Holme 2007

doi: 10.1111/j.1478-4408.2007.00064.
Innovative technologies for high

performance textiles
Ian Holme
I Holt Walk, Adel, Leeds LS16 7QB, UK
Email: [email protected]
Increasing global competition in textiles has created many challenges for European dyers and finishers.
The rapid growth in technical textiles and in their end-uses has generated many opportunities for the
application of innovative chemical finishes. Novel finishes of high added value for apparel fabrics are
also greatly appreciated by a more discerning and demanding consumer market. This review will
concentrate on some of the new approaches to producing high added value textiles that provide
consumers with greater levels of comfort, safety, aesthetics and functional performance. Some of the
technologies to be described are developed to the commercial exploitation stage, while others are still in
development but offer potential for the future. Textile finishing personnel and companies must be active
in keeping abreast of the developments in chemical finishing that are emerging globally, in order to
survive and prosper in this very competitive and cost-conscious sector of the textile industry. The future
of textile finishing within Europe depends upon rapid adoption of high performance, high added value
finishes that provide innovation and novelty to the consumer, and in seeking out new end-uses and
markets for such finishes.
Introduction North America and Europe is considered to be the high

An analysis of the global textile and apparel industries performance, high value-added route to textile
carried out in 2005 by the United Nations Conference on manufacture. This utilises the high technical skills
Trade and Development (UNCTAD) demonstrated the currently available in these industries in order to produce
growth in world trade during the period 1990–2003 [1]. textile materials of high quality, high technical
In 2003, the 20 largest textile exporters exported performance and perceived high value added to satisfy
US$172 604 million of textiles out of a world total of the growing consumer markets.
US$185 596 million, some 93% of the total. The 13 It is widely perceived that the end-uses for technical
countries in the European Union (EU) in 2003 supplied textiles will continue to increase each year and the
US$59 906 million of this total (32.3%). However, after modification of commodity fibre and fabric properties by
the ending of the Multi Fibre Arrangement there has been innovative finishes can be a cheaper route to high
a dramatic rise in exports of apparel from countries such performance than by using a high cost fibre with inherent
as China, India, Pakistan and Turkey into North America built-in performance properties. The use of novel finishes
and the European Union. and innovative technologies therefore can be applied to
The global market for fibres totalled 64 million tonnes apparel fabrics, household textiles and technical textiles
in 2004 according to the PCI Consulting Group [2]. It was to increase their appeal to the consumer and stimulate
estimated that the main end-uses were apparel (65%), the growth in niche markets.
household textiles (18%) and technical textiles (17%). It Innovation is the lifeblood of the retailers who are
is generally recognised that commodity textile and always seeking products that are better, cheaper and faster
apparel manufacture has shifted away from North delivered [3]. Consumers worldwide are more discerning
America and Western Europe into Asia and in parallel and demanding, but many will pay a higher premium for
with this change dye manufacturing has also moved into products with a perceived higher value added, providing
Asia, principally into China. Some 64 million tonnes of the consumer with greater individuality and status, as well
fibres were estimated to have been consumed worldwide as with higher standards of comfort, aesthetics,
in 2004, with synthetic fibres (40 million tonnes) appearance, handle and functional performance.
exceeding the consumption of natural fibres (24 million The major sector of technical textiles continues to grow
tonnes). The breakdown was considered to be polyester worldwide and many textile companies that have seen
(40%), cotton (36%), polypropylene/other olefins (7%), their traditional markets eroding through low labour cost
polyamide (6%), acrylic (4%), regenerated cellulosic fibres countries that dominate the commodity textile and
(4%) and wool (2%) [2]. apparel markets have switched production to technical
As the world population increases there will be an textiles, developing innovative products with high value-
increase in global fibre consumption, but in the added functional performance levels [4]. In this way,
developed countries fabrics for apparel have become niche markets have been opened up using lower volume,
lighter in weight and the use of heavy fabrics for apparel higher added value technical textiles that can be
has declined. North America and EU countries cannot marketed and expanded into major sectors of industry,
compete with low wage cost countries producing e.g. automotive fabrics, filtration, chemical protection, etc.
commodity textile and apparel items. Instead, the way Innovation in technical textiles is bounded only by the
forward for the highly developed textile industries of imagination of research, development and marketing
ª 2007 The Author. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 59–73 59
Holme High performance textiles
teams and as a result the end-uses for textile fibres are – no overdrying because of the use of controlled steam/
continuing to expand, year-on-year. air mixtures;
This study will provide a brief review of some of the – reliable process management and process control and
innovative technologies that are emerging in the textile – combinable with other finishing processes.
field. The worldwide interest and investment in
nanoscience and nanotechnology, in particular, could open Total easy-care wool knitwear
up many opportunities in the technical textile and apparel
The use of wool in knitwear is principally confined to fully
markets [5].
fashioned and flat knitting, together with some circular
knits [9]. However, wool is seldom used in warp-knitted
Easy care, durable press and wrinkle-free fabrics. High quality knitwear has traditionally been
finishes manufactured on fine gauge fully fashioned machines and
For fabrics containing cotton or other cellulosic fibres the coarser gauge flat-knitting machines. More limited
attainment of easy care, durable press and wrinkle-free quantities of knitwear and tailored garments are produced
finishes is essential to maintain the image of cotton in using circular weft-knitted fabric. Because the wool fabric
high performance apparel textiles. Traditionally such is produced in tubular form there are some limitations in
treatments utilise a chemical crosslinking agent together the knitting, dyeing and finishing steps while the fact that
with a catalyst and fibre lubricant/softener. Many garments must be produced by the cut and sew route
chemical types of finishes have been used [6,7] such as: creates waste. The cut and sew route is used for relatively
– 1,3-dimethylol-4,5-dihydroxyethylene urea (DMDHEU); fine gauge wool circular jersey products, but because the
– 1,3-dimethyl-4,5-dihydroxyethylene urea; cutting waste can reach as high as 25% of the total fabric
– glyoxal urea; this processing route is economically unattractive.
– 1,2,3,4-butane tetracarboxylic acid; Consumers now demand wool knitwear that is
– citric and malic acids; machine-washable and modern requirements for total
– polymaleic acid derivatives and easy-care wool include the need for tumble-dryability as
– phosphonocarboxylic acids. well [10,11].
In addition to these approaches research has been The increasing use of domestic washing machines after
conducted into novel chemical finishes based upon [7]: the Second World War and of tumble-dryers since the
– 1,3,5-triacryloylaminohexahydro-s-triazine-amino 1990s has intensified many research efforts to produce
derivatives; improved shrink-resist methods for wool. This ultimately
– DMDHEU/a-amino acids, e.g. aspartic acid/glutamic led to treatments based upon a two-stage process [10].
acid and The first stage involved an oxidative pretreatment using
– ionic crosslinking using cationised chitosan. either chlorination or permonosulphuric acid. This was
The advantages and limitations of chemical crosslinking followed in a second stage by the application of a
systems have been comprehensively reviewed in respect of polymer.
the type of chemical finish applied [6,7]. However, new The major method subsequently developed was the
approaches to the application of chemical crosslinking chlorination–Hercosett process applied as a continuous
agents could prove fruitful. top treatment [10,11]. The chlorination pretreatment
High-grade easy-care finishing of cellulosic fabrics is modifies the scale edges of wool and increases the critical
conventionally carried out using dry crosslinking (ca. surface tension of the fibre. This is an essential
95%), moist crosslinking (ca. 5%) or wet crosslinking pretreatment, because this allows the Hercosett polymer
(0.1%) [8]. The highest functional performance is, (a polyamide–epichlorohydrin-based product) to wet and
however, achieved through moist crosslinking but this spread over the surface of the wool. This ensures that the
has entailed the highest processing costs because of the scales are coated with a highly hydrophilic polymer that
long fabric dwell time of 24 h at 30–35 C. In the novel swells greatly when placed into water. Thus, the scales
continuous moist crosslinking treatment jointly developed are sheathed or masked and the directional frictional
by Huntsman Textile Effects (Basel, Switzerland) and effect (DFE) caused by the difference in friction between
Monforts, the Monforts MXL Process, continuous moist la (friction coefficient when rubbing in the against-scale
crosslinking is completed on the Monforts Thermex direction) and lw (friction coefficient when rubbing in the
hotflue [8]. Cotton fabric is padded with a crosslinking with-scale direction). As the DFE is the principal factor
agent, dried at 110 C for 3 min using 30% v/v steam on causing wool felting, treatments that eliminate the DFE
the Thermex hotflue to give a residual moisture content give rise to a shrink-resist effect on wool.
in the fabric of 5–6%, cooling to 20 C. There is thus no One of the major issues in the field of wool shrink-
dwell time. resist finishing is the continual search for alternatives to
The benefits of this novel approach to continuous moist chlorination pretreatments and chlorine-containing
crosslinking of cellulosic-based fabrics are [8]: shrink-resist polymers [11]. New approaches are highly
– continuous process; desirable to remove the problem of AOX (absorbable
– no separate dwell process necessary; organohalogen compounds) which is created by the
– low space requirement; reaction of chlorine on wool. In Germany, a limit has
– lower investment costs; been set for AOX at 1 ppm in drinking water. A similar
– simpler residual moisture control with constant dwell limit applies for AOX in effluent in many European
time; countries.
60 ª 2007 The Author. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 59–73
Oxidative pretreatment of wool followed by enzymatic proportion of the covalently bound lipids from the fibre
treatment to produce shrink-resist wool yarns and fabrics surface which necessitates the need for a softener.
was a feature of the Perzyme Process developed by WIRA Arristan 64 (CHT R. Beitlich GmbH, Tübingen, Germany)
Leeds, UK which was used during the Second World is a special reactive polysiloxane-based softener which
War. The wool was first given a short treatment with not only imparts a soft handle, but also enhances the
hydrogen peroxide at pH 10.5, followed by treatment shrink-resist and colour fastness performance.
with a mixture of papain and sodium bisulphite [12,13]. At present the major continuous top treatments for
One of the most novel treatments for batch processing is Superwash wool are conducted using ranges
the ARS-patented process, which was developed at the manufactured by Andar (Timaru, New Zealand), Fleissner
USA Army’s request for itch-free, washable wool (Egelsbach, Germany) and Kroy (Schia, Italy). Andar has
underwear made from American wool [14]. The ARS also introduced a novel loose wool shrink-resist
process consists of a pretreatment with a stable activated applicator for small lot processing which could open up
peroxide followed by proteolytic treatment with an new opportunities for wool knitwear end-uses, especially
enzyme, either serine or cysteine protease. for lambs’ wool.
In the ARS process wool fabric is whitened, Additive treatments alone using polymeric finishes to
biopolished and imparted with machine-washable mask the scales when applied by padding can give rise to
properties [14]. The wool fabric is first pretreated for a relatively hard handle because of interfibre bonding.
30 min at 30 C with a powerful, stable peroxide Ciba have introduced a highly crosslinked silicone rubber
(percarboximide) formed from dicyandiamide and (Dicrylan 7702) which further reacts on the wool fibre
alkaline hydrogen peroxide with gluconic acid stabiliser when a special metal-free catalyst (Phobotone Catalyst
for sustained whitening. In a subsequent treatment at 7639) is used [18]. A combination of crosslinkable
45 C for 40 min with serinase assisted by sodium silicone rubber with silicone-modified polyurethane
sulphite, or unassisted cysteinase applied at 50 C for allows tumble-drying after washing, but this performance
60 min, biopolishing and machine-washable performance is not achievable using silicone rubber alone.
is obtained without appreciable loss in strength or elastic A novel polymer termed DP5570 has been recently
recovery. developed by Devan-PPT Chemicals (Ambergate, UK) that
Another recent development is a shrink-resist process fully meets total easy care standards and is claimed to
for machine washability in which the wool is first compete economically with the Hercosett polymer as well
pretreated with hydrogen peroxide in a salt solution to as offering some additional benefits [19]. This is a low
restrict reaction to the fibre surface followed by treatment solids add-on polymer process (0.3% at pH 5–6)
with proteolytic enzyme linked to a polymer to decrease compared with Hercosett (2% at pH 7–8). The DP5570
the enzyme diffusion into the wool fibre interior [15]. In polymer can be cured at a lower temperature providing
this way, the reaction is restricted to the surface and energy savings while the treatment imparts control over
wool fibre damage is minimised. the hairiness/facing/pilling that occurs during washing
A novel continuous shrink-resist treatment for wool which remains a problem with the standard shrink-resist
tops and loose stock is the Perachem process, developed treatments. The use of DP5570 polymer is claimed to
at the University of Leeds, UK [16]. This consists of a impart a natural softness as well as yielding a whiter
preliminary step in which the surface energy of the wool wool with improved dyeability.
fibres is increased by the removal of much of the
hydrophobic covalently bound surface lipids through Ultrahydrophobic surface treatments and
treatment with a nucleophilic agent. This treatment also self-cleaning finishes
oxidises the cystine in the A-layer of the cuticle and is
The whole area of water repellency and waterproofing
followed by sulphitolysis with sulphites to generate
including oil-repellent and stain-repellent finishes has
Bunte Salt groups (–SSO 3 ). These groups create a
recently been reviewed in depth [20–24].
negatively charged wool fibre surface and give cuticle
In fluorochemicals based upon fluoroacrylates the
swelling which also contributes to the overall shrink-
perfluorinated side-chains are oriented away from the
resist effect of the treatment. Exhaustion of a cationic
fibre surface, with the –CF3 terminal groups creating a
low–AOX Hercosett resin then follows, the whole process
low-energy surface [21,22]. The optimum orientation
being carried out in a continuous six-bowl treatment. It is
takes place only if the length of the perfluorinated side-
claimed that this patented process results in a wool that
chain is at least seven carbon atoms and wash fastness on
is whiter and softer than that achieved in conventional
cotton is improved through the use of methylol groups.
chlorine/Hercosett treatments while the dyeing properties
During washing the orientation of the side-chains changes
are the same.
and has to be restored generally by heating at 70–80 C,
The German Wool Research Institute (DWI, Aachen,
typically by tumble-drying or hot ironing. Modern
Germany) has examined the application of a continuous
versions of fluorocarbons can be reorientated to restore
atmospheric plasma treatment for wool tops at 5–7 m/min
the repellency at ca. 60 C, but research is continuing to
over a width of 150 cm [17]. Using five electrodes the
lower the reorientation temperature [21–24].
energy output was raised to 3.5 kW in order to decrease
It is clear that the demands for fluorocarbon finishes
the wetting time of the wool. The effect of the plasma
will increase as many forms of textile garments,
treatment is adversely affected by a higher moisture
traditionally never given a water-repellent or stain-
content in the wool. Plasma treatments can generate a
repellent finish, will be given such treatment in the future
rather harsh handle because they remove a large
to provide a higher added value through the improved Irradiation in the presence of perfluoro-4-methylpent-2-ene
easy-care performance. Research and development to can then lead to radically bound hydrophobic end groups.
optimise the effects, decrease curing times and Pulsed plasma polymerisation of monomers containing
temperatures, promote reorientation at lower tem- long perfluoroalkyl chains linked to a polymerisable
peratures, and maintain high effectiveness through carbon–carbon double bond can provide ultra-
multiple wash cycles will continue throughout the next hydrophobic effects which can be used not only for
decade. The ability of fluorocarbon finishes to provide water-, oil- and stain-repellency [31], but can also be used
durable repellency properties without impairment of for chemical protection, e.g. in nuclear, biological,
garment breathability (i.e. high water vapour transmission chemical protection suits, for protection against nerve
rates) is an important marketing advantage [20]. agents [21,31–35].
Biomimetic finishes are an interesting area for future Glow-discharge plasma treatments can be used for
development. The self-cleaning action of the surface of activation, grafting, deposition or etching. Using an RF
the lotus leaf has given rise to the so-called ‘lotus effect’ capacitive system at 13.56 kHz wool and cotton fabric
which is being utilised to produce ultrahydrophobic samples have been treated with a trichloroethylene
finishes [21,25,26]. The surface of the lotus leaf is solution of Zonyl fluoromonomer (DuPont, Wilmington,
covered with characteristic wax microstructures, which DE, USA) in argon plasma to obtain high levels of water
can generate contact angles of up to 170, significantly and oil repellency [36,37].
higher than with smooth fluorochemical-based surface There are very clearly many opportunities for liquid-
coatings. This ultrahydrophobic (or superhydrophobic) proof and microorganism-impermeable medical textiles,
effect also ensures the rapid and effective removal by e.g. for reusable surgical gowns made from polyester
water of any soils on the surface of the lotus leaves, microfilament fabrics, suitable for repeated washing and
providing a self-cleaning effect. sterilising. Treatment of such fabrics with plasma treated/
Nature is now being copied by bio-engineering textile C2F6, plasma treated/H2 + C2F6 (1:2), and plasma treated/
materials using nanocoatings and other approaches that C2H4 + C2F6 (1:2) provides contact angles of around
generate a low surface energy finish with a surface 140 C [38].
roughness that creates an ultrahydrophobic and self- A recent development has been the introduction of a
cleaning effect. One approach is that marketed by Nano- special fluorocarbon product Anthydrin NK (Zschimmer
Tex LLC, (Greensboro, NC, USA) which produces a self- & Schwarz Mohsdorf GmbH & Co., Burgstädt, Germany)
cleaning cotton or cotton-blended fabric finish termed which is a low temperature cure product [39]. Use of a
Nano-Care [26]. The Nano-Care finish utilises whisker- special crosslinking system allows curing at around
shaped 10 nm molecules of a fluorinated monomer 110 C compared with conventional crosslinking at
copolymerised with a carboxylic acid oligomer and around 160 C. A booster product Polappret VIB is
converted to the anhydride to react with the fibre. Nano- co-applied if the finish must be fast to washing.
Pel treatments are similar to Nano-Care and are designed In two important recent publications [40,41] Gao and
for use on wool and multiple layer fabrics but Nano-Tex McCarthy [41] have criticised some previous publications
technology has also been said to simulate the surface of a on ultrahydrophobic surfaces for not adequately reporting
peach which has very fine, short hairs which are durably contact angles and for ignoring older significant literature
bonded to the fibres in the fabric. Nano-Tex technology is on this subject [42]. It was emphasised that contact angle
then licensed to other companies [27,28] and such fabrics hysteresis (i.e. the difference between the advancing and
are used in workwear, casualwear and sportswear [28]. receding contact angles) and not high contact angle
Schoeller Textiles AG (Sevelen, Switzerland) has actually controls water droplet movement (water-
introduced its NanoSphere technology which imparts repellency) [40]. A number of authors have defined
water repellency, soil-repellent, anti-adhesive and self- superhydrophobic surfaces as those exhibiting water
cleaning properties [29]. Their technology leads to the contact angles >150, while contact angle hysteresis often
formation of micro-rough three-dimensional surface is not mentioned [40,41]. The earlier publications by Fogg
structures from which water, dirt and oil simply roll off. [43] and by Cassie and Baxter [44] predate the ‘lotus
Using their NanoSphere finish dirt particles on the effect’ literature by five decades, demonstrating that
surface of the finished textile cling to water droplets and leaves exhibited advancing water contact angles >150.
when the water droplets run off the surface the dirt Gao and McCarthy established that lotus leaves in their
particles are simply washed away. NanoSphere laboratory exhibited advancing water contact angles (hA) of
technology is said to use a so-called guest–host system of 156.1 and receding water contact angles (hR) of 151.1
substances that allow spatial self-organisation and result [40]. The value of the contact angle hysteresis
in the formation of a micro-rough surface. In parallel with (coshR ) coshA) was 0.039. Application of a water-repellent
this structure formation, gel-forming additives lead to the treatment according to a patented method originally
development of the porous system of a membrane. applied to cotton [45] was then applied to conventional
Other approaches rely upon treatments that modify the polyester and to microfibre polyester fabrics. Both fabrics
fibre surface topography in combination with chemical were extracted with dry toluene and dried in air before
finishes. Research by the German Textile Research Centre being dipped in a toluene solution of 4 wt% methylsilicone
North West, Krefeld, Germany has described the followed by drying at 100 C for 1 h. On conventional
application of a photonic surface treatment using a pulsed polyester the advancing and receding water contact angles
UV-laser (excimer laser) to yield a regular micron-scaled were hA ¼ 151.2 and hR ¼ 140.1, but on microfibre
structure over a wide range of pulse energies [30]. polyester hA ¼ 170.2 and hR ¼ 165.1 [40].
It was observed that water droplets rolled easily on angles. A vessel with a perfectly hydrophobic inner
both fabrics, but much more readily on the microfibre surface would thus hold, but not touch water [41].
polyester. The force (F) required to move the droplets is It is clear that the application of such approaches to
given by: textile fabrics could produce a new generation of perfectly
F cLV ðcos hR cos hA Þ hydrophobic fabrics with outstanding water-, oil- and
stain-repellency. There are many potential end-uses for
where cLV is the surface tension of the liquid (i.e. water)
such surfaces in technical, industrial, medical and military
[40]. For conventional polyester the value of
end-uses, for protection from a wide variety of liquids.
(coshR ) coshA) was 0.109, but for the microfibre
polyester the contact angle hysteresis was considerably
lower at 0.019. Thus, Gao and McCarthy pointed out that
Hydrophilic softeners and moisture
it took six times as much force (7.85 dyn/cm vs 1.3 dyn/ management systems
cm) to move a droplet on conventional polyester Three very detailed reviews of chemical softeners and
compared with microfibre polyester [40]. It was their effects on textile materials have been recently
considered that this resulted from the nature of the published [46–48] which should stimulate developments
contact line structure and the barriers to its advancement for softening textile fabrics.
and recession, it being easier for a water droplet to recede Clariant (Basel, Switzerland) has introduced a novel
from a 2 lm diameter polyester microfibre than from the cationic silicone softener, Sandoperm SE1 oil liq which is
40 lm diameter conventional polyester fibres. It was described as a new development in the area of silicone
observed that the binary length scale topography (ca. chemistry [49]. The novelty lies in the fact that for the first
2 lm/50 lm) for the microfibre polyester diameter/ time the emulsifiers are linked through a covalent bond to
microfabric weave fineness was dimensionally similar to the silicone chain to produce a self-emulsifying amino-
that of the lotus leaf, but it has been asserted that the functional silicone fluid. By this special chemical
‘right’ single length topography is more effective at water- engineering of the molecule Sandoperm SE1 oil liq is
repellency [40]. emulsified for its applications simply by stirring it in water.
An exciting development is the recent production of a This process creates nanoemulsions wherein the particle
perfectly hydrophobic surface on silicon wafers by Gao size is extremely small and the silicone fluid is hydrophilic.
and McCarthy that has been termed ‘Lichao’s surface’ and Compared with typical macroemulsions (>150 nm
which exhibits hA/hR ¼ 180/180 [41]. The silicon wafers particles) and microemulsions (50–150 nm) Sandoperm
were submerged in toluene solutions of MeSiCl3 at room SE1 oil liq produces nanoemulsions (10 nm) which
temperature, rinsed with toluene, ethanol and water and impart an inner softness with a unique cool, natural and
dried. Vessels were closed to the air during reaction, but dry handle to woven and knitted fabrics [49]. Applicable
exposed (relative humidity ca. 40–65%) during solution to all types of cellulosic fibres, e.g. cotton, viscose, modal,
and sample introduction. Water droplets, it is claimed, do lyocell, and to polyamide, polyester and their blends, the
not come to rest on horizontal surfaces treated with this hydrophilicity imparted is classed as permanent to
procedure, and some 70% of samples treated by this washing. When applied to blends like polyester/viscose or
method exhibited a perfectly hydrophobic surface [41]. polyester/modal fibres the handle obtained can simulate a
A method for measuring extreme hydrophobicity was wool-like handle, while on synthetic fabrics a so-called
devised to distinguish between surfaces with a slight ‘silky-touch’ which is still a very soft and dry handle, can
affinity for water (hA/hR ¼ 175–179/175–179) and those be obtained.
with no affinity (hA/hR ¼ 180/180) [41]. The surface to be Sandoperm SE1 oil liq is a flexible softener which is
examined was lowered onto a supported droplet, and applicable by padding or by exhaustion and is designed to
repetitive contact, compression and release of the droplet be stable in combination with resin finishing baths in the
were recorded by video. Surfaces with contact angles presence of crosslinking agents and catalysts [49]. It is
<180 exhibited affinity for the droplet during claimed that Sandoperm SE1 oil liq does not yellow on
attachment and release, whereas droplets on a perfectly white fabrics which have been given a fluorescent
hydrophobic sample with a Lichao’s surface show no brightening treatment. Used along with Cassapret SRHA
affinity for this surface during contact or release after liq, Clariant has achieved finishes on polyester and
compression. The work of adhesion is apparently zero. polyester blend fabrics that combine soil-release properties
Stereoscanning electron microscopy of MeSiCl3-derived that are wash-permanent, extremely hydrophilic and allow
silicon wafer surfaces demonstrated a network of moisture transport, the so-called ‘silky touch’ finish.
cylindrical fibres with diameters of ca. 40 nm [41]. Gao A new era of garment performance has been introduced
and McCarthy consider that the conditions used for this with the synthesis of novel softening agents that form
modification promote ‘vertical polymerisation’ of MeSiCl3 part of a moisture management system [48,50–52]. With
into a covalently attached toluene-swollen 3-D the changing lifestyles of modern consumers, there is
methylsiloxane network [41]. Rapid extraction of toluene now more emphasis upon a more physically active and
by ethanol then induces phase separation. The siloxane is healthier lifestyle as part of a desire for a more youthful
not swollen by ethanol. If the humidity is not sufficiently approach to living, thereby providing some degree of anti-
high or the reaction time is too short, smoother surfaces ageing effect by keeping the body in good physical
with lower contact angles are generated. If the humidity condition. However, raising the level of physical activity
is too high, phase separation creates spherical-shaped leads to the production of perspiration exuded in order to
particles which generate surfaces with lower contact maintain a normal body temperature. This perspiration
must be rapidly wicked away from the surface of the skin the flame retardants used and the toxic nature of the
into the overlying garment and evaporated if the wearer is products released upon combustion of textile fabrics
not to feel discomfort through build-up of liquid [55–59]. Ideally, the best flame-retardant system for cotton
perspiration on the skin. Modern moisture management should char the fibre, releasing no toxic smoke or gases,
systems promote rapid wicking and evaporation and and prevent afterglow. Novel thin-film encapsulation of all
provide high added value to sportswear and casualwear, the fibres with an inherently flame-retardant coating system
significantly enhancing the perceived comfort level of the could be one path to progress, but the effects on fabric
wearer [48,49,51,52]. aesthetics would require optimising. Alternatively, the use
A novel moisture management agent, Ultraphil HCT of intumescent systems for flame- and heat-protection offer
from Huntsman Textile Effects is part of their High IQ some promise, but at present the chemical add-on levels
range which provides ‘cool comfort’ and is based upon a tend to be high and the activation temperature and speed
silicone microemulsion [53]. Engineered for application to of response of the system must ensure thermal protection
cotton by exhaustion, Ultraphil HCT exhibits the highest during the initial ignition period [60].
level of stability to the shearing forces found in high Flame retardancy, as a research area, has progressed
speed jet dyeing machines. Ultraphil HCT imparts only slowly, and some of the current major flame-
hydrophilicity and a very soft handle to cotton, while the retardant suppliers and their products have been
quaternary chemical nature of the structure results in a summarised elsewhere [61].
very high durability to washing. Thor Specialities (UK) Ltd (Wincham, UK) has
Hydrophilic silicones may be created using a variety of introduced two phosphorus-based products for use with a
chemical approaches [48,50,51], such as the use of: binder in flame-retardant back-coatings to replace
– polyether derivatives of silicone softeners with antimony/halogen systems [62]. Aflammit BCC is
polyglycol functionality; engineered for application to cotton and cotton-rich
– silicones with quaternary ammonium groups; blends, and Aflammit BCS is claimed to be effective on a
– silicones with tertiary amino groups; range of synthetic fibres.
– a,x-aminosilicones; A novel flame retardant applicable by exhaustion on
– silicones with amino groups modified by acylation or polyester is Cetaflam DB7 (Avocet Dye & Chemical Co. Ltd,
alkylation and Brighouse, UK) [57]. Cetaflam DB7 can be applied in jet
– blends of aminosilicones and hydrophilic polymers, e.g. dyeing of polyester at temperatures of 130 C to provide a
polyethylene and polypropylene glycols, polyethylene durable flame-retardant finish. Cetaflam DB7 is
imine, polyvinyl pyrrolidone, polyvinyl alcohol, non-foaming and the dyed and flame retarded polyester can
polytetrahydrofuran, etc. be washed off or reduction cleared after dyeing as normal.
A new hydrophilic finish from Clariant is Sandoperm Recent research has studied the co-application of
RPU Liquid, a new thermoreactive polyurethane for a crosslinking agents for cellulosic fibres such as
wash fast, very full and extremely soft handle on trimethylolmelamine or 1,2,3,4-butanetetracarboxylic acid
cellulosic and polyamide fibres [54]. Applied with with a hydroxy-functional organophosphorus oligomer
silicone softeners Sandoperm RPU Liquid produces a (Fyroltex HP from Akzo-Nobel, Arnhem, The Netherlands)
hydrophilic finish, improving the elasticity/shape [63,64]. Applied by a pad–dry–cure process using a
recovery of knitted goods. catalyst, the add-on used was relatively high which
The Nano-Dry finish from Nano-Tex LLC is a durable, adversely affected the fabric handle.
hydrophilic finish for nylon and polyester [27]. On the Devan Chemicals (Belgium) has focused upon halogen-
latter fibre polyethylene glycol and amino silicone in free flame retardants and has studied intumescent
nano-form are claimed to be applied to sportswear and finishes using three different approaches, [64] namely:
underwear requiring perspiration-absorbency. – encapsulating microscopic amounts of flame-retardant
particles in a thin polymer film, which forms a solid
Novel approaches to flame-retardant wall. This decreases the aqueous solubility of the flame
finishes retardant;
– use of nanoclay technology, in which layered silicates
Harsh handle and decreased tensile and tear strength and
in the form of reticular layers of crystals measuring a
abrasion resistance are inherent problems associated with
few nanometres and based upon a modified
the high chemical add-on and the use of flame-retardant
montmorillonite, have been used and
formulations that self-crosslink or crosslink or react with
– use of expandable graphites whereby the physical
the fibre. Thus, the major method used in the upholstery
expansion of intercalated (layer lattice-structured)
field has been the use of resin-bonded antimony–bromine
graphite is initiated by heat with vaporisation of the
flame-retardant systems applied via a back-coating
intercalates. This creates a volume expansion effect
technique so as not to impair the aesthetics of the fabric
around one hundred times greater than the original.
face [55–57]. Decabromodiphenyl oxide (DBDPO) or
For flame-retardant back-coating of textile fabrics a new
hexabromocyclododecane (HBCD) have been mainly used
approach has recently been developed [65]. The TexFRon
in conjunction with antimony trioxide. However, this
product range (ICL – Industrial Products, Israel) consists
system still has a marked effect upon the fabric physical
of aqueous self-crosslinking dispersions of nano-size
properties.
brominated acrylic copolymers. The bromine is thus
The future of flame retardancy is hindered greatly by
locked into the structure as part of the polymer chain and
environmental and ecotoxicological considerations, both of
the TexFRon coatings are designed for use with antimony [70,71,73,74]. The major types of enzymes used so far are
trioxide and are applicable by padding, dipping, coating, amylases, cellulases, lipases, pectinases, catalases,
spraying, foam application and screen printing. These proteases and laccases [68,69].
brominated acrylic copolymers are resistant to aqueous Enzymes are biocatalysts and based upon high-
leaching tests, have a solid content of 40–50% and a molecular weight protein structures. In conventional
bromine content (percentage on dry basis) of 30–46%. catalysts, the catalyst nominally takes part in the
In attempts to produce a halogen-free flame-retardant chemical reaction, but is left unaltered at the end of the
back-coating system Horrocks et al. have reported on process. However, side reactions such as hydrolysis or
phosphorus derivatives which can function, like bromine, oxidation of the enzyme may occur in textile wet
in the vapour phase [66]. One system developed was based processing and separation of the enzyme from chemical
upon an intumescent phosphorylated pentaerythritol contaminants/breakdown products from the fibres present
derivative together with relatively volatile tributyl will clearly complicate any attempts at enzyme recovery
phosphate. A phosphorus-based flame retardant or a and enzyme recycling, although if methods could be
component of the flame retardant that can be volatilised found the cost of enzyme processing could be decreased,
either as a decomposition product or by evaporation or by and water and energy also recycled. Research into this
an impinging flame could therefore offer one potential area could yield some fruitful results.
approach to a halogen-free and antimony-free flame-
retardant back-coating system. Microencapsulation of chemical finishes
Research in Russia at the Semenov Institute in Moscow and fragrances
led to the introduction of a novel flame retardant for wool
Microencapsulation technologies have now only really
termed Noflan (Firestop Chemicals Ltd, UK) [67]. This is
begun to be exploited [75–79]. Phase-change materials
an organophosphorus compound based on the ammonium
(PCMs; e.g. Outlast, Frisby) that absorb or release heat
salt of an amidoalkylphosphonic acid with a phosphorus
according to the conditions are interesting for some end-
content of 14%. This patented process involves
uses [75,78]. However, a more interesting development is
application by a pad–dry–cure technique, while wool
that of the incorporation of fragrance within the
carpets could be treated by a spray–dry–cure or spray–
microencapsulated polymer spheres, allowing a gradual
dry–steam method. Noflan promotes solid phase charring
release of an appropriate fragrance to promote aromatherapy
of wool, but is principally intended for fabric and carpet
[77–79]. Typical perceived benefits could include:
applications, especially for transportation fabrics.
– uplifting/head clearing, e.g. active sportswear;
A recent extension of Noflan technology is Noflan E
– relaxing/encourages sleep, e.g. fragrances for nightwear
[67]. This is an encapsulated form of the flame retardant
or bedding;
currently under development, directed towards
– muscle easing, e.g. for after-sport activity and
unsaturated polyesters and polyurethanes.
– clear thinking/confidence building, e.g. formal
Noflan currently contains chlorine in the form of
businesswear suits.
ammonium chloride, but research and development to
In addition, there are opportunities for health and well-
introduce a halogen-free flame-retardant system has
being by using cosmeto-textiles in which substances that
resulted in Bizon, a patented halogen-free, antimony-free,
enhance skin appearance, or vitamins can be absorbed by
phosphorus-based flame retardant [67]. This is said to
the skin [76–81]. Skin moisturisers and skin-cooling
be produced by a reaction of nitrilotris(methylene)
products, or even appropriate drug therapy could become
triphosphinic acid with urea to produce an ammonium
important markets with an ageing population. Another
salt of nitrilotris(methylene)triphosphinic acid amide.
important area could be the application of
This functions via a solid phase charring mechanism and
microencapsulated insect-repellents for protection against
has many potential applications, including polyolefines
mosquitoes and other insects [78,82].
and high temperature plastics.
Potential areas for growth in microencapsulated finishes

New approaches using enzymes The following areas are considered to offer potential
The range of enzymes available for application in textile for the use of microencapsulated finishes [75,82].
wet processing continues to increase each year and new – Phase-change materials for thermoregulation;
uses will clearly be found over the next decade. The book – Fragrance release;
by Cavaco-Paulo and Gübitz provides an excellent – Aromatherapy agents;
overview of textile processing with enzymes [68] and a – Antimicrobial finishes;
short review of the major types of enzymes and their – Deodorising finishes;
actions has also been published [69]. The use of various – Biocides;
enzymes to carry out surface hydrolysis of polyester – Insect-repellent finishes;
fibres to increase fibre hydrophilicity and modify – Insect-resist treatments;
dyeability has been reported [70–72]. The use of nitrile – Skin-moisturising agents;
hydratase enzyme to modify the dyeing efficiency of – Skin-cooling agents;
acrylic fibres has been studied and the treatment modifies – Controlled release of vitamins and pro-vitamins;
the surface of acrylic fibres converting the surface nitrile – Controlled release of other agents absorbed through the
groups into amide groups, thereby increasing the skin.
hydrophilicity and the antistatic properties of the fibres
– Depilatory agents; are most keenly felt. Outlast Technologies’ Thermocules

– UV-absorbers; have been used in gloves, socks, hats, outdoor wear, e.g.
– Antistatic agents; vests, thermals, parkas, snowsuits and trousers and in
– Flame retardants; household textiles such as blankets, duvets, mattresses
– Water repellents; and pillowcases. Other applications include microclimate
– Antisoiling agents; control in medical textiles.
– Chemical protection; Ciba Specialty Chemicals has introduced Encapsulence
– Softeners; PC140 using their in-house microencapsulation systems
– Cross-linking agents; and their microencapsulated PCM is utilised for Outlast
– Pleating agents; thermal regulation [83]. Ciba Encapsulence PC140
– Colorants; microcapsules have been incorporated into acrylic fibres
– Enzymes. using late injection technology by Acordis UK for Outlast.
In addition, there are opportunities for micro- Some 5–10% of microcapsules are permanently locked
encapsulation in other fields such as biosensors and into the acrylic fibres with no change in fibre properties
anti-counterfeiting agents [80]. or changes necessary to the fibre processing.
Phase-change materials for thermoregulation Aromatherapy/fragrance release

A new concept for the thermoregulation of skin Aromatherapy has entered into the lifestyle of many
temperature was developed in the 1980s for the US consumers in the stressful ambience of the modern global
National Aeronautics and Space Administration (NASA) village in which we all live. Aromatherapy utilises the
which was originally designed with the aim of controlling controlled release of an aroma or fragrance to promote
the thermal barrier properties of garments for use in feelings of comfort and well-being amongst consumers
space suits [80]. Although microencapsulated PCMs were [76,79,80]. Amongst the many applications for
developed these were never utilised for space suits. The aromatherapy, a number of fragrances such as camomile,
inventor, the Triangle Research and Development Co., lavender, lemon, peppermint, jasmine and rose can
(Raleigh, NC, USA) subsequently licensed the technology provide a broad spectrum of advantages when applied to
to Outlast Technologies, Inc. (Boulder, CO, USA) and performance apparel. These are summarised in Table 1
phase-change technology has been exploited in textile [79].
fibres and fabric coatings.
Phase-change materials utilise microencapsulated Table 1 Aromatherapy benefits from fragrances [79]
chemicals such as nonadecane (C19H40) and other
medium-chain length alkanes [76,78,80]. When the Benefit Fragrance
ambient temperature increases above 32.1 C (the melting
point of nonadecane) the nonadecane melts and latent Uplifting Lemon, peppermint
heat is absorbed thereby interrupting the increase in Relaxing Camomile, lavender, jasmine
temperature of a garment. Once the ambient temperature Aphrodisiac Jasmine, rose
Balancing Lavender, jasmine, rose
falls the PCMs solidify and the latent heat is released
Clear thinking Peppermint
providing a heating effect. The crystallisation temperature Confidence building Jasmine, rose
of nonadecane is 26.4 C. Thus, PCMs can be used to Head clearing Peppermint
provide a cooling effect, or a heating effect, upon the Muscle easing Peppermint
Encourage sleep Camomile, lavender
garment microclimate depending upon the ambient
temperature.
The use of PCMs has been widespread with as many as
150 companies using microencapsulated PCMs under LJ Specialities (Holmewood, UK) has pointed out that
licence from Outlast Technologies, Inc. which has an uplifting/head clearing fragrance-like microencapsulated
consolidated its position as the world leader through the peppermint could be used for active sportswear, while
acquisition of substantially all of the remaining assets of lavender on bedding has been shown in customer wearer
Frisby Technologies, Inc., (Winston-Salem, NC, USA) trials to relax customers and encourage sleep [79].
including various technology licences, the Thermasorb Peppermint is also claimed to have muscle-easing
trademark, logo, website and intellectual property rights properties, another advantage for active sportswear end-
in the field of PCM technology. Phase-change material uses. Microencapsulated fragrances that encourage clear
microcapsules have walls <1 lm thick and typically may thinking/confidence building could be applied to suitings
be 20–40 lm in diameter with a PCM loading of 80–85%. for formal wear. There are clearly a myriad of essential
The relatively high surface area for heat transfer afforded oils with many potential applications.
by the small microcapsule size ensures that the response A major advance in this field especially for wool fabrics
of the PCM to external temperature changes is very rapid has been the introduction of Sensory Perception
[80]. Technology (SPT) microcapsules manufactured by
Outlast Technologies Inc. (Boulder, CO, USA) Adaptive International Flavors and Fragrances (IFF) based in New
Comfort technology uses their patented York, USA the largest flavour ingredients house in the
microencapsulated PCMs (termed Thermocules) in a wide world [84].
variety of textile applications especially on garments for SPT microcapsules are distributed and sold globally by
those parts of the body where extremes of temperature Woolmark Development International Ltd (WDI) part of
the Woolmark Company (Ilkley, UK) which helps in the Table 2 Cognis: Skintex products and their benefits [85]
technology transfer to mills and wet finishing plants. SPT
microcapsules are based on a chemical similar to melanin Active
together with certain binders that create strong chemical Products ingredients Benefits
links with the fibres to impart high durability. SPT
microcapsules will withstand repeated domestic washing, Moisturising Squalane Moisturiser from clothes
Vitamin E
and even ironing treatments [84].
Manoı̈ de Tahiti
SPT microencapsulation technology is highly versatile; Passion fruit oil
for aromatherapy end-uses thousands of different types of Cooling Myritol Cooling skin care in the fabric
fragrances may be provided or bespoke fragrances created Menthol
Energising Menthol Revitalising aroma in the fabric
for specific textile applications. Because the SPT
Orange
microcapsules provide a reservoir of fresh perfume this Ginger
reduces the need to use quantities of the less volatile Rosemary
‘bottom’ notes and use far more of the volatile ‘top’ notes Relaxing Valerian Relaxing aromatherapy from
Amber tree fabric
instead without the associated fragrance fade problem.
resin oil
Another innovative approach could be, for example, Lavender
clothes that could actually repel or negate odours. Quest Anti-heavy Grapefruit Revitalising care for tired legs
International UK Ltd (Ashford, UK) has developed a legs Menthol
Lemon
unique set of ingredients that is the equivalent to ‘white
Thyme
noise’ to tobacco smoke, which can be added to clothes Mosquito Various Effective mosquito repellent
via SPT. Such treatments could be applicable to fibres repellenta in the fabric
and fabrics used for seats or carpeting, creating ‘smart
environments’ which always smell fresh, e.g. in public a Active ingredients being used in mosquito repellent include N,N-
dimethyl-m-toluamide (DEET), permethrin, pyrethrum and essential oils
transport systems [78].
Source: Cognis
Cosmeto-textiles and skin care benefits

There is now an increasing vogue for so-called cosmeto- turn a simple garment into one termed an ‘active-
textiles which are essentially garments that are designed wellness’ garment [78]. Cognis has introduced a variety of
to come into contact with the skin which then transfer active agents which have been microencapsulated and
some active substance that may be used for cosmetic can be applied by exhaustion onto the fabric during wet
purposes, in particular to combat ageing effects. Because processing. The properties of the Cognis Skintex System
people in the developed nations are living longer and are claimed to be retained over several domestic washing
acting younger (the so-called ‘youthful ageing’ effect) cycles.
there is now a demand for products which are designed Cognis recently launched its latest innovation, Skintex
to beautify and to combat ageing. Microencapsulation of Reloading, to meet the consumer demand for long-lasting
active ingredients, e.g. Aloe vera gels that can be released effects by making it possible to recharge textiles with new
gradually and be absorbed through the skin are typical of microcapsules. Skintex Reloading is available for the
this type of finish [76,77,80]. slimming effect, using care ingredients such as Shea
The problem of cellulite, thought to occur in some 85% butter, apricot kernel oil, rose hip oil and red algae
of women, is considered to be caused by poor micro- extract. The Reloading technology can also be used to
circulation. Sensory Perception Technology utilises kelp refresh the cooling/moisturising properties of Skintex-
bladderwrack as an iodine source which is easily treated clothing [78].
absorbed into the epidermis [84]. This speeds up the The active ingredients of the Cognis Skintex System are
micro-circulation, stimulating glands and the connective delivered by three separate means [78]. The most
tissues. This is claimed to fight the root causes of important method is by friction between the
cellulite. Worn for long periods of time next to the skin in microcapsules in the fabric and the skin. Secondly, the
hosiery and underwear, kelp can also be applied with natural biopolymer membrane of the microcapsules can
Aloe vera to promote an anti-cellulite effect. be biodegraded by enzymes naturally present in the skin.
Vitamin E has been widely used in skin creams for Thirdly, when the microcapsule biopolymer membrane
medicinal and cosmetic purposes. Its action is basically (which is insoluble at pH 6–7) comes into contact with
considered to be that of a powerful anti-oxidant, human skin (at pH 4–5) this causes the membrane to
protecting skin cells against the damaging effects of free dissolve, thereby delivering the actives. The Cognis
radicals which age the skin. Vitamin E has been used on Skintex System has been designed for use on hosiery,
walking socks using SPT microcapsules for its blister underwear and sportswear made from cellulosic fibres
healing effects and also applied along with Aloe vera and and all other fibres and blends. Cognis Skintex
kelp to underwear/hosiery to help fight the effects of ingredients have been produced for skin moisturising and
stretch marks (i.e. for maternity wear). relaxing, for combating the effects of cellulite (anti-
Cognis Deutschland (Düsseldorf, Germany) has cellulite) on the skin, while other areas include hair
introduced their Skintex Care System, termed ‘Wellness retardant and tanning purposes. A list of Cognis Skintex
to Wear’. In the Cognis-patented Skintex System, active products and their benefits is given in Table 2 [85].
ingredients are microencapsulated using chitosan, a Speciality Textile Products Limited (Loughborough,
substance made from the shells of shrimps in order to UK) market their Biocap series of functional biocapsules
which incorporate vitamins such as vitamin A, D and E such as tea tree oil, eucalyptus and clove. Essential oils
and Aloe vera for application to underwear, T shirts, are generally volatile and will rapidly evaporate from
stockings, socks and bedding [81]. surfaces so that microencapsulation within Micap yeast
microcapsules can be used to minimise evaporation and
Antimicrobial and deodorising finishes greatly extend the shelf life. Tests have demonstrated that
A major growth concept over the last 5 years has been the selective release of Micap essential oil combinations
the introduction of the concept of durable freshness upon contact with MRSA results in a superior rate of kill
applied to all kinds of textile apparel, especially those [78,90].
which are worn under conditions of strenuous physical Tea tree oil has been used in SPT microcapsules
exertion, or in hot climates. The growth of bacteria on the because it possesses natural antibacterial and antifungal
perspiration entrapped into a garment can rapidly lead to properties. A member of the Eucalyptus family it contains
the build-up of undesirable odours which then over one hundred different compounds. It has been
necessitates the garment being washed or dry cleaned to shown to be effective against a wide variety of bacteria
restore the freshness [86,87]. [78]. Tea tree oil is said to be antiseptic and has a
Garments such as intimate apparel, socks, gloves and stronger action against bacteria than many usual
especially textile products used in footwear clearly offer a household disinfectants.
large potential market for retention of freshness during
wear. In addition, there are many other areas with Medical textile applications
potential for exploitation of the durable freshness The microencapsulation of antimicrobial agents within
concept, including household textiles, e.g. carpets, textile fibres, yarns and fabrics clearly has potential for
curtains, cushions, etc., as well as opportunities in many forms of medical textiles for preventing bacterial
textiles used in automotive textiles such as car seating and fungal infections. The controlled release of antibiotics
and floor coverings, and textiles for other forms of from textiles in contact with the skin offers up the
transportation, e.g. trucks, buses, trains and aeroplanes prospect of a marked decrease in post-operative infections
[86–89]. Another important area is that of performance after surgery [91]. Surgical sutures containing micro-
sportswear for all manner of physical activities. The encapsulated antibiotics could give a controlled release of
many approaches to antimicrobial finishes are reviewed antibiotic around the site of the surgical incision speeding
in the section on antimicrobial finishes. patient recovery and preventing post-operative infection
Microencapsulation of antimicrobial agents could in the first few important days after surgery.
provide a long-term controlled release effect that could be There is also the prospect of the development of the
utilised to prevent the growth of bacteria in textiles that microencapsulation of drugs to give a controlled slow
can give rise to undesirable odours, or to combat the release of the active ingredient to be absorbed through
growth of more harmful bacteria. the skin. This may be one area where nanocapsules or
The AB Cap (antibacterial microcapsule) marketed by small microcapsules may be developed for specific
Speciality Textile Products Limited (Loughbrough, UK) applications, for use in medical dressings, etc. [80].
contains a nonionic product with a pH of 7 0.5 (1%
solution) [81]. This provides an excellent dispersion in Insect-repellent and insect-resist treatments
liquids and is effective at the 1–2% level on a wide For apparel designed to be worn in tropical climates
range of bacteria. More revolutionary still is the patented where mosquitoes abound there is clearly a market for
Silver Cap, in which an innovative manufacturing insect-repellent treatments that have a long-lasting effect.
technique places silver nanoparticles on the outer wall Microencapsulation of insect-repellent agents can be
of the microcapsules [81]. Silver ions are claimed to employed to provide a longer lasting controlled release
sterilise some 650 different viruses and can provide a effect. Thor SARL (Salaise sur Sanne, France) have
highly effective antibacterial effect when applied to developed a method of microencapsulating a synthetic
textiles. The wall material may be of natural or pyrethroid, permethrin, which is a known insecticide
synthetic polymer and may incorporate other materials, [78,82]. A particular area of use is in clothing for the
e.g. perfume, Aloe vera, colour-changing dyes or other military serving in tropical climates.
antimicrobial agents. Textiles treated with tea tree oil SPT microcapsules
Microencapsulation of antimicrobial agents is an area have been tested by the Carrol Loye Biological Research
which is now receiving attention in the fight against Institute (CA, USA) and shown to demonstrate
methicillin-resistant Staphylococcus aureus (MRSA) significant mosquito repellence properties [78,84]. The
infections. Micap plc of Newton-le-Willows (UK) has natural organic ester plant oils act effectively as a nerve
developed a mixture of three essential oils, combined in a agent on insects but more importantly recent research
specific ratio, which are microencapsulated and applied has shown that these have an unusual effect on
in a gelatine base to the wound dressing [90]. Ultimately mosquitoes which is termed ‘jamming’. This effect results
the microencapsulated essential oils will be incorporated in the ‘black box’ which helps the mosquito search for
into the wound dressing and there is interest in this victims being turned off. As a result microencapsulated
technique from companies that manufacture wound release of these plant oils has been shown to
dressings [78]. significantly decrease the bites per minute in test boxes
With the increasing resistance of microbes to from 50 to virtually none.
antibiotics, considerably more interest is now being Another area is that of microencapsulated insect-resist
shown in the antimicrobial properties of essential oils treatments for textiles containing natural protein fibres-
like wool and silk. Such finishes could provide long-term Antimicrobial finishes
protection against the ravages wrought by the larvae of
As some lifestyles have become more active, sportswear,
moths and particularly many types of beetles [88,89].
activewear and casualwear may become more easily
contaminated by perspiration leading to bacterial growth
Flame-retardant textiles
and body odours [86–89]. A number of antimicrobial
Conventional flame-retardant treatments often suffer from
treatments are now on the market that can kill bacteria
a lack of durability to soaking in water or to domestic
and enable garments to remain smelling fresh for longer
washing procedures because of the aqueous solubility of
[86–89]. An alternative approach is that of b-cyclodextrin
the flame retardant used. Microencapsulation could help
which, with a suitable reactive group, could be covalently
to protect the active flame retardants from the action of
bound to cotton [93]. It has been shown that body odours
wet treatments, prolonging the durability of the effect and
become trapped within the hydrophobic internal surfaces
enabling treated textiles to pass flammability tests which
of this torus-shaped molecule eliminating the building up
involve a presoak in water prior to testing. Moreover, the
of body odours. This area is set for growth as the
adhesion of the microencapsulated flame retardant to the
environment warms up through global warming and if
textile could be engineered by a suitable choice of
garments are required to be washed less frequently then
polymer coating to maintain the durability to leaching
this decreases environmental pollution. The use of anti-
tests or multiple wash cycles containing bleach-activated
microbials for preventing infections has already been
detergents [77,80].
discussed in detail.
By careful selection of the polymer coating used for
No one antimicrobial finish, as yet, fulfils all the
microencapsulation it may be possible to provide a
necessary criteria for all textile end-uses but some very
polymer coating that not only functions as a protective
effective and durable antimicrobial finishes have been
coating for the intumescent flame retardant combination,
developed and their utilisation in textiles, clothing and
but also may additionally provide satisfactory adhesion
footwear is increasing, as their undoubted benefits take
and contribute to the carbonific component of the finish.
hold in the conscious minds of consumers worldwide.
Antimicrobial finishes inhibit or preferably kill
Chemical protection
microorganisms by a number of different mechanisms
This is a vast subject and for recent developments the
that act around the cell wall of the microorganism
authoritative book by Scott should be consulted [92].
[86–89,92]. Thus cell wall damage, alteration of
There is now much greater interest in developing
cytoplasmic membrane permeability, alteration of the
effective methods of protection against chemicals, either
physical or chemical state of proteins and nucleic acids,
from the hazards created by accidents and spillages, as
inhibition of enzyme action, or inhibition of protein or
well as from chemical attacks. The global upsurge in
nucleic acid synthesis are all chemical approaches that
terrorist activity and the needs of the military to protect
can be utilised by antimicrobial finishes to inhibit or kill
their personnel against chemical attacks have stimulated
the microorganism.
developments in a difficult field in which to conduct
It is well known that certain other chemical finishes
research.
can also help in promoting antimicrobial action. Thus,
Chemical decontamination clothing is clearly a high
the application of easy care/durable press finishes based
priority and interfacial polymerisation and phase
upon N-methylol compounds is known to help prevent
separation techniques have been utilised in order to
rotting of cellulosic textiles [88]. In a similar way the
generate microcapsules of ethylcellulose (1–10 lm
application of hydrophobic finishing agents such as
diameter) containing a chemical decontamination agent
silicones and fluorochemicals that provide a water-
[80].
repellent effect can help to prevent microbial attack of
Against the highly potent nerve gas Sarin (isopropyl
textile fibres and fabrics. In some applications the
methylphosphofluoridate) almost total deactivation was
durability of the antimicrobial finish to washing may be
claimed for monoethanolamine and a small proportion of
improved by the use of a binder or resin system [88,89].
4-(N,N-dimethylamino) pyrimidine microencapsulated in
For apparel fabrics it is important that the anti-
methyl cellulose-based microcapsules. Laundering for 1 h
microbial finish leaves the garment comfortable to wear.
at 45 C, or irradiation in a Weather-Ometer at 40 C to
A very important consideration for antimicrobial finishes
simulate 1800 hours of sunlight exposure did not lead to
applied to apparel fabrics is that such treated fabrics and
any loss of detoxification power [80].
garments are safe to handle and use. Antimicrobial
Clearly this area of performance apparel will attract a
finishes for apparel should be non-toxic, non-irritating
very high added value, and durability of the effect to
and where handled regularly, the finish must also be non-
prolonged storage prior to use will be important. In most
sensitising.
cases such garments will probably only be used once and
Antimicrobial finishes have been developed that rely
then discarded, so that the highest performance criteria
upon the following approaches for their effectiveness
are required for a single exposure to highly toxic
[88]:
chemicals. Undoubtedly microencapsulated decontami-
– provide controlled release of the antimicrobial agent
nation agents will form only one element of a
(the major method currently used);
multifunctional chemical protection suit, which will also
– provide a barrier/blocking action using inert films or
incorporate low-energy surface finishes to prevent wetting
coatings to physically block bacteria, or films/coatings
and wicking of chemicals into the garment and hence
with direct surface activity against bacterial growth and
onto the skin [92].
– regenerable active microbial agents, which can be – greatly increase the use of fibres in technical textiles,
regenerated by treatment with a bleaching agent during biomedical and healthcare end-uses and
laundering or with ultraviolet radiation. – open up opportunities for textile sensors.
In order to increase the durability of the antimicrobial Many of the recent developments in the field of
action to washing treatments a number of approaches can nanocoating were recently described at the 3rd European
be utilised, according to the chemical nature and mode of Coating Congress in Kortrijk (Belgium) [103].
action of the antimicrobial agent, [88] e.g. Nano is derived from the Greek word nanos, meaning
– insolubilisation of the antimicrobial agent either in or dwarf, and in the basic SI system (Système International
on the fibre; d’Unités – the International System of Units) the prefix
– fibre treatment with resins, condensates or fibre nano is used as a factor indicating 10)9 [104,105]. Thus,
crosslinking agents; 1 nm is one billionth of a metre (10)9 m). By comparison
– microencapsulation of the antimicrobial agent and the diameter of a single human hair is ca. 80 000 nm, a
durable binding of the microcapsules to the fibre; human red blood cell is ca. 7000 nm wide and a water
– coating of the fibre surface; molecule is almost 0.3 nm wide [105].
– chemical modification of the fibre by covalent bond Therefore, nanoscience and nanotechnology are
formation and essentially concerned with materials that are very small
– use of graft polymers, homopolymers and/or [104–107]. The term nanoscale has generally been taken
copolymerisation onto the fibre. to lie in the range of 100 nm down to the size of atoms,
The modern approaches to antimicrobial finishing have i.e. down to ca. 0.2 nm. Nanoscience has been defined as
been summarised in detail elsewhere [86–88,92–96]. the study of phenomena and manipulation of materials at
atomic, molecular and macromolecular scales where the
Nanocoating technology and smart properties of materials differ markedly from those at a
coatings larger scale [104]. Nanotechnologies, on the other hand,
refer to the design, characterisation, production and
A comprehensive review of coating and lamination has
application of structures, devices and systems, by
been given by Woodruff [97]. This is a very interesting
controlling shape and size at the nanometre scale
area with many potential end-use applications and
[104,107,108].
possible markets for all types of textile fabrics. Coating
Nanoscience, the science of materials at the nano-scale,
technologies based upon aqueous coating systems, foam
is fundamentally different from the macromolecular scale
coating, hot melt or even warm melt systems are
for two principal reasons. Nanomaterials have a relatively
becoming more important than the older solvent coating
larger surface area compared with the same mass of
processes on the grounds of lower environmental
material produced in a larger form [5,104–106,108]. One
pollution [97–99].
consequence of this increase in surface area is that some
Microporous and hydrophilic polyurethane coatings
materials that are normally inert in their larger form
and also lamination techniques have been developed to
become reactive in their nanoscale form. Thus, the
provide waterproof ‘breathable’ fabrics with a suitable
strength and the electrical properties of the material may
level of water vapour permeability [19,90]. These provide
be altered. A second important reason is that as the size
higher levels of moisture comfort in clothing designed for
of the material approaches the lower end of the
outdoors, under foul weather or survival conditions or for
nanoscale, i.e. towards the molecular and atomic scale,
sports activities involving strenuous physical exercise.
the behaviour of matter becomes more reliant upon
The mechanisms of action of microporous and also
quantum effects [105,106,108]. As a result the optical,
hydrophilic polyurethane coatings have been reviewed by
electrical and magnetic behaviour of many materials are
Lomax [100–102].
changed from those at the nanoscale.
The Nextec EPIC process (Nextec, Vista, CA, USA)
Nanocoating the surfaces of textiles, clothing and
which gives rise to fibre encapsulation sheathes each
textiles for footwear is one approach to the production of
fibre with its own polymer coating, but leaves each fibre
highly effective antimicrobial treatments that are effective
distinct from its neighbours [103]. This maintains the
in killing the bacteria that can lead to malodour formation
water vapour permeability of the fabric, but provides
[106,107]. Purista (Arch Biocides, UK) is an antimicrobial
appropriate levels of water repellency together with its
nanocoating based upon a cationic polymer
own unique handle. If such a method could be
[poly(hexamethylenebiguanide hydrochloride)] [109]. This
developed to apply coatings that would impart total
product has a degree of polymerisation of 16 and can be
easy-care properties including water repellency
applied by exhaustion, padding or by spraying. The
properties it could give rise to a very useful fabric
Purista nanocoating is held on the fibre surface by strong
finishing technique.
electrostatic and hydrogen bonds and punctures the
Nanocoatings are now exciting considerable interest
bacterial cell wall, killing bacteria that can accumulate in
because of the current explosion of interest in nano-
textiles and clothing through the retention of human
science and nanotechnology [5,104–106]. The main thrust
perspiration exuded during physical activity and wear.
in nanocoating applied to textiles and clothing will be to:
The Purista treatment thus enables garments to be ‘fresher
– improve the properties and functional performance of
for longer’ and is currently being used in a wide variety of
existing materials;
high-street garments, suit linings, sportswear and bedding
– develop smart and intelligent textiles with novel
as well as for wound healing in the USA.
functions;
Nanocoating of textile fabrics, complete finished maintaining a pristine surface appearance [5,106]. The
garments or shoes can be obtained during plasma possibility of producing a super-repellent, anti-soil and
polymer treatments [110]. Plasma is the fourth state of anti-stain nanocoated surface that would self-clean and
matter (after solids, liquids and gases) which was first self-heal if scuffed represents the Holy Grail to footwear
termed ‘radiant matter’ by Sir William Crookes in 1878 as manufacturers. Combined with an immobilised anti-
a result of experiments in the passage of electricity microbial this should provide undreamt-of performance
through gases [111]. The word plasma is derived from a in sports shoes, boots and normal footwear. The potential
Greek term meaning something formed, fabricated and for footwear for sports and the military, children’s and
moulded and was first used by Irving Langmuir in 1928 fashion shoes is bounded only by the limitations of
[112,113]. The plasma generated by electrical discharge human imagination. Cleaning shoes could be a thing of
through a gas consists of a mixture of positive and the past!
negative ions, electrons, free radicals, ultraviolet radiation Recent work on paints in the Swedish Ministry of
and many different electronically excited molecules. By Defence is aimed at producing multispectral camouflage
varying the conditions of the plasma treatment and the coatings to conceal military hardware in the field [119].
nature of the specific gas or gases present, a variety of Ultimately the goal was to make an object invisible at all
surface treatments can be produced that change the three wavelength regions – the visible, infrared and
chemical or physical nature of the fibre surface, thereby microwave regions (where it would be detected by radar).
radically altering all treatments that depend upon fibre Deception is currently achieved using micron-sized
adhesion, e.g. coating, lamination and bonding [114]. semiconductor particles in the paint. These absorb
Plasma polymer treatments may be considered for the infrared radiation and re-emit it at a wavelength outside
application of a wide range of ultra- or super- the working limit of infrared detectors (3–5 and 8–12 lm).
hydrophobic, antistatic, insect-repellent, odour control By particle size variation the infrared emission can also
and flame-retardant treatments. Work at the University of be matched to the background. Using spray-drying
Durham and the Ministry of Defence in the UK originally spherical ceramic particles can be produced which
intended to provide anti-chemical warfare agent coatings contain nanometre-sized pores into which pigments (e.g.
has now been commercialised and extended to other green, grey and brown) can be impregnated. These
treatments [114–116]. The nanocoating of silk and cotton coloured particles are then combined with an organic
in a radiofrequency inductively coupled plasma reactor binder and can be applied by brush or spray coating.
has been carried out in collaboration with Surface Beneath the combined visible/infrared coating there is a
Innovations Ltd, Wolsingham, Co. Durham, UK. Using second layer to prevent the object being detected by radar
gases or the atomised spray pressure deposition technique [119]. It seems logical to consider such a system for use
3–5 nm thick super-repellent coatings had been generated with camouflage coatings for textiles, although the nature
[114–116]. Such coatings exhibited critical surface of the organic binder will need to be matched to the
tensions as low as 6 mN/m, well below chemical warfare fabric end-use.
agents such as mustard gas (43 mN/m), VX (30.4 mN/m)
and GD (25.0 mN/m). Current research is in hand on Conclusions
antimicrobial coatings and smart proteins [116,117]. The
It has not been possible within this short review to
P2i Ltd pulsed plasma polymerisation technology is
discuss all the innovative technologies that are emerging
designed for treatment of finished end products, e.g.
within the textile industry. Nanotechnology in the form
whole garments, gloves, socks, shoes, etc. and provides
of nanofibres, nanoparticles and nanocoatings holds out
an environmentally friendly closed treatment system
much promise for the future. Nanofibres embedded
[116,117].
within composites, for example, could open up many
Another interesting approach is the coating of textiles
opportunities for material reinforcement.
with nanoparticles of titanium dioxide. Research work in
It is clear that all textile scientists and technologists
Switzerland has demonstrated that nanoparticles
must keep abreast of the latest developments. Textile
composed of a mixture of 80% anatase and 20% rutile
finishers in particular could harness many of the exciting
titanium dioxide can effectively decolorise red wine
opportunities now emerging in order to enhance and
stains in the presence of water, oxygen and a range of
extend the appeal, the markets and the end-uses for
radiations from sunlight to neon light [118].
textiles. The frontiers of the art of the possible are
In the USA, research is currently being conducted on
continually expanding and imaginative research and
body armour consisting of Kevlar bullet-proof vest
development will be needed to convert ideas into reality.
material which has been dipped in a shear-thickening
In this way, the undoubted aesthetic and functional
fluid consisting of colloidal silica particles (average size
performance of textiles can be enhanced to excite the
ca. 450 nm) which are supported in a liquid phase [119].
imagination of the consumer and extend the markets and
Under the impact of a high-velocity bullet the particles
end-uses for textile materials.
cluster and jam under the applied stress leading to a high
strength ceramic materials response, but under normal
conditions the colloids do not shear thicken.
Acknowledgement
Another fertile area for smart coatings is for I would like to thank Prof. N A Ibrahim, Head of the
nanocoatings that when subjected to wear or abrasion Textile Research Division, National Research Centre,
become scratched or scuffed, but due to their special Dokki, Cairo, Egypt for his permission to publish this
physicochemical characteristics will self-heal, thereby updated paper.
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doi: 10.1111/j.1478-4408.2007.00064.

Innovative technologies for high

Introduction North America and Europe is considered to be the high

Potential areas for growth in microencapsulated finishes

– Depilatory agents; are most keenly felt. Outlast Technologies’ Thermocules

Phase-change materials for thermoregulation Aromatherapy/fragrance release

Cosmeto-textiles and skin care benefits

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