state of the art and representative nanomaterials of finished textiles · 2016. 11. 11. ·...

www.ecotexnano.eu | LIFE2012 ENV/000667 | [email protected] | @LIFE_ecotexnano 1

State of the art and representative nanomaterials of finished textiles

Project acronym: ECO-TEXNANO

Project full title:

Innovative tool to improve risk assessment and

promote the safe use of nanomaterials in the textile

finishing industry

Reference number: LIFE12 ENV/ES/000667

Deliverable: State of the Art and representative nanomaterials of

finished textiles

Version: v1. March 2014

Associated Action: A1

Action leader: LEITAT


Table of contents

1. Scope and objectives of the Deliverable ......................................................................................... 3

2. Overview of nanomaterials in the textile finishing industry ........................................................... 3

3. Finishing processes of textiles: Nanomaterials & Conventional products ...................................... 4

3.1. Conventional products used in finishing processes of textiles................................................ 4

Conventional products used in finishing processes and properties provided to textile ................ 4

Conventional finishing textile processes (padding, exhaustion, spray, coating, pad-batch, etc) ... 5

3.2. Nanomaterials used in finishing processes of textiles ............................................................ 7

3.2.1 Nanomaterials contained in textiles and their properties ..................................................... 7

3.2.2 Nanotechnology finishing textile processes ......................................................................... 15

3.2.3 Human health & Environmental risks of nanomaterials ...................................................... 27

3.3. Comparison among conventional products and nanomaterials used to reach specific

properties .......................................................................................................................................... 29

4. Methodology for the nanomaterials selection.............................................................................. 29

5. Selection of representative nanomaterials used in finishing processes of textiles ...................... 31

6. Conclusions .................................................................................................................................... 38

7. References ..................................................................................................................................... 39


1. Scope and objectives of the Deliverable

The present document is part of the Ecotexnano project (LIFE+ project), whose overall goal is to

improve the environmental performance as well as minimize risks in the textile finishing industry

through the use of the best nanomaterials available in the market. Ecotexnano project will provide a

user friendly tool for the textile finishing industry with the aim to improve the knowledge on risk

assessment of nanomaterials and to promote the safe use along their life cycle.

This deliverable, “A1 State of the Art and representative nanomaterials of finished textiles”, is a

preparatory action of the Ecotexnano project, which presents a detailed overview of the most relevant

finishing processes used in textile industry. Both products, conventional and nanomaterials, are

described and compared in this report. A comprehensive list of nanomaterials applied in textile

finishing processes is compiled based on Ecotexnano partners’ experience and relevant projects and

studies dealing with nanomaterials.

The main goal of this report is to select the most representative nanomaterials that are being used in

textile finishing processes in order to establish the scope of the implementation actions of the

Ecotexnano project. The methodology followed for the selection of the four most representative

nanomaterials is described in this document, as well as, the justification of the final selection. This

preparatory action has allowed to determine what nanomaterials will be applied in the two pilot scale

trials (Action B3 Demonstration of pilot scale trials), and also what nanomaterials will be introduced in

the Ecotexnano tool.

2. Overview of nanomaterials in the textile finishing industry

Nano finishing is the term used to describe the application of particles (between 1 nm and 100 nm in

size) that may be applied to the surface of fibres (free or bound) during final finishing. These nano-size

materials may enhance the physical properties of textiles in areas such as antibacterial properties, fire

retardant properties, self-cleaning, ultraviolet protection, hydrophobic, etc. Multifunctional properties

are achieved through changing fabric at molecular level by nanotechnology process, improving the

quality of life and contributing to industrial competitiveness in Europe.

Nowadays, a great variety of textile products are used in this sector, some synthetically produced and

some naturally grown. The EU industry has a leading role in the development of new products,

technical textiles and non-wovens for novel applications such as geo-textiles, hygiene products, the

automotive industry or the medical sector. Examples of technical textiles products are high tenacity

yarns, or special elastic or coated fabrics, all of which have high technology content. The consumption

by volume of technical textiles in Europe market is growing day by day. The value of the global market

for nanofibres has been forecast to grow at a compound annual growth rate of 34.3% between 2009

and 2015, and 37.2% between 2015 and 2020.

Ecotexnano will focus on nanomaterials that may be applied in future to textile products, mainly:

nanosilver (nano-Ag), nano titanium dioxide (nano-TiO₂), nano silica (nano-SiO₂), nanozinc oxide

(nano-ZnO), nano alumina (nano-Al₂O₃), layered silica (e.g montmorillonite, Al₂[(OH)₂/Si₄O₁₀]•nH₂O),

carbon black, and carbon nanotubes (CNT).


In relation to the toxicity testing methods of these nanomaterials, some new methods and modified

versions of pre-existing methods have been developed for assessing the toxicity of nanomaterials. The

current state of the art show the increase of research projects aimed at studying several toxicological

parameters. Some European projects such as EURO-NanoTox, Neuronano or Nanommune are working

to investigate their toxic effects along their life cycle. ECO-TEXNANO will collect the available

information on these project results, making it accessible to the industry and other stakeholders and

using as a basis for the development of the tool.

Regarding ecotoxicological properties of nanomaterials, most of the data is limited to species used in

regulatory testing and freshwater organism and quantitative data on ecotoxicological effects are still

scarce even at the single organism level. Nowadays, several projects are being carried out in this field

for example Nanopolytox, Nanofate, Marina or Ennsatox. In the same way, ECO-TEXNANO will collect

the available information on these project results, making it accessible to the industry and other

stakeholders and using as a basis for the development of the tool.

In addition, since 2008, the International Consortium for the Environmental Implication of

Nanotechnology (iCEINT) has been working to assess the potential impacts of NMs on environmental

health.

In relation to the risk assessment of nanomaterials, currently, no standard methods have been

developed due to the limited amount of empirical data on nanomaterials, the uncertainty regarding

the units of measurement and the impossibility to establish a no effect threshold level. According to

the Working Party on Manufactured Nanomaterials (OECD), the risk assessment for chemicals will

continue guiding approaches to the risk assessment of nanomaterials and no changes are expected. In

this sense, ECO-TEXNANO project will work on the development of an innovative tool to improve risk

assessment and promote the safe use of nanomaterials in the textile finishing industry.

Reliable information to assess the environmental impact of nanomaterials will be assessed in ECO-

TEXNANO project containing data on physicochemical, toxicological and ecotoxicological parameters,

conditions of use and exposure data, enhancing the knowledge base on risk assessment of

nanomaterials.

3. Finishing processes of textiles: Nanomaterials & Conventional products

3.1. Conventional products used in finishing processes of textiles

Conventional products used in finishing processes and properties provided to textile

There are many well-known conventional finishing products such: softeners, silicones, resins,

hydrophilic, hydrophobic, oleophobic, foaming agents, antislip agents, cross-linking agents, anti-static

agents, flame-retardants, anti-microbial, biocides, optical brighteners, improvers of mechanical

properties , active principles with microcapsules like antimosquito, anti-odour, antistress... and also

fashion finishing effects such: wet touch, chewing touch, self shiny effect, smooth touch...


ECOTEX-NANO will focus on Antimicrobial, flame retardant, self-cleaning (soil release) and UV

protection.

Antimicrobial: The most common method is the use of biocides (yarns, particles and finishing)

containing silver. There are other types of products such as quaternary amines, copper, zinc or

chitosan acting in different ways such as attacking the cell membranes of bacteria and degrading

them. Antimicrobial property of silver is well known and is one of the best metals with

antimicrobial activity against gram negative and gram positive. Some antimicrobial products

based on this compound are SILPURE1 (finishing company Thomson Research Associates - TRA)

or Trevira Bioactive (antimicrobial fibre company Trevira). Products as antimicrobial silver are

usually applied in the medical (bandages to prevent wound infections - Silverlon®, Silpure etc. -

Wear surgical masks, bedding), home textiles (towels, bedding curtains ...), clothing (fabric military

uniforms, sportswear, underwear...) or textile construction1.

Flame retardant: Flame retardant can be classified in organophosphorus, organohalogen and

minerals. Concerning the mechanism of action, there are several mechanisms by which a flame

retardant works correctly. Some materials break down at high temperatures by endothermic

process, other flame retardant works as an intumescent by creating a thermal insulation barrier on

the fabric surface, others works as diluents of combustible gas and the last one reacts chemically

by generating radicals on surface with much lower potential to propagate the combustion.

Soil-Release: Soil-release is one of the properties of easy-care finishing. Mostly is known as a

finishing with self-cleaning effect, but in this case the mechanism is not photocatalysis. Soil-

release is a finishing which can remove dust, and/or oil easily. Normally, soiling of fabric is due to

one of this three methods: by mechanical adhesion, by electrostatic forces, by redeposition of soil

during washing. Due to the different possibilities, a unique mechanism for dirt removal is not

enough. So, soil-release finishing has an interesting behaviour depending if it is in contact with air

or with water. In this sense, the perfluorinated chains have the unusual property of being hydro-

oleophobic in contact with air, and hydro-oleophilic in water (washing process).

UV Protection: The ultraviolet protection factor (UPF) depends on their construction,

composition and swelling capacity of the fibres, colour, and presence in finishing of optical

brighteners and ultraviolet absorbers. But the UV protection of fibre can be improved by

incorporating of TiO2 into its structure and/or sufficient weight of the fabric. But in summer, light

weight is required, so in this case, a UV absorber and/or stabilizer can be finished which offers

god performance.

Conventional finishing textile processes (padding, exhaustion, spray, coating, pad-batch, etc)

Coating (Blade Coating)


The doctor blade coating is a method to confer a new property onto the textile, but unlike exhaustion

and impregnation method, the property remains only on the surface of the fabric. The functional

agent is formulated as a paste with a viscosity greater than water. This technique allows for a thin layer

of finish on the fabric. During this process, the thickness of the coating by varying the pressure of the

blade on the fabric is controlled. Also a variant exists where foam is used in order to minimize the

quantity of product.

Impregnation: padding technique

Pad-dry method is one of the most commonly used finishing processes in textile industries. It consists

of impregnating the fabric into a finishing solution, and then, the fabric is squeezed into two rolls in

order to eliminate the excess of water and finishing solution into the fabric structure by applying

pressure. This method is sometimes followed by a thermo-fixation step realized in a stenter machine in

order to dry and polymerize the finishing solution onto the fabric.

Figure 1. On the left: Scheme of padding process .On the right: a lab padding machine (Roches)

Exhaustion method

Exhaustion is a conventional textile process of dyeing and finishing , which consists in impregnating

the fabric into a finishing solution till the complete exhaustion of the bath, by applying temperature

and agitation (of fabric or bath depending the technique). The main advantage of exhaustion method

versus impregnation is that is capable to use less concentration of finishing products due to

temperature used and longer process times.

Spray Coating (Liquid)

Spray coating consists in application of finishing solution by spray guns or automatic nozzles with less

consumption of product and less penetration inside the fiber, resulting in a superficial coating. It is not

a common process in textile industry, but some companies use it for special effects.

Extrusion

It is not a finishing technique, but sometimes, the functional properties are introduced directly on the

fibre extrusion. The main advantage is that introducing the functionality inside the fibre, a better

performance of fastness to washing, rubbing, light… is ensured. A well-known example are Ultra-Fresh


and Trevira Bioactive. Both products incorporate the antimicrobial agent inside the fibre during

extrusion process. Also, Moshy products work on the same way2.

Figure 2.Antimicrobial agent working process, incorporated by extrusion

3.

Powder coating

Spraying powder is a relatively new method that can be used to coat some textiles products in powder

form. This technique is performed by an electrostatic gun which allows a controlled and uniform

coating. On textile industry, the powder was fixed on the fibres through a resin pretreatment. After

spraying the product on the textile surface, heat is applied and resin is cross-linked onto the fibres

with functional particles inside. In fact, the powder coating technique is based on to charge

electrostatically the surface in order to distribute the powder onto the surface, and then make the film

by heating process.

Figure 3. Spray nozzle (liquid)

3.2. Nanomaterials used in finishing processes of textiles

3.2.1 Nanomaterials contained in textiles and their properties

The use of nanotechnology in the textile finishing is fast growing in the recent years. The application of

nanomaterials are aimed at providing multi functional properties such as fire resistance, stain

resistance, antibacterial, UV resistance, water repellent, mechanical resistance, etc. These properties are

added after the base textile has been manufactured by changing fabric at molecular level.

http://cfnewsads.thomasnet.com/images/large/022/22562.jpg


Nanomaterials are being used in different kind of textiles such as clothing, technical textiles (e.g.

protective clothing, vehicle seat covers, filter materials), home textiles (e.g. kitchen towels, bed and

table linen, cleaning rags) and household textiles (e.g. furniture fabrics, textile floor coverings, curtains).

Table 1 shows an overview of properties provided by nanomaterials, as well as the most common

applications in textile products.

Properties of nanotextiles

Typical applications Nanomaterials

Antibacterial Sport clothing

Medical textiles

Filter materials

Silver

Zinc oxide

Copper oxide

Magnesium oxide

Aluminum oxide

Silicon dioxide

Chitosan

Fire resistance Upholstery textiles Protective clothing

Military clothing

Multiwalled Carbon nanotubes (MWCNT)

Carbon nanotubes (CNT)

Silicon dioxide Montmorillonite (nanoclay)

Boroxosiloxane

Antimony ash

UV protection Summer clothing

Sport garments

Zinc Oxide

Titanium dioxide

Magnesium oxide

Aluminum oxide

Clay nanoparticles

Self-cleaning, Hydrophobic & Oil repellence

Sports garments

Upholstery textiles

Home textiles

Technical textiles

Zinc Oxide

Titanium dioxide

Nanosilica


Mechanical resistance

Technical textiles

PPE (protective clothing)

Military clothing

Composites

Multiwalled Carbon nanotubes (MWCNT)


Silicon dioxide

Nanoclay

Electroconductive & Antistatic

Technical textiles

PPE (protective clothing)

Carbon black


Copper

Polypyrrol

Polyaniline

Table 1. Nanomaterials and their properties that provide to textile products

Chitosan, silicon dioxide, titanium dioxide and zinc oxide are mentioned in the references specified for

antimicrobal properties in textiles. It should be pointed out that these substances are either not

notified in the EU's existing active biocidal substances process or are listed in Annex I of the Biocidal

Products Directive. They may therefore neither be used in this function nor advertised as antimicrobial

in textiles.

The following paragraphs describe the most relevant properties associated with nano-finishing of

textiles, as well as the most relevant nanomaterials:

a) Antibacterial:

Textile and clothing are carriers of microorganisms such as bacteria and fungi because of the adhesion

of these organisms on the fabric surface. Antibacterial finishes are applied in sport clothing, inner

wears and medical textiles as a safe and effective means against various bacteria, fungi and chlamydia.

These textiles are generally treated with silver ions, but also with Zinc Oxide (ZnO) nanoparticles,

Copper Oxide (CuO) nanoparticles, Aluminium Oxide (Al2O3) and Magnesium Oxide (MgO)

nanoparticles.

Nanosilver is used in a wide variety of clothes such as shirts, sportswear, socks, underwear, caps,

gloves, etc with the aim to provide antibacterial activity to the textile. Nanosilver reduces

bacterial activity and thereby reduces the need of washing. Nanosilver has a large relative

surface area, thus increasing their contact with bacteria or fungi, increasing their effectiveness.

Silver is safer4 than some organic anti-microbial agents that have been avoided because of the

risk of their harmful effects on the human body. Silver has been proven against a wide variety of

micro-organisms, over 650 disease-causing organisms in the body even at low concentrations.

The advantage of using silver nanoparticles is that there is continuous release of silver ions and

the devices can be coated by both the outer and inner side thereby, enhancing its antimicrobial

efficacy5.


Zinc oxide: when nano-ZnO6 is impregnated onto cotton textiles demonstrates an excellent

antibacterial activity against two representative bacteria, Klebsiella pneumonia and

Staphylococccus aureus. The use of 0,6% nano-ZnO for coating can be sufficient to provide

antimicrobial property to wearable cotton textiles, whereas 1% of nano-ZnO is recommended for

medical textiles due to its high antimicrobial activity. ZnO nanoparticles scores over nano-silver in

terms of cost-effectiveness, whiteness and UV-blocking property. An experimental study using

sonochemical technique showed that the deposition of ZnO nanoparticles onto the surface of

cotton bandage is simple, efficient and inexpensive. Sonochemical irradiation has been proven as

an effective method for the deposition and insertion of nanoparticles on textiles. The process

consists on the continuous pulling of the textile bandage through the solution containing metal

salts, which generates ZnO nanoparticles under ultrasonic radiation that are deposited on

fabrics. The research showed that the coating does not involve any toxic materials and

demonstrated an excellent antimicrobial activity against Staphylococcus aureus (Gram positive)

and Escherichia coli (Gram negative) with low coating concentrations (less than 1%). However,

the minimum concentration for efficient killing of bacteria is 2 wt.% ZnO. Regarding the washing

performance of textiles impregnated with metal oxides nanoparticles, literature reveals that

their content do not change after at least 20 washing cycles. Compared with laboratory

experiments, the pilot scale system increased productivity and reduced energy consumption by

one order of magnitude.

Copper oxide: same researchers (Gedanken et al.) demonstrated that CuO nanoparticles provide

antibacterial and antifungal properties to textiles. The method used consisted on to prepare

cotton bandages that were coated with CuO nanoparticles in a one-step reaction via ultrasound

irradiation. The physical and chemical analysis showed that nano CuO are finely dispersed on the

cotton surface without significant damage to its structure. The experiment demonstrated an

excellent bactericidal effect against Staphylococcus aureus and Escherichia coli when the fabrics

were coated with 1.4 wt.% CuO nanoparticles. The coated fabrics can have potential applications

in bed lining; wound dressing and as active bandages.

Aluminium oxide and Magnesium oxide: a research on Al2O3 and MgO deposition on the surface

of cotton fabrics was also conducted using ultrasound irradiation. The physical and chemical

analysis showed that nanoparticles are finely dispersed on the cotton surface without any

damage to the yarn’s structure and no aggregation was observed. MgO presented a stronger

bactericidal effect than Al2O3. An effective antibacterial activity was detected with concentration

of metal oxide nanoparticles about 1 wt%.

Chitosan: Chitosan is a linear polysaccharide, and is an effective natural antimicrobial agent

derived from Chitin. It has received considerable attention for its commercial applications in

biomedical, food, and chemical industries. Chitosan and chitosan oligomers have attracted

considerable interest due to their biological activities, that is, antimicrobial, antitumor, and


hypocholesterolemic functions. 7,8, 9 In addition, chitosan is biodegradable, non-toxic and is

compatible, so its use in pharmaceuticals, food, textiles, etc, is justified and also widespread.

Its antimicrobial activity has been widely studied, and in year 2000 was studied the fact that once

chitosan was dissolved in saline or distilled water had antimicrobial and antifungal effect on some

filamentous fungi, yeasts and bacteria. Previous studies had suggested that the positive charges of

chitosan structure interfered with the negative charges on the wall of the bacteria, causing it to

break and therefore his death. (Begin 1999). The molecular weight appears to be the most suitable

for an effective antimicrobial action is 1.5 kDa, although these data are not definitive and depend

on the selected organisms and the testing performed.10

b) Fire resistance:

Textiles are flammable to varying degrees because of their ignitability and their potential to propagate

flame. The flammability of untreated textiles depends on the chemical composition of the raw

materials (see Table 2). There is a growing market demand to increase flame resistance of textiles with

the aim to offer safer products and meet fire safety regulations.

Fibre Flammability Characteristics of Untreated Fibres

Fire hazard

Cotton Ignite easily, burn heavily. Do not melt away from flame

+++++++

Flax

Viscose Burns rapidly, similar to cotton ++++++

Acetates Burn heavily; can melt away from flame; form burning droplets

+++++

Acrylics Burn rapidly; form burning droplets; produce dense black smoke

++++

Polyesters Burn slowly and hot; can melt away from flame; form burning droplets

+++

Polyolefins

Polyamide

Other synthetics

Wool Difficult to ignite; burns slowly; might self-extinguish

++

Modified acrylics Burn very slowly; tend to melt away from flame; might self-extinguish

+


Aramide Does not burn; strong char formation

Table 2. Common textile fibres and degrees of flammability. Source: Adapted from the Nanomaterial Case

Study: A Comparison of Multiwalled Carbon Nanotube and Decabromodiphenyl Ether Flame-Retardant Coatings

Applied to Upholstery Textiles. February 2012 EPA Environmental Protection Agency

Flame retardant materials are usually classified according to their chemical structure such as

halogenated, nitrogen-based, phosphorous-based, inorganic, etc. A traditional flame retardant widely

used in textile products is the decabromodiphenyl ether (decaBDE), which is used to treat mattress

textiles, upholstery, window blinds, tents, interior fabrics in cars, etc. According to the VECAP Progress

report11

, in 2011 the majority of the volume (52%) covered by the EFRA Association was sold to textile

applications while previously this only represented 37% of the volume covered. Although decaBDE has

not been manufactured in the EU since 1999 (EC, 2002), the substance is imported. According to the

2010 VECAP report around 2,250 tonnes per annum are used in textiles.

DecaBDE is not used in applications which are in prolonged contact with skin (e.g clothing textiles, bed

covers or protective clothing) in response to concerns regarding potential human health. Regarding

environmental point of view, decaBDE is very persistent substance in terms of the Annex XIII12

(REACH

criteria) as demonstrated by several studies (e.g. Shaefer & Flaggs (2001a), Feibicke et al., 2009 [ABST],

Orihel et al. (2009) [ABST], Muir (2011) [ABST], Sellström et al. (2005) and Nyholm et al. (2010)) which

reported that the primary degradation half-lives in sediment and soil exceed 180 days.

As a result, alternative flame retardants, mainly nanomaterials, are being evaluated as potential

replacements for this used substance.

Multi-Walled Carbon Nanotubes: MWCNTs are carbon nanostructures composed of multiple

concentrically nested graphene sheets which are used as finishing agent in flame-retardant

coatings in a variety of textiles such as upholstery textiles. MWCNTs inhibit flames by forming a

protective layer that seals against combustion. Their effectiveness depends on the formation of a

highly uniform network-structured layer of floccules, which are loosely bound MWCNT bundles,

with no breaks or cracks. The formation of the floccules layer, and therefore the flame-retardant

behaviour, also was found to vary according to a variety of factors, including dispersion (which

can be enhanced with surface 15 treatments), size, shape, aspect ratio and loading concentration

(Cipiriano et al., 2007; Kashiwagi et al., 16 2007; Kashiwagi et al., 2005b; Kashiwagi et al., 2005a;

Kashiwagi et al., 2004). An MWCNT can be created with dozens of variations of these properties.

Altering just one of these properties influence their behavior in environmental media and

impacts on humans. For example, long, straight MWCNTs injected under the skin of rats can

produce more inflammogenic effects than shorter bundles of MWCNTs administered in the same

manner (Johnston et al., 2010)13. Despite MWCNT presence in the market is still limited; the use

of such nanoenabled products is expected to increase in the future as an emerging application.

Montmorillonite: this is the most used clay particle in textile coating, because of its role in flame

retardant textile (cotton or polyester) coating. However, the integration of nanoclay-composites

alone is not enough to provide a fabric with combustion protection. Enhanced properties can be

achieved by combining nanoclay with low concentrations of conventional flame retardants.


Montmorillonite, (Na, Ca) (Al, Mg) 6(SiO10)3(OH) 6-nH2O, provides a combination of hardness,

scratch resistance and flexibility and provides excellent chemical resistance and adhesion14. As

Montmorillonite is biodegradable has very less effect on the environment and human being.

Silicon dioxide: fire retardant coatings with SiO2 are applied to textiles in order to increase the

fire retardance via insulation.

Antimony pentoxide: using a colloidal antimony pentoxide with halogenated flame retardant, an

improving performance of finishing is achieved. This is because the antimony halides released,

when chlorinated or brominated materials are thermal degraded, react with radicals in the flame

resulting in an inactive molecule which much lower potential to propagate the combustion. The

ratio used is between 5:1 to 2:1 (halogen-antimony)

c) UV protection:

The incorporation of nanoparticles like ZnO, TiO2 or clay nanoparticles into textiles are becoming more

demanding, as they provide protection from harmful UV radiation. In comparison to conventional UV

absorbers (organic and inorganic), nanoparticles are more efficient at absorbing and scattering UV

radiation, because they have a larger surface area per unit mass and volume than the conventional

materials. Textiles coated with nanoparticles keep the UV blocking property more time than

conventional materials. Hence, these nanoparticles increase the effectiveness of blocking UV radiation.

The ability of a textile material to block UV light is given by the Ultraviolet Protection Factor (UPF).

Titanium dioxide: It has been demonstrated15 that when a thin layer of TiO2 is formed on the

surface of the treated cotton fabric provides excellent UV-protection. Moreover, the effect can

be maintained after 50 launderings. Another experimental study21 about TiO2 nanocoatings

deposited on Poly (lactic Acid) textile fibres showed an excellent protection with a UPF factor

over 75.

Zinc Oxide: the same study mentioned above15 revealed an excellent UV-protection when cotton

fabrics are treated with zinc oxide nanorods of 10 to 50 nm in length. ZnO nanoparticles inlayed

in polymer matrices (e.g. soluble starch) have a good potential for applications such as UV

protection ability in textiles.

In a research study16

conducted by LEITAT, ultraviolet resistant cotton fabrics were developed by

coating with ZnO and TiO2 nanoparticles. The ZnO nanoparticles applied on cotton yarns were

found to withstand the knitting operation. Meanwhile, the TiO2 nanoparticles applied on the

bleached as well as reactive dyed cotton fabrics by the sol-gel and linking agent methods were

found to be intact after various cycles of domestic washing. Knitted fabrics containing ZnO

nanoparticles showed moderate to high UPF values, whereas 50+ UPF values were measured for

the TiO2-coated samples. Further it was found that the rutile phase was better than anatase phase

in blocking UV rays. The developed process can be easily adapted to the existing textile machinery,

making it industrially viable.


Montmorillonite: nanoclay particles are composed of various hydrous aluminosilicates and they

have properties that lock UV light. Nano clay particles of montmorillonite are one of the most

commonly used UV blocker in textiles. It also increases around 40% tensile strength and 60%

flexural strength17.

d) Self-cleaning & hydrophobic & oil repellence:

The self-cleaning property is desirable for many textile applications as they can be water-repellent,

stain resistant, etc. Various types of nanoparticles such as silica, TiO2 and ZnO nanoparticles can be

used to produce a nano/micro structure surface, but the most successful experiences18

have been

achieved with silica nanoparticles.

Silicon dioxide: an experimental study19 was conducted in order to determine the influence of

nano-SiO2 on the hydrophobic properties of modified surfaces. An hydrophilic surface with the

nano-SiO2/epoxy ratio of 0 and 0.5 was modified to hydrophobic surface with the nano

SiO2/epoxy ratio of 1.0 and 1.5, and also to superhydrophobic surface with the nano-SiO2/epoxy

ratio of 2.0 and 2.5. Superhydrophobic surface was created by multicoating process, which is a

cheap method to prepare superhydrophobic and self-cleaning surface. The increase of nano-SiO2

contents increased the contact angle of films, causing the change from hysrophilic surface to

superhydrophobic surface.

Nanosilica and nanoclay based nanoparticles are used to provide hydrophobic properties to

textiles. Several studies20 demonstrate that with the help of nanosilica and nanoclay along with

a surface tension lowering agent, hydrophobic properties can be achieved on cotton fabric.

Furthermore, environmental advantages are produced when nanosilica and nanoclay are used,

due to the amount of fluorocarbon based resin finishes on the fabric is reduced. Hydrophobic

nano-roughened surfaces can be prepared by controlling surface topography by several

methods, such as electrochemical method, organic/inorganic hybrid method, sol-gel method,

plasma method, etc. M Joshi et al paper reveals that fabrics treated with silica using finishing

liquor give hydrophobic effect to the cotton fabric. The columnar structure created by the

combined effect of silica and other additives makes the water penetrated is much less as

compared to a fabric without treatment. In addition, it has been demonstrated that the water

repellency rating is increased when the roughness is higher. A surface with a water contact angle

larger than 150° is commonly considered as superhydrophobic surface property.

Titanium dioxide: based on the results from an experimental study 21 TiO2 nanocoatings

deposited on Poly (lactic Acid) textile fibres exhibited good self-cleaning properties. A TiO2 thin

film exhibits a contact angle of several tens of degrees depending on surface roughness. When

this surface is exposed to UV light, the contact angle is reduced, becoming the textile less

hydrophobic. It was demonstrated, nevertheless the washing treatment, the adhesion of TiO2

nanocoatings to the PLA fibres was still maintained.


Flourine-based: These polymers are hydrophobic and oleophobhic in air and hydrophilic and oil-

releasing during laundering. This is called “dual-action” mechanism. When fabric is dried,

hydrophilic blocks are shielded by fluorocarbon segments, resulting in a repellent surface, but

when it is immersed, the hydrophilic blocks can swell, yielding the hydrophilic surface necessary

for oily soil release. These finishing products are normally impregnated using padding

equipment.

3.2.2 Nanotechnology finishing textile processes

SOL-GEL COATING

One of the latest trends along with microencapsulation, is the application of sol-gel coating on textiles.

The sol-gel method is also known as soft chemistry that allows applying a nanometer layer, doped

with the agent or the active ingredient on the textile. So, sol-gel coating allows to achieve hybrid

materials, nanostructured, porous and with new features.

Sol-gel is a new method for inorganic reactions that do not need high temperature (> 700 ° C) to

develop new mineral structures, but the development of low temperature inorganic or organometallic

networks in three dimensions from liquid monomers. These new synthetic pathways allow organic

chemistry therefore compatible with mineral chemical synthesis because temperatures are similar.

This reaction has allowed the emergence of many new applications in the areas of:

Catalysis 22

Materials for electronics 23

Metallurgic 24

Filtration 25

Ceramic and glass 26

Materials for photovoltaic 27

Memories 28

Sensors 29

Television 30

These methods are also suitable to functionalize textile products using a Sol (solution) based on

metal oxides (mainly Si or Ti, Zr). The coatings can be prepared at room temperature and normal

pressure using common equipment to perform coatings for be applied by conventional finishing

process of textiles, such as exhaustion or impregnation. This ease of implementation at industrial

level has many advantages compared to other existing methods to perform thin layers of metal

oxides as many applications which involves gaseous phase and require vacuum systems.

The sol-gel process involves the production of inorganic networks through the hydrolysis of a metal

oxide precursor and the formation of liquid colloidal suspension (sol) that become gel to form a

continuous network on the surface of textiles (xerogel).


The xerogel is dried by heat treatment or evaporation under vacuum to form a dense resistant film.

Figure 4. Sol-gel technologies and their products. Source: NTSE

The films obtained by modified silicon oxide Sol and other metal oxides are generally transparent,

thanks to its thickness, generally from nanometric order, and do not influence the colour of the fabric

and only a little bit of its handlingxxxi

. In addition, the layers obtained are resistant to light and

temperature, and are chemically and biologically stables.xxxi, xxxii

The properties that have been investigated for textile applications are:

Increased chemical resistance and abrasion of the fabrics primarily by the intrinsic properties

of the film obtained from the surface of the textile. xxxiii

Water repellence by the intrinsic properties of the film, but essentially using doping in the sol

or in the process of post functionalization of obtained xerogelxxxiv.

Decrease the release of formaldehyde by formation of a blocking layer on the surface of the

fabricxxxv.

Fire resistance by introducing the phosphate xerogel of SiO2 xxxvi.

UV protection by forming a mixed oxide SiO2 - TiO2 xxxvii.

Improvement of the properties of fixing dyes for dye absorption in the xerogelxxxviii.

antimicrobial properties by incorporating of silver nanoparticles in the matrix sol-gel or silver

cation fixation by absorbing a AgNO3 solutionxxxix.

≡Si-OR + H2O ≡Si-OH + ROH (1)

≡Si-OH + HO-Si≡ ≡Si-O-Si≡ + HOH (2)

≡Si-OR + HO-Si≡ ≡Si-O-Si≡ + ROH (3)

H+/OH

-


Photocatalysis and self-cleaning properties by forming a titanium oxide layer or deposition

of titanium oxide nanoparticles in SiO2 matrix xl.

PLASMA TECHNOLOGY

Plasma is a partially ionized gas composed of electrons, ions, photons, atoms and molecules of gas in

any excited state. Also known as the fourth state of matter.

Figure 5. Composition plasma schemexli (a).Representation of plasma as a 4th state of matterxlii (b). Plasma

reactor workingxliii

(c).

Different types of plasma processing (see Figure 6):

• Ion implantation (1)

• Sputtering (2)

• Etching (3)

• Plasma enhanced chemical vapour deposition, PECVD (4, 5, 6)

• Plasma fixation (4, 5, 6)

• Surface functionalization (7)

• Superficial grafting induced by plasma (8)

Figure 6. Plasma processing

Plasma technology is at a mature stage in industries such as automotive, packaging, pharmaceutical,

semiconductor and aerospace industries, among others. On textile industry is an emerging

(b) (a) (c)


technology which have done extensive research studies where it has obtained successful results on

various textile substrates.

Plasma classification

According to the existing pressure in the area where the plasma is generated, it can be classified

into:xliv

- Low pressure plasma (or vacuum). Discharges at low gas pressure (0.1-100 Pa). The sources

used in low pressure plasma systems are low frequency (Low Frequency, 40 kHz), RF (13:56 MHz)

and microwave (2.3 GHz). Operating in discontinuous (or loads) and carry a high investment cost.

However, it allows polymerization processes and the incorporation of particlesxliv,xlv,xlvi,xlvii. In

addition, these systems are easily controlledxlvii.

- Atmospheric Pressure Plasma. Discharges at atmospheric pressure. The most common

atmospheric electrical discharges are atmospheric pressure glow discharge (APGD) and dielectric

barrier discharge (DBD). It works in continuous and at high speeds (Plasmatreat GmbH). Now, the

research is focused on improving these machines to make them capable to do deposition

process with liquids.

Plasma treatment modifies chemical and physically the surface of textile fibres. It can be used as pre-

treatment to conventional finishing processes (difficult surfaces) or as a finishing process itself

(plasma polymerization).

Surface Activation and plasma pre-treatment onto textiles consist in to increase the affinity of

physicochemical surface of the fibres for better fixation of dye molecules and/or finishing products.

Surface activation processes are carried out in all kinds of plasma equipment (atmospheric or

vacuum) using non-polimerizant gases such nitrogen, oxygen, air, argon, helium and / or hydrogen,

among other. Surface activation is based in two effectsxlvi

:

Physical surface modification: By removing physical (sputtering or etching processes) of the

surface layers more inert. Modifies the surface roughness.

Chemical surface modification: By incorporating and / or creation of new surface functional

groups, which generally interact with dye molecules and finishing products to a greater

extent than the original surface functional groups.

Improvements in textile substrates for these types of processes are:

Increase the speed of absorption of dyes and/or finishing products. It is due the

improvement of wettability introduced as a result of plasma treatments.

Increase the capacity of adhesion of dyes and/or finishing products. It is due the

modification of the surface morphology (eg, an increase in surface roughness) and/or the

creation of new chemical functional groups on the surface.

Plasma polymerization and grafting induced by plasma are carried out in low pressure plasma

equipments and are the unique techniques capable to deposit polymeric thin films (< 1μm) as of

organic and organometallic compoundsxlviii

.


Figure 7. Morphology of a deposited thin film by plasma polymerization. Left: non treated fibres. Right:

plasma treated fibres.

In the process of plasma polymerization, a monomer vapour is introduced into the vacuum chamber

which generates a plasma state. This monomer polymerizes forming a solid film, with a high

crosslinking degree, which remains deposited on the surface xlix , l , li , lii . In grafting processes, the

monomer is linked with different active centres located in the polymer chains of the substrate. The

grafting process can take place in several ways. Before activating the surface of the solid substrate

using a plasma, usually from an inert gas, and then applying the monomer (Fig. 8a). Applying

directly monomer and generating a plasma state in it. Thus, the monomer interacts with the polymer

chains located on the surface of the substrate, being linked to these chains forming graft copolymers

(Fig. 8b) liii.

Figure 8.- Graftinc processes schemesliv

.

Moreover, it has been shown that plasma polymerization processes coexist two phenomena, ablation

and polymerization, which are carried out simultaneously. In general, each of these phenomena

predominate over the other for certain power levelslv. Furthermore, it is interesting to note that these

surface treatments do not alter the intrinsic properties of polymers lvi .

There are lots of studies of the application of grafting and plasma polymerization technologies. In

some cases, these methods have been developed for continuous and uniform application of amount

of gases and monomers desired on different polymeric substrates:

Hydrocarbonated compounds onto PE.xlviii,lvii,lviii

(a)

(b)


Flourinated compounds ontopolymers.lix,lx,lxi

HMDSO ontopolymers.lxii,lxiii,lxiv

Tetrametilsilà (TMS) or TMS+O2 onto PE, PTFE and PC.lxv

Glycidyl methacrylate, chitosan and cyclodextrines on PP.liv

Dioxane and xylene onto carbón fibres .lxvi

Ethylenediamine and n-buthylamine onto cellulose acetate membrane.lxvii

Acrylic acid on poluester.lxviii

Acrylic acid, acrylamide, metacrylic acid, Glycidyl methacrylate onto Polydimethylsiloxane

(PDMS).lxix

Diethylene glycol vinyl ether (EO2), allylamine (AA) and Maleic anhydride (MA) onto silicon.lxx

The main properties achieved by surface functionalization of polymeric substrates based on surface

grafting processes and plasma polymerization are:

Permanent hydrophilic character.xlviii,lxxi

Achievement of good biocompatibility.lxx

Permanent hydrophobic character.lxxii

Modification of water permeability in function of pH.lxviii

Increase of polymeric finishing adhesion.lvii,lxv

Achivement of antimicrobial character.liv

Increasing of surface hardnes.lxv

Corrosion protectionlxxiii

Tensile strength improvement.lxvi

Immobilization of polyethylene oxidelxxiv

, collagenlxxv

, fibronectinlxxvi

and gelatinlxxvii

.

Optical properties.lxxviii

Particle encapsulation: salicylic acid, ibuprofen, etc.lxxix

Diffusion control in biomedicine applications.lxxx

The main advantages and drawbacks of plasma technology are:

Advantages:

• Minimum consumption of product.

• No water consumption.

• Low energy consumption (removal of the stages of drying).

• Short times treatments (seconds or minutes).


• Does not produce wastewater.

• Modification of the surface properties without changing the intrinsic properties of the fiber.

• Availability of processes for almost all types of fibres.

• High operating speeds (only continuous).

Drawbacks:

• Operation in discontinuous or loads (plasma vacuum).

• High investment costs.

• High sample preparation times (mainly the removal of moisture in natural fibres).

• Difficult process control (atmospheric plasma).

• Industrial machinery in development and in improving process.

ELECTROSPINNING

Electrospinning is a versatile method based on an electro-hydrodynamic process for forming

continuous thin fibres ranging from several nanometers to tens of micrometers. This method can be

used for the one-step forming of thin fibrous membranes.lxxxi,lxxxii,lxxxiii , lxxxiv,lxxxv

A wide variety of

materials, such as polymer-solvent systems and polymerless sol-gel systems can be electrospun.lxxxvi

Electrospun nanofibres with high surface areas have drawn significant attention for their practical

applications, such as high-performance filter media, protective clothes, composites, drug delivery

systems, scaffolds for tissue engineering, sensors, and electronic devices, as Figure 9 shows.lxxxiv

Figure 9. Broad spectrum of electrospun nanofibres applications in various fields.

The functionalities of the nanofibres are based on their nanoscaled-size, high specific surface area,

and high molecular orientation, and the fact of being possible to control their fibre diameter, surface

chemistry and topology, and internal structure of the nanofibres. In addition, processing innovations

to improve not only the control of morphologies but also the production capacity of electrospun

nanofibres are in progress. In particular, the high-throughput electrospinning systems are ongoing

developments (e.g., multi-needle and needleless processes).lxxxvii

Nanofibres are a unique nanomaterial because of the nanoscaled dimensions in the cross-sectional

direction and the macroscopic length of the fibre axis (see Figure 10). Therefore, nanofibres have

Medical

Energy

Engineering

Textile

Filtration

Agriculture


both the advantages of functionality (due to their nanoscaled structure) and the ease of manipulation

(due to their macroscopic length). Furthermore, three-dimensional nanofibre network assemblies

provide good mechanical properties and good handling characteristics.

Figure 10. Characteristics of nanofibres .

Nanofibre synthesis by Electrospinning

Electrospinning process of polymer nanofibres is shown schematically in Figure 11. This technique is

based on three main components: a high voltage supply, a syringe connected to a needle of small

diameter and a metallic collecting plate. In this process, to make an electrically charged jet of

polymer solution or melt out of the needle, a high voltage is applied between two electrodes

connected to the spinning solution and to the collector which is normally grounded, respectivelylxxxviii

.

The electric field is subjected to the tip of the needle containing a droplet of the polymer solution.

The surface of the droplet is electrified. Increasing the intensity of the electric field changes the

hemispherical surface of the fluid at the tip of the needle to a conical shape known as the Taylor

cone. After a special intensity of the electric field (this intensity is the optimum intensity to generate

the nanofibres and it depends of several parameters such as, conductivity and viscosity of

electrospinning solution, distance tip-collector, solution flux, collector rotation, needle size,…), the

repulsive electrostatic force dominates the surface tension and a charged jet of the polymer

solution/melt is ejected from the tip of the Taylor cone. Due to the mutually repulsive forces of the

electric charges of the jets, the polymer solution jet undergoes an instability (bending instability) and

is elongated. The bending instability makes the jet very long and thin. Evaporation of the solvent

while occurrence of bending instability results in formation of a charged polymer fibre which is

deposited as an interconnected web on the collector.lxxxix,xc


Figure 11. A schematic diagram for electrospinning processing of polymer nanofibres .

- Conditions of application of nanomaterials (concentration, process time,

temperature, etc).

SOL-GEL CONDITIONS:

Although it is not a massive application technique, most tests done in the textile industry have been

made with the conventional impregnation method.

A. B.

Figure 12. A. Original fabric. B. Sol gel coated fabric

PLASMA CONDITIONS:

The type of gas to be employed in plasma treatments is a decisive condition and parameter for the

properties which have to be induced to the fabrics. These gases can be non polymerizing gases,

polymerizing gases or vaporized liquid monomers.

Plasma treatments with non polimerizing gases: air, O2, N2, Ar, He

Sputtering/Etching:

These techniques are used to remove surface impurities (i. e. hydrophobic layers) and to increase the

superficial roughness of the fibres . They have been used during cleaning and desizing processes of

textiles.


Functionalization/activation:

These techniques are used to introduce polar groups (such as COOH, OH, NH2); enhancement of the

surface energy). They have been employed to improve wettability of textiles.

Figure 13. Improvement of wettability of textiles (contact angle decrease)

Plasma treatments with polymerizing gases/vaporized liquid monomers: CF4, SF6, C6F14, AAc.

Plasma polymerization/Plasma enhanced chemical vapor deposition (PECVD):

This technique permits to obtain a thin film deposition and is similar to a coating process. The

coating thickness is located between 10 and 50 nm, which is considered as a nanocoating. Also, in

this application type, the nature of the precursor gases will determine the properties of the deposited

coating.

Low-pressure plasma:

Figure 14. Low-pressure plasma equipment (40 KHz LF-generator, Diener electronic GmbH + Co. KG.)

Plasma treatments using different gases

PECVD processes using precursors (gas, vapour)


Atmospheric-pressure plasma:

Figure 15. Atmospheric-pressure plasma equipment (Openair

®, Plasmatreat GmbH)


Atmospheric-pressure plasma:

Figure 16. Atmospheric-pressure plasma equipment (APGD, GRINP S.r.l.)


PECVD processes using precursors (gas, vapour)

Example of atmospheric plasma conditions:

Operating parameters:

Frequency = 20-45 kHz

Flow of gas = 1.0 L/min

Distance between electrodes = 0.50 mm

Speed of treatment = 1.6 m/min


Power of discharge = 2.0 kW

Variables:

Type of gas used: helium, oxygen, air, argon

Temperature = 20, 30, 45, 60, 75 and 90ºC

ELECTROSPINNING CONDITIONS

The electrospinning process is governed by many parameters, classified broadly into solution

parameters, process parameters, and ambient parameters.xci

Each of these parameters significantly

affect the fibres morphology obtained as a result of electrospinning, and by proper manipulation of

these parameters we can get nanofibres of desired morphology and diameters.xcii

Such parameters

and their effects on fibre morphology are shown in the table.

Parameters Effect on Nanofiber Morphology Ref.

Solution Parameters

Viscosity Low-beads generation, high-increase in fibre diameter, disappearance of beads

xciii, xciv, xcv, xcvi

Polymer concentration

Increase in fibre diameter with increase of concentration xcvii, xcviii, xcix

Molecular weight of polymer

Reduction in the number of beads and droplets with increase of molecular weight.

c, ci, cii

Conductivity Decrease in fibre diameter with increase in conductivity xciii, xcix, ciii

Surface tension No conclusive link with fibre morphology, high surface tension results in instability of jets

xcvi,civ, cv, cvi

Processing parameters

Applied voltage Decrease in fibre diameter with increase in voltage xcvii, xcix, ci

Distance between tip and collector

Generation of beads with too small and too large distance, minimum distance required for uniform fibre s.

xcv, cvii, cviii, cix

Feed rate/Flow rate Decrease in fibre diameter with decrease in flow rate, generation of beads with too high flow rate.

xcvi, cv, cx

Ambient parameters

Humidity High humidity results in circular pores on the fibres cvi, cxi, cxii

Temperature Increase in temperature results in decrease in fibre diameter. cvi, cx

Table 3. Electrospinning parameters (solution, processing and ambient) and their effects on fiber morphology.


NANOMATERIALS ADDITIVES AND AUXILIARIES APPLICATION CONDITIONS:

Nanocoatings on textiles can be obtain by either innovative methods such as plasma, grafting and

sol-gel, or can be obtained as well by the application of nanomaterials in the form of additives or

formulated into commercial available textile auxiliaries. In the last cast, the application of these

additives and auxiliaries is realized by means of the conventional application techniques used in

textile and previously detailed (padding, exhaustion, coating, spray or electrostatic pulverization…).

However, due to the nanometric size, the application conditions can be optimized. The conventional

textile application techniques used up to now for nanomaterials application are padding, exhaustion

and coating. Application conditions depend on the type of resin used and the composition of the

fabric where the finishing product will be placed and the machinery you need to use. There are not

different application conditions from conventional ones, simply by working with nanoparticles.

3.2.3 Human health & Environmental risks of nanomaterials

In 2006, the Organization for Economic Cooperation and Development (OECD) launched a

programme of work to ensure that the approaches for hazard, exposure and risk assessment for

manufactured nanomaterials are of a high quality and science-based. OECD promotes international

co-operation on the human health and environmental safety of manufactured nanomaterials, and

involves the safety testing and risk assessment of manufactured nanomaterials. Currently, the most

commercial relevance nanomaterials are being evaluated in terms of toxicology, ecotoxicology, and

environmental behaviour. The 13 nanomaterials under study are fullerenes (C60), single-walled

carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs), silver nanoparticles, iron

nanoparticles, TiO2, AlO, CeO, ZnO, SiO2, dendrimers, nanoclays and gold nanoparticles. The aim of

this action is the collection of data on the behavior of nanomaterials in order to determine their

impacts on human health and environment.

Human health and environmental risks of nanomaterials depends on different factors such as type,

shape, function and application. Due to the wide variety of nanomaterials used in textiles it is not

possible to extract a general conclusion on potential risks. Despite some nanomaterials have the

potential for toxic or ecotoxic effects; since it is possible that they are not absorbed into the system.

The form in which nanoparticles come into contact with human organism and the environment is one

of the main factors to be considered when assessing the exposure risk. Further research is needed to

determine how nanomaterials are released from the textile products, how they behave in the

environment, how stable they are, how their properties change, etc.

Human health risks of nanomaterials:

The possible intake paths of nanomaterials released from textiles are dermal and inhalativecxiii

.

Related to dermal intake, several skin penetration studies reveal that healthy intact skin is a good

barrier for ZnO and TiO2 nanoparticles, which are also used in sun creams. Nanoderm EU project

concluded that there is no risk at all for products containing TiO2 nanoparticles for healthy skin, while

in psoriatic skin deeper penetration is produced. Regarding inhalative intake, there are few studies

available on the chronic inhalation toxicity of nanomaterials. These studies evaluated the effects of

applying high concentration in rats and the results show inflammatory reactions and tumors.

However, high concentrations are unlikely, and it is unclear if effects should be expected in the low-


dose range. The Federal Ministry for the Environment (BMU) and BASF are testing various

concentrations of nanoCeO2 in rats. NanoCeO2 is considered a representative of the group of

granular biodurable dusts of relatively low toxicity that also includes TiO2 and aluminum oxide.

Regarding carbon nanotubes with a fibre length of more than 15 μm (long CNTs) can be

carcinogenic potential if inhaled due to their similar structure to asbestos and other mineral fibres.

Inhalation studies reveal that CNTs can cause inflammatory fibrotic lesions in the lungs that can lead

to the formation of granulomas.

Environmental risks of nanomaterials:

There are few Life Cycle Assessments (LCA) of textiles containing nanomaterials. The following lines

present different LCAs conducted in nanotextiles products.

One studycxiv

compared a T-shirt treated with nanosilver with a conventional biocide (triclosan) and a

non-treated control product considering the complete life cycle. Flame spray pyrolisis (FSP) process

and plasma polymerization with silver co-sputttering (PlaSpu) were investigated for the incorporation

of nanosilver in T-shirts. The findings show that FSP process is environmentally and economically

more efficient than with PlaSpu. The ecotoxicity of the T-shirts increased during washing if biocidal,

either nanosilver or triclosan, were added. The study concluded that the use phase is most important

in terms of climate footprint when FSP nanosilver or triclosan applications are evaluated. Energy

savings can be achieved if consumers adjust their laundry behaviour (loads and frequency) due to

textiles with active biocidal agents need fewer washing cycles, which saves energy, water and laundry

detergents. The footprint increases during the production phase of nano-silver T-shirts, while in the

use phase can drop significantly depending on the consumers’ behaviour.

Self-cleaning surfaces treated with nanomaterials can result in saving detergents and energy.

Regarding nanomaterials used to provide UV protection to textiles, a studycxv

concluded that

nanomaterials can help to improve the durability of the textiles, causing also a longer life cycle of the

textile product.

Textile finishing processes in the manufacturing phase, laundry processes in the use phase and

disposal are the main sources of releasing nanomaterials into the environment. During textile

finishing processes, nanomaterials can enter wastewater treatment plants. One studycxvi

shows that

typically more than 90% of the nanomaterials investigated (TiO2, ZnO, silver and CeO2) can be

separated via the sewage sludge. However, to date, this statement cannot be extended to other

nanomaterials due to the lack of data. Further research is required on their behaviour in the soil,

accumulation in soil-dwelling organisms and plants.


3.3. Comparison among conventional products and nanomaterials used to reach specific properties

The main advantage and constrains between both processes are related below:

Advantages Constrains

Nanomaterial

1. Increase of surface area. 2. Better handling and softness 3. Less quantity of product for the same performance.

1. Difficult to disperse. 2. Migration problems in study phase. 3. Application in investigation. 4. Low availability in conventional textile application method.

Conventional

1. Easy to disperse. 2. Economic 3. Well-known by textile industry. 4. Good availability for any range of textile application.

1. Less surface area. 2. Handling

4. Methodology for the nanomaterials selection

The methodology followed for the nanomaterials selection is based on a semi-quantitative scoring

system, which provides an intermediary level between the qualitative assessment and the

quantitative assessment, by evaluating different criteria with a score. After compiling a

comprehensive list of nanomaterials used in textile finishing sector, these have been evaluated by

means of a semi-quantitative scoring system. The following eight criteria have been considered to

assess the nanomaterials identified from the State of the Art:

1) Commercial availability: all the nanomaterials selected have to be commercially available

2) Human health and environmental risks: less impacting nanomaterials in terms of human

health risks and environmental risks are better scored. Toxicological (e.g. acute toxicity,

irritation/corrosion, sensitization, carcenogenicity) and ecotoxicological (e.g. aquatic toxicity,

degradation, fate and behaviour in the environment, effects on terrestrial organisms)

information of nanomaterials have been considered to rank this criterion.

3) Environmental impacts: this criterion promotes those nanomaterials which mitigate the

negative environmental impacts, such as reduction of energy and water consumption, decrease

of the raw materials, etc.

4) Performance of nanomaterial in textiles: Performance of nanomaterial is classified in two

categories: bad or good. The performance of nanomaterials will be determined based on

existing research data.

5) Price of formulated nanofinishing products: cheaper commercially available nanoproducts

(less than 100 € per kg) are awarded with more points.

6) Feasibility to apply in pilot scale trials: an essential criterion consists on the feasibility of

replacing a conventional product with a nanofinishing textile agent without changing existing

machinery in the two pilot scale trials (Vincolor and Piacenza). As selected nanomaterials have to


be applied in these two industries, the companies’ preferences also have been considered.

Vincolor is interested in fire resistance and self-cleaning properties, while Piacenza is interested

in antibacterial, UV protection, mechanical resistance or hydrophobic properties. Therefore,

nanomaterials able to provide these properties are better scored.

7) Level of transferability: the objective of this criterion is to promote those nanomaterials more

replicable to be applied in the textile finishing industry.

8) Availability of data: the existing safety and environmental information that is likely to be

available on nanomaterials.

The maximum possible score for each nanomaterial is 17 points. The scores to be assigned to the

different criteria are presented in the table below:

Human health & Environmental risks

High or unknown data 0 points

Medium 1 point

Low 2 points

Environmental impacts

Negative impacts or unknown

data

0 points

Positive impacts 2 points

Performance of nanomaterial

Bad or unknown data 0 points

Good 2 points

Price of formulated nanofinishing product

Higher than 100 € per kg 1 point

Lower than 100 € per kg 2 points

Feasibility to apply in pilot trials

Not feasible 0 points

Feasible 4 points

Level of transferability

Difficult 0 points

Easy 2 points

Availability of data

Low 0 points

Medium 2 points

High 3 points


5. Selection of representative nanomaterials used in finishing processes of textiles

Nanoparticles can be applied on different types of substrates, such as glass, plastics or textiles, using

different types of methodology as explained before (padding, coating, extrusion, exhaustion, spray,

etc.). A wide variety of nanoparticles is available and has been applied on textiles in the form of

additives or raw material. However, nanoparticles formulated in textile auxiliary products are more

difficult to found, even if antibacterial textile auxiliaries based on nanoparticles are more commons.

Nanomaterials employed as additives for different properties are detailed in the next tablecxvii

:

NANOMATERIALS AS ADDITIVES PROPERTY

Silver (Ag), quitosan, titanium dioxide (TiO2), zinc oxide (ZnO).

Antibacterial

Carbon nanotubes, fluoroacrylate, silicon dioxide (SiO2), titanium dioxide

Self cleaning or dirt repellent (soil release)

Titanium dioxide, zinc oxide Ultraviolet protection

Carbon nanotubes, boroxosiloxane, monmorillonite or nanoclay, antimony trioxide

(Sb3O2), antimony pentoxide (Sb2O5) Flame retardant

Nanomaterials employed as formulated textile auxiliary are detailed in the next table:

NANOMATERIALS AS TEXTILE AUXILIARY (commercial name)

COMPOSITION SIZE (nm) PRODUCING COMPANY

PROPERTY

NPS 100

NPS 200 Silver (Ag) 5 – 50 NANOPROTECT

Antibacterial

Nano Textile Coating antimicrobial with

TiO2cxviii

Titanium dioxide (TiO2)

Nano size NANONEXT

Polyprotec 8741 Silver (Ag)

TiO2 Nano size POLYSISTEC

Silpure Silver (Ag) 180 ULTRA FRESH

SilverSol™ Silver (Ag) 3 – 5 NANO SILVER


Centerbac SLN Silver (Ag)

TiO2 Nano size COLOR CENTER

Nanocoatings for textile

cxix

Silicon dioxide (SiO2)

Nano size NANOCARE Self cleaning or dirt repellent

Textile & leather MAX

Textile & leather

Multi-split cleaner

Not specified Nano size NANOPROTECT

Dirt repellent

Nano Textile Coating antimicrobial with TiO2

TiO2 Nano size NANONEXT

Nano Textile Coating XPZ Professional

Not specified Nano size NANONEXT

Nano Care Textile Not specified Nano size NOVATIO

NanoSphere® Not specified Nano size SCHOELLER

TECHNOLOGIES

Nuva® N1811 (Nuva ® N4547)

C6-based range of fluorochemicals

Nano size ARCHROMA

P&T 230 P&T 230Ag

P&T Nanovis

SC Glass - self cleaning window


Nano size NANOPROTECT

Self cleaning

Cristal Activ TMcxx

Titanium dioxide

(TiO2) Nano size CRISTAL

Nano TiO2 dispersion (in study)


Nano size COLOR CENTER

Nyacol colloidal zinc oxide

cxxi

Zinc oxide (ZnO) 50 – 90 NYACOL

Ultraviolet protection SiO2 7015WJ

25wt% Silicon Oxide in Water

30 NANOAMOR

Nano TiO2 dispersion Titanium dioxide

(TiO2) Nano size COLOR CENTER

Nanomer ® (for plastic materials)

cxxii

Montmorillonite nanoclay

200-300 length

1 (height) NANOCOR

Flame retardant Nyacol ® A1530

Nyacol ® A1540N

Nyacol ® A1550

Antimony pentoxide (Sb2O5)

35 NYACOL


According the methodology described in chapter 4, the four nanomaterials which have obtained a

better score, and hence have been selected for their application in pilot scale trials are the following:

Nanomaterial

C6 based fluorochemical

Soil-release

Silver Nano-dispersion (Ag)

Antibacterial

Antimony pentoxide

(Sb2O5)

Flame retardant

TiO2 Nano-dispersion

UV protection

Human health and

environmental risks Medium Medium Unknown Medium

Environmental impacts Unknown Unknown Unknown Unknown

Commercial availability Yes Yes Yes Yes

Price of formulated

nanofinishing product 9-11€/Kg 120€/Kg 22€/Kg 9,85€/Kg

Feasibility to apply in

pilot scale trials High High High High

Level of transferability Medium-high Medium-high Medium-high Medium-high

Availability of data (environmental and

safety) MSDS MSDS - MSDS

Proximity to the

industry Spain, Italy

Spain (delivery 2 months)

USA

(European distributor)

Spain

Conventional finishing

to compare with Conventional FC Conventional

Conventional halogenated

flame retardant Conventional

C6 based Fluorocarbon:

This material is based on C6 fluorocarbon (exempt of PFOA, PFO’s) and is commercially available in

Europe. The price of the material is between 9 and 11 €/kg depending of quantity requested. Due to

the chemical composition of fabrics that Vincolor wants to use, some problems could appear during

application process. Even so, it has been selected because was the only product that could have

good adhesion because is formulated to work with blends with cotton fibres and synthetic. The level

of transferability to another textile sector does not depend on the nanomaterial used. The

transferability depends on the industry needs to provide this functionality, the capabilities of the


company to use the proper method of application, the chemical composition of selected fabrics, and

internal regulations of the sector (prohibition of chemicals).

Private enterprises, such as DuPont, have developed repellent and surfactant products based on

sustainable short-chain technology (six or less fluorinated carbons) that deliver superior performance,

supported by extensive environmental, health and safety testing. Extensive studies show that those

products and potential degradation products including perfluorhexanoic acid (PFHxA) have a

favourable environmental, health and safety profile, rapid bioelimination, and are not

bioaccumulative.cxxiii Further studies on toxicology, proved that these products have low acute oral

and dermal toxicity, low acute aquatic toxicity, low repeated-dose toxicity and not expect to be

harmful to human health or the environment at environmentally relevant concentrations. Although

short-chain fluorinated DWR (Durable Water Repellent) chemistries cannot break down in the

environment into perfluorooctanoid acid (PFOA) and perfluorooctane sulfonate (PFOS), degradation

by-products of short-chain fluorinated chemistries may also be substances of concerncxxiv. Potential

by-products of the short short-chain fluorinated chemistries include perfluorohexanoic acid (PFHxA)

and perfluorobutane sulfonic acid (PFBS) as stated above. Both of these substances are persistent in

the environment. They are, nonetheless, recognized to be less toxic and bioaccumulative according

to available studies. Given that substances associated with short-chain fluorinated chemistries are

persistent in the environment, uses which may cause widespread dispersion run the risk of not being

approved for use in certain countries. For example, the Australian government has taken measures to

restrict any use of PFBS-based substances that would result in widespread dispersion in aquatic

environments.

Silver Nano-dispersion (Ag):

This material is based on a nano-dispersion of metallic silver is commercially available in Europe. The

price of the material is about 120€/kg depending of quantity requested because it is a product

manufactured on Demand Book. Taking into account the chemical fabric composition and finishing

infrastructure that Piacenza has, no problems are expected during application process. The level of

transferability to another textile sector does not depend on nanomaterial used, so a high level it is

expected. The transferability depend on the industry needs to provide this functionality, the

capabilities of the company to use the proper method of application, the chemical composition of

selected fabrics, and internal regulations of the sector (prohibition of chemicals).

Regarding human health risks, in vitro, Ag-nanoparticles are toxic to cells derived from skin, liver,

lung, brain, vascular system and reproductive organs (somewhat in contrast to the relative low

toxicity in vivo). Some studies have shown that Ag-nanoparticles have the potential to affect genes

associated with cell cycle progression, DNA damage and apoptosis in human cells at non-cytotoxic

doses (Ahamed et al. 2010).

When assessing the (consumer) exposure to nanomaterials the characteristic of main importance is

the way the nanomaterials are incorporated into the product (e.g. free nanoparticles or

nanomaterials integrated into larger scale structures or fixed in a matrix) in combination with the

application of the product (with either direct or indirect human exposure, via release of particles out

of the product). In textiles, the most important exposure route is dermal and oral (toys) and the

potential exposure is unknown as there is no sufficient information available.

The Danish Environmental Protection Agency (EPA) analysed various textiles products containing

(nano) silver available on the Danish market. In total 16 products were analysed with different

analytical techniques. Twelve products containing silver were analysed further for the presence of

nanoparticles using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX)


spectroscopy. In 4 out of 12 products, silver particles (>200nm, 2 products) or threads (structure like

particles, 2 products) were detected. It should, therefore not be considered as nanomaterials in terms

of EU definition. Migration of silver from products to artificial saliva, sweat or waste water after

washing varied between various fabrics. They concluded that despite the potential for migration or

leaching of silver out of the products, there is little risk of biological effects in the environment

resulting from the use of nanosilver in textiles (Tonning et al. 2012).

Lorenz et al. (2012) investigated eight different commercially available silver-textiles during a washing

and rising cycle. Only half of the textiles leached detectable amounts of silver, of which 34-80% was

in the form of particles larger than 450 nm.

In addition, the Dutch Institute for Food Safety (RIKILT, Wageningen, Netherlands) published a report

on washing out of Ag from textiles. The silver is present in agglomerates of primary nanoparticles of

50-300 nm. The amount of released silver varies between products, depending of the amount of

silver present in the product and the level of silver bound to the textiles fibres. Three products

underwent 10 washings and released 11, 44 and 100% of the silver respectively from the fabrics.

(Peters et al. 2011)

Recently, Von Götz et al published a study (2013), in which dermal exposure to (nano) Ag has been

modelled based on migration data of Ag nanoparticles from textiles into artificial sweat. The

exposure assessment was based on data from a T-shirt and trousers, because no migration from

dissolved and particulate silver (<450nm) has been found from the socks investigated in this study.

The conclusion of this study is that in contrast to total silver, dermal exposure to nanosilver particles,

agglomerates and aggregates from functionalized textiles remains noteworthy potential pathway

when compared to other exposure routes.

Different occupational exposure limits and guidelines exist for silver, but values depend on the form

of silver as well as the individual agency making the recommendations. The American Conference of

Governmental Industrial Hygienists (ACGIH) has established separate threshold limit values for

metallic silver (0.1 mg/m3) and soluble compounds of silver (0.01 mg/m3). The Occupational Safety

and Health Administration (OSHA), the Mine Safety and Health Administration (MSHA) and the

National Institute for Occupational Safety and Health (NIOSH) recommend permissible exposure

limits on 0.01 mg/m3 for all forms of silver. Occupational exposure can occur during production,

packaging, mixing and loading of the material during manufacture of treated articles as well as their

handling and packaging. Secondary tasks including cleaning etc. provides another source of

exposure as does manipulation and handling of treated materials, e.g. cutting and sewing nanosilver

textiles. Consequently, dermal and inhalative exposures are expected for workers by a variety of

pathways.

Concerning environmental risks, nanosilver is released from a variety of sources in a variety of

different formscxxv. Silver released from applications in contact with water (textiles, pipes, personal

care products, etc.) reaches the sewer system. Lorenz et al. (2012) identified different forms of silver

for releases from textiles. For example, includes Ti/Si-AgCl nanocomposites, AgCl nanoparticles, large

AgCl particles, nanosilver sulphide and metallic nano-Ag with AgCl being the most frequently

observed chemical form. If the sewer system is connected to a wastewater treatment plant (WWTP),

approximately 95% of the silver entering the WWTP sorbs to sewage sludge and may then be

transferred to fields with the sludge. The fraction passing the WWTP enters the surface water.

Accordingly, silver levels need to be predicted for soil treated with sewage sludge and for freshwater

receiving WWTP effluents. These levels need to be compared to threshold concentrations for adverse

effects are determined for all environmentally relevant forms of silver, not only for ionic silver and

metallic silver nanoparticles.


Some studies have measured silver concentration in water bodies and sediments in several parts of

the world, mainly in Europe and North America. Typical levels in freshwater moderately affected by

human activity are around 1-10 ng/L (Wen et al. 1997; 2002; Tappin et al. 2010; Lanceleur et al. 2011).

Waters affected by untreated wastewaters, photographical industry or mining show higher

concentrations that are in the range of 100 ng/L to 1 mg/L (Wen et al. 2002; Lanceleur et al. 2011).

Silver concentrations in river sediments are on the order of 1 mg/Kg for industrialized regions (Gobeil

1999; Lanceleur et al. 2011) and may reach up to 10 or 100 mg/Kg at highly contaminated sites

(Dissanyake et al. 1983; Lanceleur et al. 2011). The geogenic background level is around 0.07 mg/kg

(Pais and Benton Jones 1997).

Aquatic silver toxicity has been found to depend on the free Ag+ ion concentration as well as other

dissolved chemical species of silver. Solubility and composition of the water are of outmost

importance for silver salts as well as for metallic silver (Ag0) for determining the detrimental effects of

silver (Ratte 199). Since different species of silver speciation is of outmost importance for the

assessment of toxicity.

Antimony pentoxide (Sb2O5)

This material is based on a nano-dispersion of antimony pentoxide and is commercially available in

USA and Europe through distributors. The price of the material is about 22,60€/kg depending of

quantity requested. Taking into account the chemical fabric composition and finishing infrastructure

that Vincolor has, no problems are expected during application process. It should be noted that it is

a nanodispersion that works as an additive on conventional halogenated flame retardants enhancing

their performance due de synergies produced. The level of transferability to another textile sector

does not depend on the nanomaterial used, so a high level is expected. The transferability depends

on the industry needs to provide this functionality, the capabilities of the company to use the proper

method of application, the chemical composition of selected fabrics, and internal regulations of the

sector (prohibition of chemicals).

TiO2 Nano-dispersion:

This material is based on a nano-dispersion of titanium dioxide and is commercially available in

Europe. The price of the material is about 9,85€/kg depending of quantity requested. Taking into

account the chemical fabric composition and finishing infrastructure that Piacenza has, no problems

are expected during application process. The level of transferability to another textile sector does not

depend on nanomaterial used, so a high level it is expected. The transferability depend on the

industry needs to provide this functionality, the capabilities of the company to use the proper

method of application, the chemical composition of selected fabrics, and internal regulations of the

sector (prohibition of chemicals).

The health and environmental hazards were demonstrated for a variety of manufactured

nanomaterials. It should be noted that not all nanomaterials induce toxic effects. Arguably, some

manufactured nanomaterials have been in use for a long time, such as TiO2 and carbon black, and

show low toxicity.cxxvi

Chronic effects have been observed from TiO2 nanoparticles production industry in six European

countries were more likely to develop lung cancer compared to the general populationcxxvii,cxxviii

. There

was enough concern for the National Institute for Occupational Health and Safety (NIOSH) to

propose a draft permissible exposure level (PEL) of 1.5 mg/m3 and a recommended exposure level

(REL) of 0.1 mg/m3. The PEL for nanoparticles is 15 times lower than the PEL for TiO2

microparticlescxxix

.


Warheit et al. (2007) reported on a base set of toxicity tests for detection of the acute toxicity of

ultrafine TiO2 particles using assays as described in various OECD guidelines. The results of most of

the studies demonstrated low hazard potential in mammals or aquatic species following acute

exposures to the ultrafine TiO2 particle-types testedcxxx

. In the studies, particle sizes were

approximately 140 nm in diameter when TiO2 was dispersed in water, but increased up to

approximately 2000 nm when present in phosphate buffered saline (PBS), thus indicating the

importance of nanoparticles characterisation as they are used in various test conditions.

Some studies determined the content of TiO2 1, 14 and 28 days after intravenously administration of

TiO2 nanoparticles in rats with a dose of 5 mg/kg body weight and a size range 20-30 nm. There

were no detectable levels of TiO2 in blood cells, plasma, brain or lymph nodes. The TiO2 levels (µg/g

organ) were highest in the liver, followed in decreasing order by the levels in the spleen, lung and

very low in the kidney, and highest on day 1 in all organs. TiO2 levels were retained in the liver for 28

days; there was a slight decrease in TiO2 levels from day 1 to days 14 and 28 in the spleen, and a

return to control levels by day 14 in the lung and kidney. A limitation of this study is that most of the

particles administered were in the fine fraction up to 1 μm, whereas only 10% by weight was in the

nanosize range (<100nm).

Several studies using different types of test (Comet, micronucleus and gene mutation assay) have

indicated that some nanoparticles may be genotoxic. For the most used test, Comet assay

demonstrate a positive outcome on genotoxicity including TiO2. In the micronucleus assay positive

results were obtained for nanoformulations of TiO2. For the gene mutation assays some studies

showed a positive result for several nanomaterials including TiO2. It was reported that the smaller

particles (~20nm) induced DNA damage while larger particles (~200nm) did not (Gurr et al. 2005,

Mroz et al. 2008, Rahman et al. 2002).

A variety of genotoxicity (Ames test, clastogenicity in mammalian cells) and photogenotoxicity

(Photo-Ames test, photo-clastogenicity in mammalian cells) tests have been performed under GLP

conditions on 14 different sunscreen-grade TiO2 (anatase and rutile; coated and uncoated; particle

size range 11-60nm + one pigment grade – 200 000 nm). All results were negative. They were

provided as an unpublished industry safety dossier but reviewed, summarised and published in the

Opinion of the Scientific Committee on Cosmetic Products and Non-Food Products Intended for

Consumers Concerning Titanium Dioxide (SCCNFP, 2000). Negative photo-clastogenic results were

also found in chromosome aberration tests on Chinese hamster ovary cells with a variety of TiO2

particles (anatase, rutile; particles size: 14-60 nm) (Theogaraj et al. 2007).

However, others (Rahman et al. 2002, Wang et al. 2007) documented that ultrafine TiO2 particles

increased the number of micronuclei in Syrian hamster embryo cells and a human B-cell

lymphoblastoma (WIL2-NS) cells. In the latter model mutation frequency was increased in the HPRT

test and DNA damage was indicated by the Comet assay.

Positive results in micronucleus test and oxidative DNA damage were found recently in fish cell lines

derived from rainbow trout and goldfish skin (Reeves et al 2008, Vevers and Jha 2008). It was

suggested that several types of TiO2 (anatase; particle size of 255– 420 nm) were not genotoxic but

photo-genotoxic in mouse lymphoma and Chinese hamster lung cells (Nakagawa et al. 1997). This

was further supported by the study of Dunford et al. (1997) which showed DNA oxidative damage in

human fibroblasts (MRC-5) using the Comet assay. Similar to silica (SiO2) positive results were

observed for TiO2 in all three types of genotoxicity assays (Landsiedel et al. 2008).


It has been shown that waste water treatment plants (WWTPs) are capable of removing the majority

of TiO2 nanomaterials from influent sewagecxxxi

. However, TiO2 particles measuring between 4 and 30

nm were still found in the treated effluent. These nanomaterials are then released to the surface

waters where they can interact with living organisms. TiO2 nanomaterials that are absorbed in the

treatment plants may still end up in the environment if the biomass is land applied and it later

leaches out of the soil. Though the release of TiO2 nanomaterials to the environment has been

shown, it is difficult to quantify how much is released. Once in the environment, even less is known

about how organisms are affected by nano-TiO2. Phytotoxicity studies have shown that nano- TiO2

particles inhibited growth of some plants by reducing the hydraulic conductivity while others have

shown that the particles may improve growth by enhancing photosynthesis in leaves and nitrogen

fixing in rootscxxxii

. It has been shown that fish absorb TiO2 nanoparticles through their grills. Once

into the bloodstream, particles can translocate to various organs in the body. Concentrations as low

as 16mg/L of nanosized TiO2 have been shown to inhibit the growth of algae in natural waters. TiO2

has been shown to bioaccumulate, with higher concentrations in Daphnia magna at 21 days than at 3

dayscxxxiii

.

6. Conclusions

Nanofinishing can replace traditional finishing agents applied to textile products, providing products

of higher quality and lower production costs. As a consequence, it is expected that in the next few

years nanotechnology will penetrate deeply in the finishing textile sector, and an increasing number

of textile companies will invest in the development of processes involving nanotechnology. However,

there are still concerns to be taken in consideration before the commercialisation of nanoproducts,

such as costs and impacts of uncontrolled release of nanomaterials. Therefore, there is a general

need to conduct further investigations to reduce the knowledge gaps in nanomaterials, especially in

terms of human health and environmental risks. This will help to understand both the hazards of

nanomaterials and potential exposures.

In the state of the art have been identified a wide list of nanomaterials that can provide properties to

textiles (e.g. fire resistance, self-cleaning, antibacterial, UV resistance, water repellent, mechanical

resistance, etc). However, to date there are few commercially available nanomaterials with a proven

experience to be applied directly to textiles. Many of the nanomaterials sold for the textile sector

need to be formulated for an effective performance. One of the major challenges when working with

nanoparticles in coating and finishing applications is to obtain a good pre-dispersion of the

nanoparticles. These nanoparticles dispersions are often not commercially available or not tailored to

textile products. On the other hand, there are nanaomaterials that are sold just for research purposes,

and not for textile industries. One of the aims of this report is to select four commercially available

nanomaterials that provide different properties to textiles in order to apply in the two pilot scale

trials and demonstrate their effectiveness. Different criteria have been considered for the selection

procedure, such as human health & environmental risks, environmental impacts, performance of

nanomaterials, commercial availability, price of nanomaterial, feasibility to be applied in pilot scale

trials, level of transferability and availability of data. According these criteria, the four nanomaterials

selected have been:

1. Silver to provide antibacterial properties

2. C6 based fluorochemical to provide soil release properties

3. Antimony pentoxide as a flame retardant

4. Titanium dioxide to provide UV properties


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http://www.nanowerk.com/

http://www.nanonext.net/

http://www.nanocare-ag.com/

http://www.cristal.com/

http://www.nyacol.com/

http://www.nanocor.com/

http://ec.europa.eu/health/ph_risk/committees/04_scenihr/docs/scenihr_o_023.pdf

http://ec.europa.eu/health/ph_risk/committees/04_scenihr/docs/scenihr_o_023.pdf

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