystalline phase26,27 and even supramo-
lecular entities9,28,29 are mainly utilized for constructing SMPs,
while SCPs are mainly observed in the liquid crystalline elasto-
mers (LCEs) and cross-linked polymers with stress induced
crystallization.22,11 To display shape memory functionality, the
polymer network of SMPs has to be temporarily fixed in
a deformed state under environmental conditions. The reversible
molecular switches can prevent recoiling of deformed chain
segments when the switch is turned ‘‘off’’, e.g. resulting from the

Jinlian Hu obtained her PhD Shaojun Chen studied for his

from University of Manchester PhD in polymer science at the
Institute of Science and Tech- Hong Kong Polytechnic
nology, and now is the professor University. He has studied shape
of Hong Kong Polytechnic memory polymers for more than
University. Her research fields 8 years, and his research interest
include shape memory materials includes synthesis and charac-
and textiles. She has published terization of smart polymers,
several books, more than 200 functional polymers and supra-
papers and been awarded more molecular polymers for textile
than 10 patents. applications.

Jinlian Hu Shaojun Chen

3346 | J. Mater. Chem., 2010, 20, 3346–3355 This journal is ª The Royal Society of Chemistry 2010
 View Online

recrystallization of a semi-crystalline soft phase. Under an
environmental trigger such as heat or light, the original shape will
be mostly recovered from the deformed shape in the SMPs since
the switch is turned ‘‘on’’, e.g. resulting from the crystal melting
of the soft phase. However, the geometry of SCPs is determined
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by its original three dimensional shape. The process of stimulated
deformation with subsequent recovery can be repeated many
times and the geometry of shape changes can not be varied in the
SCPs.1 For example, the LCEs change their shapes when the
temperature is raised above Ti due to the phase transition from

Fig. 1 Actively moving behaviors of SMPs (a) and SCPs (b). The photos show that the flower made of thermally-induced SMP recovers its original
shape very quickly when the conditional temperature is raised to above its transition temperature while the SCP film bends on heating as well as reverse
bending on cooling process. Adapted with permission from ref. 10.

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Fig. 2 Illustration of molecular structure of AMPs. The model indicates
Published on 10 March 2010 on http://pubs.rsc.org | doi:10.1039/B922872A
that the AMPs consist of switches and netpoints. The netpoints can be of
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a chemically cross-linking, physical cross-linking and other entangled
chains like interpenetrated networks and CDs interlocking. The switches
include crystallization soft phase, amorphous soft phase, liquid crystal-
line phase and supramolecular switches.
LC phase to isotropic phase. However, the changed shape will
recover to its original shape when the temperature is cooled down
below Ti since it enters into the LC phase again.
SMPs were firstly discovered in 1984 and have continued to
evolve.4,30–36 According to the netpoints, SMPs can be divided
into physically cross-linked SMPs17,37 and chemically cross-
linked SMPs.2,30 On the basis of the switches, they are further
classified into SMPs with the amorphous switching segments
and SMPs with the semi-crystalline switching segments.2 Addi-
tionally, degradable SMPs are usually highlighted because of
their considerable research interest for medical applications like
those by Lendlein et al.38,39 Sometimes, the SCPs are also
described as two-way SMPs or reversible SMPs due to the
similar two-way shape-memory effects (SMEs) associated with
the two-way shape memory alloy.2,11,40 Based on the nature of
stimulus, SMPs are widely described as the thermally-induced
SMPs, light-induced SMPs, electro-active SMPs, pH-responsive
SMPs and water/moisture-driven SMPs in the previous
reviews.1,2,4,12,30
AMPs have drawn wide attention particularly due to the shape
moving functionality triggered by various stimuli, low cost, low
weight and easy manufacture process. Recent developments
include medical, spacecraft and textile applications. Several
reviews have covered the medical applications of SMPs.41,42 In
the following sections, the textile applications of AMPs will
mainly be described from the fibre spinning, fabric
manufacturing, finishing technology and WVP investigations.
2. Actively moving polymers for fibres/fabrics
2.1. Wet spinning SMP fibres
The SMPs have been investigated for several decades, but until
recently fibre spinning technologies have achieved good prog-
ress in the production for textiles with shape memory func-
tionality. In 2006, Hu et al. first reported the development of
SMPU fibre with complete shape recoverability by wet spin-
ning.43 Through the comparative studies with other man-made
fibres, the elastic modulus (E0 ) of SMP fibres (SMFs) was found
3348 | J. Mater. Chem., 2010, 20, 3346–3355
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Fig. 3 Comparison of elastic modulus between SMPU fibre and existing
man-made fibres. The logE’ curves show that the SMP fibres like PU56-
120 and PU66-120 show significant modulus decrease at the normal
apparel using temperature range, e.g. from 20  C to 60  C, while the other
man-made fibers have little change in the modulus during this tempera-
ture range. Adapted with permission from ref. 43.
to decrease significantly at the transition point during the
normal apparel using temperature as shown in Fig. 3. However,
the E0 of other man-made fibres change little and their transition
temperature is not in the normal apparel using temperature
range. At the same time, Hu et al. found that thermal shrinkage
and irreversible strain were the two opposite factors to influence
the SME of SMFs.44 To achieve complete thermal responsive
recovery, the steam vapor thermal set treatment technology was
suggested to diminish the thermal shrinkage of SMFs because
the high pressure steaming had a huge influence on the
morphology of SMFs like the crystallinity of hard segments,
phase separation and fibre’s tropism structure. As a result, the
SMFs are expected to sense their environment and adapt to
them microscopically at the normal apparel using condition. Hu
et al. studied these functionalities in relation to the preparation
technologies. In addition to the traditional wet spinning process,
the fibres were heat set before they were taken up on the winder.
Their comparison study between shape memory polyurethane
(SMPU) films and SMFs showed that the hard segments of
SMFs were more readily aggregated into hard domains, and the
SMFs showed lower shape fixation, but higher shape recovery
and higher recovery stress.45 Wet spinning leads the application
development of SMPs in the textiles field. SMPs products are
allowed to be produced directly using the SMFs by weaving or
knitting methods. As one kind of new textile fibre, the proper-
ties of SMFs are brought forward to meet the textiles process.
Wet spinning SMFs as a good start of application in textiles
give many theoretical and practical directions such as the rela-
tionship between spinning parameters and fibre properties, and
the utilization of SMFs in textiles and garments. However, the
output and efficiency restrict the development of wet spinning
SMFs due to its lower spinning velocity. The tenacity, breaking
elongation and tactility should be considered when making the
SMFs. Materials researchers are encouraged to improve the
molecular weight of polymer or viscosity of fibre spinning
solution because another problem associated with wet spinning
fibre is its low tenacity.
This journal is ª The Royal Society of Chemistry 2010

2.2. Melt spinning SMP fibres
The study of bulk polymerization provides the foundation to
achieve melt spinning of SMFs without solvent.16,46 Investiga-
tions on the relationship between the molecular structure like
soft segment, hard segment and molecular weight of SMPs and
SMEs result in the birth of melt-spun SMFs.47,48 The comparison
study of wet-spun SMFs and melt-spun SMFs showed that the
melt-spun SMFs showed higher tenacity, shape recovery and
shape fixation as compared with wet-spun SMFs (see Fig. 4). The
reason is proposed that the melt-spun SMFs have the higher
phase separation and the melt spinning technology allows
producing well-organized soft phase and hard phase.49 In addi-
tion, using the melt spinning method, a multi-walled carbon
Published on 10 March 2010 on http://pubs.rsc.org | doi:10.1039/B922872A
nanotube (MWNT) was also incorporated into the SMFs to
improve the shape recovery and recovery force. Even electro-
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active SME was also achieved in this kind of SMP/MWNT
fibre.50 Similar to the wet-spun SMFs, the melt-spun SMFs were
also subject to different heat treatments to eliminate internal
stress and structure deficiency caused during the melt spinning
Fig. 4 Strain-stress curves of wet-spun SMFs (a) and meting-spun SMFs
(b). The curves show that the wet-spun SMFs have shape fixity of 80%
and shape recovery of less than 85%, while the melt-spun SMFs have
shape fixity of above 85% and shape recovery of about 90%. Adapted
with permission of ref. 49.
This journal is ª The Royal Society of Chemistry 2010
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process. Thus, the melt-spun SMFs are expected to obtain
comprehensive outstanding properties through the thermal
treatment.51 Before these investigations, Kaursion et al. had
obtained the melt-spun SMFs in 2006 using the commercially
available SMP (MM-4510). Their investigations also suggested
that the shape recovery and mechanical properties of SMFs
could be improved with the post-spinning operations and heat-
setting operations. The reason is that polymer chain will be more
tropism, which is increased with the increase of drawing ratio,
and the phase separation morphology can be modified efficiently
by the heat treatment.52
During the melt spinning process, 100% of the polymer melt is
changed to the fibre form. The advantages of melt spinning are
not limited to its simple technology. This kind of fibres can be
stretched as they leave the spinnerets, facilitating the production
of very thin fibres. However, the challenges of melt spinning
SMFs are the uniformity of fibre drawing, mechanical properties
and thermal resistance of the final fibre. Thus, the materials
scientists are encouraged to improve the structures of SMPs or
SMFs for uniform drawing, heat tolerance and modify the
thermal degradation of SMPs etc.
2.3. Electro-spinning SMP nanofibres
Polymer nanofibres have been attractive materials for a wide
range of applications due to their large surface area to volume
ratio and unique nanometre scale architecture built by them.
Electro-spinning is a process that produces polymer fibres with
ultrafine diameters. In 2004, SMP nanofibres with average
diameter of 400 nm were firstly electro-spun from the SMPU
solution by Jung et al.53 In addition to good shape recovery and
shape retention, many unique properties are developed in the
electro-spinning SMP nanofibres. For example, in the SMP
nanofibre/nonwoven electro-spun from the SMPU solutions
incorporating polymeric styryl dye (StD), acid-sensitivity, which
showed a color change from reddish orange to yellow peak in the
Fig. 5 Dependence of WVP of nanofibre nonwoven on relative
humidity. The plots show that the SMPU nanofibre nonwoven have
much high WVP at low relative humidity, e.g. below 50%, but a small
WVP at higher relative humidity, e.g. above 80%. However, the elastic
PU film and SMPU bulk film show little change to the variation of
humidity.
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presence of acid, is also achieved.54 In 2005, SMPU nonwoven 2.4. Shape changing polymer fibres
containing nanofibres with average diameters of 800 nm were
The textiles applications are moving to the development of
also electro-spun from SMPU with 40–50 wt% hard segment
SMP fibres. SCPs are actually more attractive because of their
content by electro-spinning process.55 Recently, Hu et al.
designed changes upon heating as well as upon cooling.
reported the electro-spun SMPU nanofibres with diameters
However, the disadvantage of SCPs like high cost and low
ranging from 50 nm to 700 nm using the biodegradable PCL-
quantity manufacture prevent them from practical application
based-SMPU.56 Their systematic investigations on the influence
in the textiles field. Their present investigation is limited to only
of electro-spinning parameters showed that the diameters and
Lab’s exploration. For example, after triblock thermoplastic
morphology can be controlled by the applied voltage, feeding
LCEs was synthesized, thin well-aligned fibres had been drawn
rate and particularly the solution concentration.57,58 Compared
from the melt because of the plasticity at above the nematic–
with the wool fabric and cotton fabric, the resulted SMPU
isotropic transition temperature of LCEs. The resulted LCEs
nonwoven fabric was observed to not only exhibit good SME,
fibres showed magical thermal actuator behaviors: reversible
e.g. 98% shape recovery and 80% shape fixation, but also have
contraction upon heating and elongation upon cooling.
the excellent water vapour permeability (WVP) properties as
Published on 10 March 2010 on http://pubs.rsc.org | doi:10.1039/B922872A

Because high alignment and uniformity are achieved by the

shown in Fig. 5. The water vapour resistance increases with the
nematic ordering and the simultaneous telechelic cross-linking
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increase of relative humidity. The water vapour transport is

during the high shear of fibre drawing, the LC phase transition
lower at the higher relative humidity. In addition, unique prop-
of monodomain results in the spontaneous large shape
erties of nanofibres inspired the incorporation of Ag nano-
changing.60 In addition, Yoshino et al. reported the synthesis
particles for use in antimicrobial nanofilter applications.
and physical properties of chemical cross-linked liquid-crystal-
Additionally, it was found that the PCL-SMPU nanofibre mats
line polymer (CLCP) fibres. In addition to the thermal-induced
electro-spun with AgNO3 also exhibited a higher tensile strength,
deformations by heating the fibre to all isotropic phase, photo-
higher tensile modulus and lower elongation than those of pure
induced bending behavior was also expected in these CLCP
PCL-SMPU nanofibre mats.59
fibres since their CLCP film showed both thermally-induced
The appearance of SMP nanofibres leads the research of
shape changing and light-induced shape changing.61 Interest-
AMPs into the nano-meters scale filed. High orientation provides
ingly, cross-linked nanofibres with uniform alignment of the
the AMP higher mechanical properties and better shape moving
nematic directors were also electro-spun by the electro-spinning
behavior. Large surface area to volume ratio endows the AMPs
method from main-chain LCEs. In the resulting electro-spun
good sensitivity to not only heat, but also moisture, chemistry
LCE nanofibres, the nematic phase became oriented along the
gas etc. It even modifies their antibacterial properties, biode-
fibre axis during electro-spinning and the nematic director was
gradable properties etc. For example, pyridine containing pyri-
found to be oriented macroscopically, i.e., a monodomain fibre
dine quaternizated with 1-iodooctadecane are expected to show
was formed.62 These investigations reinforce the understanding
better antibacterial properties after it is electro-spun into anti-
of AMPs and promote the SCP from the film application in the
bacterial nanofibre nonwoven because the antibacterial agent
medical field to fibre applications in the textiles field. However,
can be dispersed homogeneously on the surface of nanofibre as
before SCPs become popular textile products, the materials
shown in Fig. 6. However, thermal-shrinkage should be avoided
scientists are urgently encouraged to modify the synthesis
in the SMP nanofibre/nonwoven. The promotion of phase
technology, decrease the cost and improve the quantity of
separation in the SMP nanofibres may improve their SMEs
SCPs.
through the thermal treatment.6

2.5. Shape memory polymer fabrics

Fig. 6 SEM image of nanofibre nonwoven incorporated with antibac-
terial agent. The SEM image shows that the antibacterial agent is
distributed homogeneously on the surface of nanofibre. Accordingly,
excellent antibacterial properties are expected in this nonwoven nano-
fibre.
Primitively, SMFs can not be used directly in the textile appli-
cations because of its bad tactility. However, their knitted fabrics
will be better. In 1992, Kazuyuki et al. have reported the tech-
nology of SMP woven fabrics by weaving yarns of SMFs along
or blending with other fibres.63 Recently, Hu et al. reported the
manufacture of SMPU knitted fabrics containing 100%, 50% or
16% SMF and 50% or 84% cotton fibre. Their preliminary
investigation on SMEs of SMPU knitted fabric showed that the
SME could be improved by increasing the content of SMPU
fibres because the SMEs of fabrics are mainly determined by the
morphology and alignment structure of SMFs. A comparison
study between Lycra and SMPU knitted fabrics was made to
validate the SMEs of SMPU knitted fabrics.64 Fig. 7 shows the
shape memory behaviors of SMPU fabrics. It is found that the
SMPU fabrics have the ability to fix a temporary crease shape at
room temperature and recover to its original smooth shape upon
heating. In addition, when a given size garment made with SMFs
is deformed to fit different wearer’s figures, the enlarged garment

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Fig. 7 Shape memory behavior of shape memory fabric (a) original 3D shape mold at 160  C; (b) crease shape at room temperature; (c) smooth shape
after recovery upon heating. These pictures show that SMPU fabrics have the ability to fix a temporary crease shape at room temperature and recover to
its original smooth shape upon heating.
Published on 10 March 2010 on http://pubs.rsc.org | doi:10.1039/B922872A
will adapt to a new size without tension due to the good shape
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fixation as shown in Fig. 8. Upon heating to switch temperature
of SMFs during drying process, the temporary size will recover to
its given size again.65
Because of large recovery stress, garments with shape
memory alloys exhibit dynamic distortion such as sleeve rolling
up, but apparels with SMFs mainly concentrate on the applied
shape memory function for sculpt or fashion. Considering
different textile applications, a series of SMFs with different
linear density and switch temperature have been developed in
Hu’s group. For example, for underwear applications, the
SMFs were designed to have a switch temperature of around
body temperature. For outwear applications, the switch
temperature could be designed to 55  C which approached the
tumble dry temperature. It was also found that the fabric
structure and SMFs contents have huge influence on the shape
memory function. As for the woven fabric, the structure with
less crossing points presented better SME because friction
between yarns may block the shape memory fixation and shape
recovery. Underwear made of the body temperature SMFs had
good tactility and the size could be adjusted according to the
body line. Due to the sharp change properties around the switch
temperature, further study and comparison like damping
property should be carried out on the SMP fabrics in the future
study.
Fig. 8 SMPU fabric, garment fits different wearer’s figure without
tension. The model shows that the enlarged garment made with SMFs
will adapt to new size without tension. Upon heating to switch temper-
ature of SMF fabrics, the temporary size will recover to its given size
again. Adapted with permission of ref. 65.
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3. Actively moving polymers for finishing technology
In addition to manufacture shape memory fabrics with SMFs as
described above, fabrics/textiles can also be prepared to show
shape memory functionality by applying SMPs onto fabrics/
textiles through specific finishing processes. On the basis of the
thermally-induced SMEs of SMPs, the resulting fabrics are also
expected to posses SMEs. For example, the shape memory fabric
through finishing treatment can recover to a flat appearance
from the wrinkle deformation when the condition temperature is
raised to above the transition temperature (Tr).
Hu et al. had systematically investigated the evaluation
method of shape memory fabrics according to the flat appear-
ance, crease retention and bagging recovery.66 Fig. 9 shows the
SME of shape memory fabrics treated by finishing technology.
Hu et al. have applied SMPU in fabric finishing and garment
finishing since 2004.67,68 They have synthesized various water-
soluble SMPUs with shape recovery temperature of 55  C to
achieve the anti-wrinkle and wrinkle recovery;67 and they also
applied the water-soluble SMPU on textiles to achieve water-
proof, warmth retaining and water vapor permeable textiles.68
Additionally, they developed an novel react-able water-soluble
SMPU finishing agent by terminated technology to achieve
excellent flexible, tactility and washable textiles.69 In addition to
the cotton fabric, the wool fabric was also treated to show SMEs
with the SMP finishing agents.70 These finishing technologies
could also be applied to garments for which the process include
washing, dehydration, confecting agent and finishing agent
treatment, drying, curing and cooling etc.71
Hu et al. even explored the underlying microscopic mechanism
and concept of the transfer of SMEs from the SMPU to cotton
fibrics in the finishing process using Raman spectroscopy. It was
found that the SMPs took a critical role in reducing the residual
stress of weft fibres through forming coating on the fibre surface
after finishing process, establishing the prerequisite for reserving
the SMEs to fabric. It was proved that the strength reduction in
fibres finishing process is not only caused solely by a chemical
reaction, but also by a physical modification of the cotton
structure. It was suggested that the role player by SMPU in the
finishing process is essential when dimethyloldihydroxy-
ethyleneurea (DMDHEU) participates in it. The grafting SMPU
onto cotton fibres was a prerequisite for reserving the SMEs by
reducing the residual stress inside the weft fibres.72 However, the
big problem of shape memory finishing technology is the balance
among flat appearance, mechanical properties keeping and
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Fig. 9 SME of fabrics treated through textile finishing. These pictures show that shape memory fabric shows good flat appearance, crease retention and
bagging recovery.
tactility of textiles. High cross-linkable and low temperature
react-able SMP finishing agents may be attractive to the shape
memory finishing technology.
4. Study of water vapor permeability for textile
applications
In addition to the shape moving behavior, AMPs also show some
other remarkable changes in physical and mechanical properties,
which enable the materials to exhibit some novel functions or
make them be adaptable to the external changes. WVP would be
one of the significant changing parameters of thermally-induced
SMP membranes. This WVP property enables the thermally-
induced SMP a broad application in textiles industry. Particu-
larly, SMPU became one of the good candidates in breathable
laminated nonporous fabrics due to their unique WVP properties
as shown in Fig. 10. At the temperature range below Tr, WVP is
very low due to the high aggregation of molecular chains, while it
increases sharply to a high value after the temperature is raised to
above Tr due to its increased radius and number of free volume
holes. Additionally, SMPU shows higher WVP at higher
humidity and lower WVP at lower humidity.73 Thus, the SMPU
coating which derives the development of smart garments has the
advantage of controlling the WVP according to both the
surrounding temperatures. The SMPU nonporous laminated
fabric then will show quite different WVP properties above Tr
and below Tr. That is, this behavior could provide thermal
insulation at cold and high permeability at room temperature or
above. Fabrics laminated with the SMPU would provide better
comfort in both cold and warm climates.74
In the last decades, the controlling of WVP was one of the
most attractive topics to scientists and much work has been
carried out. For example, Yontz et al. studied the effect of soft
block composition of a hydrophilic polyurethane-urea on the
water vapor transporting (WVT) rates by varying PEO contents
from 0 to 50 wt%.75 It was found that WVT increases signifi-
cantly with the increase of temperature at the temperature range
3352 | J. Mater. Chem., 2010, 20, 3346–3355
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23  C to 37  C. The relationship plot of WVT and temperature
showed an almost perfect fit to the Arrhenius relationship. In
2000, Jeong et al. had investigated the WVP properties of SMPU
with the amorphous reversible phase. They found that the
neutralized DMPA unit enhanced the sensitivity of the thermo-
responsive WVP by amplifying the increase of WVP at the
temperature range of above Tg.74 Accordingly, water vapor
permeable fabrics were prepared by coating the SMPU
membrane onto polyester woven fabrics. It was found that the
WVP of SMPU-coated fabrics decreased dramatically with the
increase in concentration of the coating solution, whereas only
a slight change was observed by varying the PU hard-segment
content. It was proposed that the high WVP of SMPU-coated
fabrics should result from the smart permeability characteristics
of SMPU.76 In addition, Cho et al.76 and Hu et al.77–79 both found
that the WVP of SMPU with the semi-crystalline reversible phase
increases significantly at the Tm due to crystal melting of soft
segments. This research enabled the identification of the key
parameters governing the WVP of thermal-induced SMPUs
membrane and open the way for new tailor-made polymeric
materials with specified properties. This property can be applied
to the development of breathable textiles, biomedical and many
other industrial applications.3 In 2007, Chen et al. had synthe-
sized two segmented thermo-sensitive polyurethane (TSPU)
membranes with functional gates for controlling WVP because
the size and shape of free-volume holes available in membrane
materials control the rate of gas diffusion and its permeability.80
In addition, Huang et al. had also found that the temperature-
sensitive WVP was changed slightly with the hard segment
content.81
As for the application in coated or laminated clothes, Hu
et al. suggested that the film should be a smart one. They found
that the WVP of SMPU film can control its WVP through
adjusting the temperature by itself. The WVP of SMPU film
increases significantly at the Tg and the addition of PEG
affected the WVP dramatically.82 Additionally, Hu et al. found
that the WVP of a SMPU film was also influenced by both the
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Fig. 10 WVP of SMPU film at different temperature (a) and at different
humidities (b). These plots show that the WVP of SMPU film increases to
high value at a critical temperature, e.g. the Tm of soft segment, and show
much higher WVP at the higher humidity vapor partial pressure, e.g.
above 8. Adapted with permission of ref. 73.
hydrophilic group and crystalline soft segment.83,84 For
example, SMPU without PEG showed a lower WVP. However,
the WVP increased with the increase of PEG content in the
polyurethane with PEG, i.e. the SMPU with higher content of
PEG has higher WVP due to the increasing number of polar
groups in the polymer backbone. Additionally, the soft segment
crystal melting further enhances the WVP of SMPU
membranes. Furthermore, Mondal and Hu had investigated the
WVP of cotton fabrics coated with the SMPU membrane,83
whose phase transition temperature was tailored to the room
temperature. Similarly, an abrupt change in WVP was observed
in the resulting fabrics when the experimental temperature
reached the Tm of soft segment of SMPU. Moreover, the WVP
of coated fabrics was dependent on the primary structure of
SMPU. In addition, it was also found that when the poly-
caprolactone glycol was introduced to the polytetramethylene
glycol based SMPU, the WVP decreased due to the increased
interaction between the polymer chains. In contrast, the WVP
increased with the increase of polyethylene glycol in the SMPU
backbone due to the increased hydrophilicity in the SMPU.83
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Recently, Huang et al. developed another type of temperature-
sensitive polymer membranes by combination of hydrophilic
SMPU and thermo-sensitive poly(N-isopropylacrylamide-co-
sodium acrylate)85 hydrogel micro-particles using a composite
coating method. As a result, these two intelligent polymer
components endowed the composite membranes with ‘‘double
switch’’ on the WVP. Poly(NiPAAm-co-SA) hydrogel micro-
particles exhibited a reversible volume transition at lower crit-
ical solution temperature (LSCT) around 34–36  C. The size of
gel particles varied more than 10-fold between temperature
above and below LCST. It likely acted as a sensor of temper-
ature and as a switch to regulate the WVP of composite
membranes. It was also found that the WVP increased
dramatically at the temperature range of 35  C to 40  C in the
hydrophilic SMPU based membranes.85
These investigations provide the support that the fabrics
coated or laminated with SMP show significant transition in
moisture permeability at the temperature below and above Tr.
Therefore, the clothing materials would not only be waterproof
at any temperature, but also provide more comfort in both cold
and warm climates. Accordingly, Diaplex Co., Ltd. announced
the successful development of ‘‘smart fabrics’’ with the SMP for
the outerwear industry. According to their report, the resulting
Diaplex fabrics showed excellent waterproof and breathable
features with 20 000–40 000 mm H2O in the water pressure
resistance and 8 000–12 000 g m2 24 h in the moisture
permeability. Such properties provided the resulted garments
with high performance and enabled wearers to be comfortable
in various conditions. Therefore, it was proposed that by
combining the excellent WVP of SMPs with micro-porous
coating and laminated technology of garments, SMP coatings
and laminates would find a wide application in textiles/
garments field, e.g. sportswear, footwear, gloves and socks.
However, the WVP of present products at the higher temper-
ature range still should be improved. Reducing the rubber
modulus of SMPs and modifying membrane coating tech-
nology would be two research directions. In addition, it is also
desirable to further improve the WVP values for some appli-
cations.
5. Conclusions and outlook
This review presents the most important areas and directions
of AMPs in textile applications. In addition to the general
investigation on the molecular structure and principle of
actively moving polymers, their recent development in textile
fields are highlighted from the fibre spinning (including wet
spinning, melt spinning and electro-spinning), fabric
manufacturing, shape memory finishing technology and WVP
investigation. Many textile applications of AMPs concentrate
on the thermally-induced SMPs to date. However, as for the
smart textile applications, multi-responsive which shows
response to light, electric and moisture, and multi-functional
SMPs by incorporating anti-bacterial function and health care
may be more attractive. Shape changing is generally observed
in the LCEs, their high cost and complex manufacture limited
their applications greatly. Scientists are inspired continuously
to improve the fabrication technology and reduce the cost of
AMPs.
J. Mater. Chem., 2010, 20, 3346–3355 | 3353
 View Online

Acknowledgements 37 S. Hayashi, Us-Japan Workshop on Smart Materials and Structures,

The authors would like to acknowledge the finance support from
the Hong Kong ITF research project ‘High Performance
Advanced Materials for Textile and Apparel’ (No. GHS/088/04)
and the help of Dr Jing Lu, Dr Yong Zhu and Mr. Hongsheng
Luo.
References
1 M. Behl and A. Lendlein, Soft Matter, 2007, 3, 58.
2 C. Liu, H. Qin and P. T. Mather, J. Mater. Chem., 2007, 17, 1543.
3 S. Mondal and J. L. Hu, Des. Monomers Polym., 2006, 9, 527.
4 M. Behl and A. Lendlein, Mater. Today, 2007, 10, 20.
5 A. Lendlein and S. Kelch, Angew. Chem., Int. Ed., 2002, 41, 2034.
Published on 10 March 2010 on http://pubs.rsc.org | doi:10.1039/B922872A
1996, 29.
38 A. Lendlein and R. Langer, Science, 2002, 296, 1673.
39 A. Lendlein, J. Canisius, J. Schulte and K. Kratz, SMST-2003:
Proceedings of the International Conference on Shape Memory and
Superelastic Technologies, 2004, 563.
40 Z. G. Wang, X. T. Zu, P. Fu, J. Y. Dai, S. Zhu and L. M. Wang,
Materials Science and Engineering a-Structural Materials Properties
Microstructure and Processing, 2003, 360, 126.
41 A. Lendlein and M. Behl, Smart Materials & Micro/Nanosystems,
2008, 54, 96.
42 W. Sokolowski, A. Metcalfe, S. Hayashi, L. Yahia and J. Raymond,
Biomed. Mater., 2007, 2, S23.
43 Y. Zhu, J. L. Hu, L. Y. Yeung, Y. Liu, F. L. Ji and K. W. Yeung,
Smart Mater. Struct., 2006, 15, 1385.
44 Y. Zhu, J. L. Hu, L. Y. Yeung, J. Lu, Q. H. Meng, S. J. Chen and
K. W. Yeung, Smart Mater. Struct., 2007, 16, 969.
45 F. L. Ji, Y. Zhu, J. L. Hu, Y. Liu, L. Y. Yeung and G. D. Ye, Smart

6 S. J. Chen, Q. Cao, B. Jing, Y. L. Cai, P. S. Liu and J. L. Hu, J. Appl.

Polym. Sci., 2006, 102, 5224. Mater. Struct., 2006, 15, 1547.
Downloaded by Hong Kong Polytechnic University on 20 June 2011

7 S. J. Chen, Q. Cao and P. S. Liu, Acta Polymerica Sinica, 2006, 1. 46 S. J. Chen, J. L. Hu, Y. Q. Liu, H. M. Liem, Y. Zhu and Y. J. Liu,
8 Q. Cao, S. J. Chen, J. L. Hu and P. S. Liu, J. Appl. Polym. Sci., 2007, J. Polym. Sci., Part B: Polym. Phys., 2007, 45, 444.
106, 993. 47 J. L. Hu, J. Lu and Y. Zhu, Polym. Rev., 2008, 48, 275.
9 S. J. Chen, J. L. Hu, C. W. Yuen and L. K. Chan, Mater. Lett., 2009, 48 Q. H. Meng and J. L. Hu, Polym. Adv. Technol., 2008, 19, 131.
63, 1462. 49 Q. H. Meng, J. L. Hu, Y. Zhu, J. Lu and Y. Liu, Smart Mater. Struct.,
10 S. J. Chen, J. L. Hu, H. T. Zhuo and Y. Zhu, Mater. Lett., 2008, 62, 2007, 16, 1192.
4088. 50 Q. H. Meng, J. L. Hu and L. Yeung, Smart Mater. Struct., 2007, 16,
11 T. Chung, A. Rorno-Uribe and P. T. Mather, Macromolecules, 2008, 830.
41, 184. 51 Q. H. Meng, J. L. Hu, L. Y. Yeung and Y. Hu, J. Appl. Polym. Sci.,
12 S. Mondal, Mini-Rev. Org. Chem., 2009, 6, 114. 2009, 111, 1156.
13 S. Zhang, Z. J. Yu, T. Govender, H. Y. Luo and B. J. Li, Polymer, 52 J. Kaursoin and A. K. Agrawal, J. Appl. Polym. Sci., 2007, 103, 2172.
2008, 49, 3205. 53 Y. C. Jung, J. W. Kim, B. C. Chun, Y. C. Chung and J. W. Cho,
14 H. Y. Luo, Y. Liu, Z. J. Yu, S. Zhang and B. J. Li, Biomacromolecules, Quality Textiles for Quality Life, 2004, Vols. 1–4, 43.
2008, 9, 2573. 54 J. H. So, S. H. Lee, J. Jung, K. J. Yoon and J. W. Cho, Quality
15 H. Y. Luo, M. M. Fan, Z. J. Yu, X. W. Meng, B. J. Li and S. Zhang, Textiles for Quality Life, 2004, Vols. 1–4, 121.
Macromol. Chem. Phys., 2009, 210, 669. 55 D. I. Cha, H. Y. Kim, K. H. Lee, Y. C. Jung, J. W. Cho and
16 S. J. Chen, J. L. Hu, Y. Q. Liu, H. M. Liem, Y. Zhu and Q. H. Meng, B. C. Chun, J. Appl. Polym. Sci., 2005, 96, 460.
Polym. Int., 2007, 56, 1128. 56 H. T. Zhuo, J. L. Hu and S. J. Chen, Mater. Lett., 2008, 62, 2074.
17 H. M. Jeong, S. Y. Lee and B. K. Kim, J. Mater. Sci., 2000, 35, 1579. 57 H. T. Zhuo, J. L. Hu, S. J. Chen and L. P. Yeung, J. Appl. Polym. Sci.,
18 B. K. Kim, J. S. Lee, Y. M. Lee, J. H. Shin and S. H. Park, 2008, 109, 406.
J. Macromol. Sci., Part B: Phys., 2001, 40, 1179. 58 H. T. Zhuo, J. L. Hu, S. J. Chen and Y. Zhu, Proceedings of the
19 P. Ping, W. S. Wang, X. S. Chen and X. B. Jing, Biomacromolecules, International Conference on Advanced Textile Materials &
2005, 6, 587. Manufacturing Technology, 2008, 463.
20 B. S. Lee, B. C. Chun, Y. C. Chung, K. I. Sul and J. W. Cho, 59 H. J. Jeon, J. S. Kim, T. G. Kim, J. H. Kim, W. R. Yuc and
Macromolecules, 2001, 34, 6431. J. H. Youk, Appl. Surf. Sci., 2008, 254, 5886.
21 S. Neuss, I. Blomenkamp, R. Stainforth, D. Boltersdorf, M. Jansen, 60 S. V. Ahir, A. R. Tajbakhsh and E. M. Terentjev, Adv. Funct. Mater.,
N. Butz, A. Perez-Bouza and R. Knuchel, Biomaterials, 2009, 30, 2006, 16, 556.
1697. 61 T. Yoshino, J. Mamiya, M. Kinoshita, T. Ikeda and Y. L. Yu, Mol.
22 K. Hiraoka, N. Tagawa and K. Baba, Macromol. Chem. Phys., 2008, Cryst. Liq. Cryst., 2007, 478, 233.
209, 298. 62 S. Krause, R. Dersch, J. H. Wendorff and H. Finkelmann, Macromol.
23 J. V. Selinger and B. R. Ratna, Phys. Rev. E: Stat., Nonlinear, Soft Rapid Commun., 2007, 28, 2062.
Matter Phys., 2004, 70, 041707. 63 K. kobayshi; and S. Hayashi, Us Pat., 5128197 1992, 1992.
24 M. H. Li, P. Keller, J. Y. Yang and P. A. Albouy, Adv. Mater., 2004, 64 Y. Liu, A. Chung, J. L. Hu and J. Lv, J. Zhejiang Univ., Sci.: A, 2007,
16, 1922. 8, 830.
25 D. L. Thomsen, P. Keller, J. Naciri, R. Pink, H. Jeon, D. Shenoy and 65 J. Hu, Y. Zhu, J. Lu, L.-y. Yeung and K.-w. Yeung, In The 9th Asian
B. R. Ratna, Macromolecules, 2001, 34, 5868. Textile Conference. Federation of Asian Professional Textile
26 J. L. Hu, F. L. Ji and Y. W. Wong, Polym. Int., 2005, 54, 600. Associations:, 2007, Taiwan.
27 J. L. Hu, Z. H. Yang, L. Y. Yeung, F. L. Ji and Y. Q. Liu, Polym. Int., 66 Y.-k. Li, Hong Kong Polytechnic University – Dissertations, 2007.
2005, 54, 854. 67 J. L. Hu and Z. H. Yang, CN 1648143 2004.
28 S. J. Chen, J. L. Hu, C. W. Yuen and L. k. Chan, Polymer, 2009, 50, 68 J. L. Hu and H. J. FAN, CN 1648145 2004.
4424. 69 J. l. Hu and Y. Q. Liu, China Patent: CN1704523 2004.
29 J. H. Li, J. A. Viveros, M. H. Wrue and M. Anthamatten, Adv. 70 J. L. HU, Y. J. Liu, G. H. Zheng and Y. Liu, China patent:
Mater., 2007, 19, 2851. CN1818198 2006.
30 D. Ratna and J. Karger-Kocsis, J. Mater. Sci., 2008, 43, 254. 71 H. J.L.;, Y. J. Liu and Y. Liu, China patent: CN1818198 2008.
31 Y. Zhu, J. L. Hu, K. W. Yeung, Y. Q. Liu and H. M. Liem, J. Appl. 72 H. Liem, L. Y. Yeung and J. L. Hu, Smart Mater. Struct., 2007, 16,
Polym. Sci., 2006, 100, 4603. 748.
32 Y. Zhu, The Hong Kong Polytechnic Universtiy, 2008. 73 J. L. Hu, Y. M. Zeng and H. J. Yan, Text. Res. J., 2003, 73, 172.
33 H. Zhang, H. T. Wang, W. Zhong and Q. G. Du, Polymer, 2009, 50, 74 H. M. Jeong, B. K. Ahn, S. M. Cho and B. K. Kim, J. Polym. Sci.,
1596. Part B: Polym. Phys., 2000, 38, 3009.
34 T. S. Wilson, J. P. Bearinger, J. L. Herberg, J. E. Marion, 75 D. J. Yontz, Polymer Science and Engineering, University of
W. J. Wright, C. L. Evans and D. J. Maitland, J. Appl. Polym. Sci., Massachusetts at Amherst., 1999.
2007, 106, 540. 76 J. W. Cho, Y. C. Jung, B. C. Chun and Y. C. Chung, J. Appl. Polym.
35 R. A. Weiss, E. Izzo and S. Mandelbaum, Macromolecules, 2008, 41, Sci., 2004, 92, 2812.
2978. 77 X. M. Ding, J. L. Hu and X. A. Tao, Text. Res. J., 2004, 74, 39.
36 Y. L. Wang, Y. G. Li, Y. F. Luo, M. N. Huang and Z. Q. Liang, 78 X. M. Ding, J. L. Hu, X. M. Tao, C. P. Hu and G. Y. Wang, Quality
Mater. Lett., 2009, 63, 347. Textiles for Quality Life, 2004, Vols. 1–4, 1279.

3354 | J. Mater. Chem., 2010, 20, 3346–3355 This journal is ª The Royal Society of Chemistry 2010

79 X. M. Ding, J. L. Hu, X. M. Tao, C. P. Hu and G. Y. Wang, J. Appl.
Polym. Sci., 2008, 107, 4061.
80 Y. Chen, Y. Liu, H. J. Fan, H. Li, B. Shi, H. Zhou and B. Y. Peng,
J. Membr. Sci., 2007, 287, 192.
81 H. Huang, D. Zhang, T. J. Wang, Z. P. Mao, W. D. Yu and H. J. Yan,
Proceedings of the 2007 International Conference on Advanced Fibers
and Polymer Materials, 2007, Vols. 1 and 2, 546.
Published on 10 March 2010 on http://pubs.rsc.org | doi:10.1039/B922872A
Downloaded by Hong Kong Polytechnic University on 20 June 2011
This journal is ª The Royal Society of Chemistry 2010
View publication stats
View Online
82 C. Y. Lin, K. H. Liao, C. F. Su, C. H. Kuo and K. H. Hsieh,
J. Membr. Sci., 2007, 299, 91.
83 S. Mondal and J. L. Hu, Carbohydr. Polym., 2007, 67, 282.
84 S. Mondal, J. L. Hu and Z. Yong, J. Membr. Sci., 2006, 280,
427.
85 H. Huang, Z. P. Mao and W. D. Yu, Textile Bioengineering and
Informatics Symposium Proceedings, 2008, Vols. 1 and 2, 286.
J. Mater. Chem., 2010, 20, 3346–3355 | 3355