Bioprocessing for Sustainable Production of Coloured textiles · Textile pretreatments: scale-up of technologies abling to increase dyeability of selected ... - Silk - Linen - Wool

Work Package 2 – Selection of textile substrates and chemicals

Lead contactor for this deliverable: SETAS Coordinator organisation: University of Siena Coordinator: Rebecca Pogni Dissemination Level: CO Confidential, only for members of the consortium (including the Commission Services)

Bioprocessing for Sustainable Production of Coloured textiles

CIP Eco-innovation – First Application and market replication projects ECO/09/256112/SI2.567273

www.biscol.unisi.it

Starting date: September 1st, 2010 Duration: 36 months

Deliverable 2.1 Report on quantification and composition of the most used textile

support

Bioprocessing for Sustainable Production of COLoured textile

WP2/Deliverable 2.1 Page 2 di 29

1. INTRODUCTION AND OBJECTIVES..................................................................................................................... 3 2. RESULTS AND DISCUSSION ................................................................................................................................... 5

2.1. TEXTILE FIBERS...................................................................................................................................................... 5 2.1.1. Definition of textile fiber and its polymeric nature ......................................................................................... 6 2.1.2. Defining characteristics of the fibers .............................................................................................................. 6 2.1.3. Classification of textile fibers.......................................................................................................................... 8 2.1.4 Textile fibers names dratf regulation ............................................................................................................. 16

2.2. SYSTEM THINKING AND GREEN CHEMISTRY IN TEXTILE INDUSTRY: ENVIRONMENTAL IMPACT ...................... 17 2.3. EVALUATION OF TEXTILE FIBER MARKET........................................................................................................... 20

3. CONCLUSION ........................................................................................................................................................... 24 REFERENCE LIST ....................................................................................................................................................... 25 APPENDIX...................................................................................................................................................................... 26 A1. FROM TREES TO CELLULOSIC FIBERS........................................................................................................ 26



1. Introduction and objectives

The textile and clothing industry is one of the world’s most global industries, and constitutes an

important source of income and employment for many EU countries. their end products constitute

the world’s second largest industry, ranking only below food products. At least 10% of the world’s

productive energies are devoted to this activity. Industries including retail apparel marketing,

construction, agriculture, machine tools, automobiles, petrochemical, carpet, and recreation all rely

upon the textile manufacturing industry for raw materials.

The business of the textile industry is production of value-added products from fiber, often through

intensive hand labor (Fig. 1). It comprises the following activities:

• the treatment of raw materials, i.e. the preparation or production of various textile fibres, and/or the manufacture of yarns (e.g. through spinning).

o ‘Natural’ fibres include cotton, wool, silk, flax, jute, etc. o ‘Man-made’ fibres include cellulosic fibres (e.g. viscose), synthetic fibres (i.e.

organic fibres based on petrochemicals, such as polyester, nylon/polyamide, acrylic, polypropylene, etc), and fibres from inorganic materials (e.g. glass, metal, carbon or ceramic).

• the production of knitted and woven fabrics (i.e. knitting and weaving); • finishing activities – aimed at giving fabrics the visual, physical and aesthetic properties

which consumers demand – such as bleaching, printing, dyeing, impregnating, coating, plasticising, etc;

o the transformation of those fabrics into products such as: o garments, knitted or woven (= the so-called ‘clothing’ industry); o carpets and other textile floor coverings; o home textiles (such as bed linen, table linen, toilet linen, kitchen linen, curtains, etc); o technical textiles

Fig. 1. Textile Production. Textile production is based on the conversion of polymers, natural or synthetic, first into fiber and then into bundles of fibers called yarn. Yarn is then converted into fabrics, a largely two-dimensional surface, where it is used for apparel, industrial, home furnishings and many other uses.



Textile industry accounts for 5.7% of the production value of world manufacturing output, 8.3% of

the value of manufactured goods traded in the world, and over 14% of world employment. In the

EU in 1999, 120,000 textile and clothing companies employed over two million people, thus

accounting for 7.6% of total employment of EU manufacturing industry. In terms of production and

turnover, the sector’s share was about 4%. High labor costs in developed regions have led to the

transfer of the textile industry into the less industrially developed regions of the world, where less

expensive labor and less stringent enforcement of environmental regulations results in lower

production costs, at least in the short-term.

Α recent survey of the textile/clothing industry in Europe by the European Commission illustrated

the size and importance of the textile industry in the European economy and highlighted the

challenge it faces (Table 1). While the textile industry employed 1.35 million in the mid-90s, this

workforce was reduced to fewer than 1,100,000 at the turn of the twenty-first century. Almost a

quarter of the jobs in textile/clothing disappeared between 1990 and 1996, and this trend has been

continuing since, albeit at a slower pace. It is estimated that 92,000 jobs were lost in 1999, but

despite this, the textile/clothing sector continues to employ two million people today, and remains

an important source of jobs in the EU, especially for the female population.

Table 1 The data of the European Textile/Clothing Industry.

Parameter Assortment 1999 2000 2001 2002 Textile 1210 1156 1142 1092

Clothing 1194 1106 1038 980 Total employment (x 1000) Total 2404 2262 2180 2072

Textile 76 75 72 70 Clothing 125 120 113 107

Total number of firms including firms with less than 20 persons (x

1000) Total 201 195 185 177

In this contest BISCOL project will be focused on the dyeing industry proposing a new dyeing

process as global alternative for the bioconversion of raw materials into competitive eco-viable final

products. To reach this scope different expertises optimized during other research projects by

partners of consortium will be combined, in particular:

Synthesis of bio-dyes: new bio-dyes will be synthetised at industrial scale by scale-up of

bioreactor containing laccase enzyme, able to bio-synthetised new coloured compounds.

Textile pretreatments: scale-up of technologies abling to increase dyeability of selected

textiles versus bio-dyes.

Synthesis of new auxiliaries: new auxiliaries at lower environmental impact, will be

synthetised at industrial scale and combined with bio-dyes.



Optimisation of dyeing process: reduction of energy demand of dyeing process (e.g.

lowering temperature and time of treatments) will be combined with the use of new bio-dyes

and auxiliaries and treated textile in order to validate at industrial scale the proposed new

dyeing process.

WP2 is the first technological workpackage which lead to decisions concerning target dyes to

biosynthetised, textile fibers to dye and auxiliaries to optimise dyeing process. In particular

Deliverable 2.1 describes the selection of textile substrates (at least two) giving particular attention

to the highest sustainability and the lowest environmental impact of the proposed approach which is

the main project goal.

2. Results and Discussion

2.1. Textile fibers For millennia man uses natural products with a fibrous matrix to transform them into yarns and then

fabric to warp up, to protect against the cold, to adorn himself and also to show off their social and

economical status.

The most important natural textile fibers, such as:

- Silk

- Linen

- Wool

- Cotton

represent the oldest textile products, originated from east countries, in fact:

The chemical textile fibers are the result of technology developed from the XX century beginning

to nowadays. They evolved starting from "artificial" fibers, obtained from natural products using

regeneration or moifying processes of raw materials; and "synthetic" fibers were obtained by

polymerization reactions.

Silk It was used for millennia by the Chinese; only in 300 AD it was introduced in the West, when the sericulture landed at Mediterranean land sides

Linen It was used by the ancient Asian people and by Egyptians; later it landed in Europe Wool It was used in Central Asia, but the major development of the most well-known and

valuable wool occurred in Europe, and more recently in England; later also Australia, South Africa and Argentina have become major producers of wool;

Cotton It was used in India; it landed in Europe around 1200 and later in America. Only after the invention of machine for shelling cotton flaskes, this fiber become the most important and widespread natural fiber



2.1.1. Definition of textile fiber and its polymeric nature The definition provided by UNI 5955/86 states that: "A textile fiber is a matter characterized by

flexibility, sharpness, a high length/cross-section ratio and molecules oriented in the longitudinal

direction.

The structure of each textile fiber includes the following points:

the chemical structure based on a polymeric system,

specific physical properties,

determined shape and form.

Both natural and chemical fibers have the same chemical structure based on the "polymeric

system”. This is characterised by:

high molecular weight

linearity of macromolecules

orientation of macromolecules

high melting points

presence of crystalline and amorphous areas

2.1.2. Defining characteristics of the fibers

□ Section: it represents the typical cross and longitudinal section shape of each fiber.

Natural fibers are characterised by defined section, while the man-made fibers’ cross-

sections are determined by the opening size in the extrusion and spinning processes.

□ Density or specific weight: It is the mass per unit of volume usually expressed in g/cm3.

For a low density value, fiber will be voluminous and light fiber, and the corresponding

thread or yarn will show a greater opacity.

□ Moisture recovery: it describes the textile fiber aptitude to absorb and keep water. It

indicates fiber hygroscopicity: natural fibers are more hygroscopic than synthetic fibers.

□ Toughness: It is the strength compared to the linear mass. It indicates the tensile strength

of a fiber. It is also known as ulltimate strength. Different measurement systems can be

used; the most common are g/den, g/dtex and cN/tex. Fibers and yarns can be tested for

toughness in dry or wet conditions. In the case of wet tests usually a reduction in material

toughness is reported, while an increase is shown in vegetable fibers.

□ Loss of toughness in wet conditions: It is the percentage between the toughness in dry

and in wet conditions.



□ Break extension: It is textile fiber ability to stretch during extension. It is defined by the

difference between the initial length of the material and its length at the time of the break

in percentage.

□ Elastic modulus: The elastic modulus or Young's modulus is a measurement of the initial

slope of the load-elongation curve. It describes the relationship between load and

elongation, and it expresses the force required to cause the unit elongation of the material.

For textile it is the initial modulus, corresponding to deformation induced by low loads,

similar to effects of work and use stress. A very high elastic modulus indicates low

deformation of the fiber, which will be rather rigid, resilient and not much creased. A low

modulus indicates high deformability of the fiber, which will be more softer, less resistant,

easily creased. A fiber with high modulus, high elasticity and good resilience, has "wash

and wear" properties.

□ Elasticity: it is the ability of a textile to recover its pristine structure after a deformation as

elongation, compression, bending.

□ Resilience: it is the ability of a textile to recover its thickness after a surface pressure.

□ Tendency to crease: it is the elasticity loss of a fiber, which does not recover its pristine

shape after deformation incurreddue to bending actions.

□ UV resistance: it is the ability of a fiber to maintain its characteristics after

exposure to ultraviolet light. Some synthetic and artificial fibers of new generation are

able to protect skin from exposure to UV rays.

□ Weather resistance: it is the ability of a fiber to maintain its characteristics after exposure

to particular weather conditions (dry, rain, light, wind, etc.).

□ Resistance to chemicals: acids, alkalis, solvents, oxidants. It is the ability of a fiber to

maintain its characteristics after exposure to certain chemicals under controlled conditions

(time, temperature, concentration, etc.).

□ Flammability: it is the ability of a material to burn with flame emission after exposure to

a heat source.

□ Softening point: it is the temperature at which the fibers begin to soften, becoming sticky.

□ Melting point: it is the temperature at which the polymer changes from solid to fluid or

liquid state.



2.1.3. Classification of textile fibers Textile fibers are broadly classified into two major groups: natural and chemical, depending upon

the nature of their source. Each class is composed of different fibers.

Fibers classes

Natural Vegetable fibers Animal fibers Mineral fibers

Organic fibers from natural polymer (artificial fibers) from synthetic polymer (syntethic fibers) from paper

Textile fibers

Chemical Inorganic Fibers

Glass Ceramic Metal

Natural fibers still account for a major share (some 45%) of the total textile fiber consumption

around the world. The term ‘‘man-made’’ is applied to all fibers that include those regenerated from

natural products as well as those that are synthesized from basic chemicals. There are a variety of

texts dealing with the general classification, properties, and chemical compositions of textile fibers

and the synthesis of manmade fibers. In recent years, the original list of man-made fibers has been

supplemented by a variety of newly synthesized fibers, engineered specifically for high

performance end uses, such as aramid, polysulfide, and polybenzimidazole to name a few.

Synthetic fibers include all textile in which the fiber-forming material(s) is from basic chemicals.

Actually there is a new class of synthetic fibers, produced from material derived from a natural

renewable origin, such as corn, known as polylactic acid or polylactide (PLA).



Class Name Source Composition NATURAL FIBERS Vegetable Fibers

Cotton* Linen* Jute Hemp Agave (fiber) Kapok Ramie Coir (fiber) Pina

Cotton bolls Stem of the flax Stalk of the jute Stalk of the hemp Agave leaf Seeds of kapok Bark of vegetative stalks Coconut shell Pineapple leaf

Cellulose Cellulose Cellulose Cellulose Cellulose Cellulose Cellulose Cellulose Cellulose

Animal Fibers Wool* Silk* Nap

Sheep and goat fleece Silkworm Animal hair

Protein Protein Protein

Mineral Fibers Asbestos Variety of rocks silicate rocks (Ca) - (Mg) ARTIFICIAL Cellulosic Fibers

Cupro* Viscose* Modal* Lyocell* Acetate* Triacetate*

Cotton waste Wood pulp Linters

Regenerated cellulose Acetylated cellulose

Proteic Fibers Corn, soy, casein, etc.. Protein Rubber Rubber Natural rubber Rubber Polyisoprene SYNTHETIC Chemistry Chemical composition Organic Fibers

Polyamide* Aramid Polyester* Acrylic* Modacrylic* Spandex* Olefin* Chlorofibres* Fluorocarbon

Aliphatic polyamide Aromatic polyamide Diol and terephthalic acid Acrylonitrile (85%) Acrylonitrile (35 to 84%) Polyurethane (85%) Polyethylene (85%) Polypropylene (85%) Vinyl chloride (85%) Vinylidene chloride (85%) Tetrafluoroethylene

Textile Paper Paper Pulp Cellulose Inorganic Glass fiber

Graphite Ceramics Metal

Silica sand and limestone Coal Clay and silica Gold, silver, aluminum, stainless steel

* Primary fibers used for knitted fabrics Natural fibers:

COTTON: A unicellular, natural staple fiber hitch is the seed hair of plants of the genus

Gossypium. It is almost pure cellulose and a distinguishing characteristic is its irregular

spiral configuration. The fiber is fine and its length varies from less than 1/2 inch to over 2

inches. The quality and color of cotton fiber, normally creamy white but sometimes much

darker, is determined by the plant variety as well as the location, soil and climatic conditions

under which it is cultivated. The largest cotton producers by far today are China, the U.S.,

and Russia. Other growers with high output are India, Pakistan, Brazil, Turkey, and several

South America and African countries.Characteristics : for marketing, cotton fibers are



graded and classed for length, fineness, strength, and color. It is a highly versatile fiber with

high strength and a high moisture regain of 8%, which contributes to its comfort.End uses :

cotton is the most widely used natural fiber. Because of its versatility and comfort, cotton is

widely used throughout the world in a very broad range of textile materials. Today cotton is

often blended with other staple fibers, especially polyester, to take advantage of the

characteristics of both fibers.

LINEN:Linen is woven from fibers produced by the flax plant, and the term "linen" cannot

be applied to any other kind of fiber except that of natural flax. Among the properties of

linen are rapid moisture absorption, fiber length of a few inches to one yard, no fuzziness,

soil-resistance, natural luster and stiffness. The fabric unless specially treated tends to crease

considerably. Most appropriately used in cool sportswear.

WOOL: A protein fiber usually associated with fiber or fabric made from the fleece of sheep

or lambs. However, the term 'wool' can also apply to all animal hair fibers, including the hair

of the Cashmere or Angora goat or the specialty hair fibers of the camel, alpaca, llama, or

vicuna. Wool is very resilient and resistant to wrinkling. It is renewed by moisture and well

known for its warmth. It absorbs and releases moisture slowly, which allows excellent

insulating capabilities and breathability. It can even hold 30% of its own weight without

feeling damp.

“Eco Wool” – Sheared from free range roaming sheep that have not been subjected to toxic

flea dipping, and have not been treated with chemicals, dyes, or bleaches. Eco wool comes

in natural tones of white, grey and black.

SILK: A fine lustrous fiber composed mainly of fibroin and produced by certain insect

larvae to form cocoons, especially the strong, elastic, fibrous secretion of silkworms used to

make thread and fabric.



LINEAR FORMULA LONGITUDINAL SECTION CROSS SECTION

COTTONGlucose units

—(C6H10O5)—n

two glucose units form the monomer cellobiose

LINENGlucose units

—(C6H10O5)—n


WOOL

—(C42H157O15N5S)—n

SILK

—(C24H36O8N8)—n


COTTONGlucose units

—(C6H10O5)—n


LINENGlucose units

—(C6H10O5)—n


WOOL

—(C42H157O15N5S)—n

SILK

—(C24H36O8N8)—n

Regenerated fibers:

CUPRO: Like tencel and rayon, the base material for cupro is a regenerated cellulose fiber .

Cupro gets its name from cuprammonium, the process that is used to process the wood pulp

or cotton linters that are its base material. In this process, the wood pulp or cotton liners are

dissolved in an ammoniac copper oxide solution. Cupro fabric breathes like cotton, drapes

beautifully, and feels like silk on your skin. Its slinky, curve-hugging drape makes it great

for elegant dresses and blouses.

VISCOSE: The generic name for fibres formed by the regeneration of cellulose from

viscose by treatment with a solution of electrolytes (salts and acids).

MODAL: Modal is a cellulose fiber made by spinning reconstituted cellulose from beech

trees. It is about 50% more hygroscopic (water-absorbent) per unit volume than cotton. It

takes dye just like cotton, and is color-fast when washed in warm water. Modal is essentially

a variety of rayon. Textiles made from Modal are resistant to shrinkage and fading. They are

smooth and soft, more so than mercerized cotton, to the point where mineral deposits from

hard water do not stick to the fabric surface. Modal fabrics should be washed at lower

temperatures and ironed after washing.



POLYNOSIC FIBER: A regenerated cellulose fibre that is characterised by a high initial

wet modulus of elasticity and a relatively low degree of swelling in sodium hydroxide

solution.

Regenerated and modified fibers:

ACETATE: a manufactured fiber in which the fiber-form substance is cellulose acetate

(FTC definition). Acetate fabrics are fast-drying, wrinkle and shrinkage resistant, crisp or

soft in hand depending upon the end use, and luxurious in appearance. The end uses of

acetate include lingerie, dresses, blouses, robes, other apparel, linings, draperies, bedspreads,

upholstery, carpets, umbrellas, formed fabrics, and cigarette filters.

TRIACETATE: Triacetate is derived from cellulose by combining cellulose with acetate

from acetic acid and acetate anhydride. The cellulose acetate is dissolved in a mixture of

methylene chloride and methanol for spinning. As the filaments emerge from the spinneret

the solvent is evaporated in warm air - dry spinning - leaving a fiber of almost pure cellulose

acetate. Triacetate fibers contain a higher ratio of acetate-to-cellulose than do acetate fibers.

ACRYLIC: A manufactured fiber in which the fiber-forming substance is any long chain

synthetic polymer composed of at least 85% by weight of acrylonitrile units [-CH2-



CH(CN)-] (FTC definition). Acrylic fabrics have low moisture absorbency and dry

relatively quickly. In general, acrylic fibers are resistant to the degrading effects of

ultraviolet rays in sunlight and to a wide range of chemicals and fumes. They provide

warmth in fabrics which are lightweight, soft, and resilient.

MODACRYLIC: A manufactured fiber similar to acrylic in characteristics and end-uses.

Modacrylics have a higher resistance to chemicals and combustion than acrylic, but also

have a lower safe ironing temperature and a higher specific gravity than acrylic.


ACETATE

⎯[(C6H7O2)(OCOCH3)]⎯2,3

TRIACETATE

⎯[(C6H7O2)(OCOCH3)]⎯3

ACRYLIC

⎯(CH2 -CHCN)⎯n

MODACRYLIC

⎯(CH2 -CHCN)⎯n


ACETATE

⎯[(C6H7O2)(OCOCH3)]⎯2,3

TRIACETATE

⎯[(C6H7O2)(OCOCH3)]⎯3

ACRYLIC

⎯(CH2 -CHCN)⎯n

MODACRYLIC

⎯(CH2 -CHCN)⎯n

Synthetic fiber:

POLYAMIDE: a synthetic fiber produced from melts or solutions of polyamides. Polyamide

fibers are usually produced from linear aliphatic polyamides, most often polycaproamide

and polyhexamethylene adipamide, with molecular weights varying from 15,000 to 30,000.

Polyamide fibers are characterized by high tensile strength and excellent resistance to wear

and impact. They are stable to the action of many chemical reagents and biochemical agents,

and they have an affinity to many dyes. The maximum operating temperature of fibers made

from aliphatic polyamides is 80–150°C, and of fibers made from aromatic polyamides,



350°–600°C. The fibers dissolve in concentrated mineral acids, phenol, cresol,

trichloroethane, and chloroform.

POLYESTERE: A manufactured fiber in which the fiber forming substance is any long-

chain synthetic polymer composed of at least 85% by weight of an ester of a substituted

aromatic carboxylic acid, including but not restricted to substituted terephthalic units and

parasubstituted hydroxy-benzoate units.

ELASTANE: A man-made fibre containing at least 85% polyurethane which is capable of

high stretch followed by rapid and substantial recovery to its unstretched length. also known

as spandex, especially in the USA).

POLYPROLEFINE: A fibre made from a synthetic linear polymer obtained by polymerising

an unsaturated hydrocarbon (e.g. ethylene CH²-CH² or propylene CH² = CH-CH3) to give a

linear saturated hydrocarbon. (See also polyethylene fibre and polypropylene fibre).

LINEAR FO RMUL A L ONG ITUDINAL SECTION CROSS SECTION

PO LYAMIDE

PO LYESTER

EL ASTANE

-(R-O-C O-NH-R’-NH-C O-O)-n

POL YPROLE FIN

⎯ (CH2-CH -CH)⎯ n

LINEAR FO RMUL A L ONG ITUDINAL SECTION CROSS SECTION

PO LYAMIDE

PO LYESTER

EL ASTANE

-(R-O-C O-NH-R’-NH-C O-O)-n

POL YPROLE FIN

⎯ (CH2-CH -CH)⎯ n

The choice of textile fibers to be used as raw materials in a specific application depends on an

unique combination of different properties: dimensional or geometric, physical, mechanical,

general.



The longitudinal and transverse dimensions, i.e., fiber length and fineness, respectively, are two of

the most important dimensional properties that influence processing performance and the final end-

use properties. Both these dimensional properties of natural fibers vary considerably depending on

the type and origin of the materials. The ralationships between the fiber length and fineness of

different natural fibers of different types have been reported in literature. The length and diameter

of man-made fibers can be accurately determined and controlled during extrusion (spinning).

Consequently, man-made fibers are far more uniform in their longitudinal nad transverse

dimensions that natural fibers.

Another important characteristic of fibers that will be selected in BISCOL project is the dye

affinity. Several fibers can exhibit very different dye affinities. Some fibers are more easily dyed

and in greater depth that filaments. The dyeing of acrylic fibers has proved difficult to a certain

extent, while polyacrylonitrile fibers begin to exhibit adequate affinity only at relatively high

temperatures. The wool fiber is composed of keratin protein, which consists of long polypeptide

chains built by eighteen different amino acids. The wool fiber is readily destroyed by alkali, but

withstands acid conditions fairly well; some hydrolysis of peptide linkeges occurs on prolonged

boiling with acids, however. The carboxylic acid and amino groups in the keratin molecule confer

affinity for basic and acid dyes. Basic dyes are actually little used on wool since their fugitive

properties render them unsuitable for such and expensive and durable fiber. Acid dyes, however,

are extensively used.

The earliest cellulosic fibers were linin and cotton, both of which have been used since remote

antiquity. The dyeing properties of the various cellulosic fibers are broadly similar, but application

conditions are affected by differences in physical properties.

Fastness of dyed textiles is evaluated in regard to natural destructive agents, such as daylight,

weather and atmospheric gases, as well as to various treatments the material is likely to undergo,

such as washing, dry-cleaning, ironing, steaming, etc.



2.1.4 Textile fibers names draft regulation

Launched in 2006, the modernisation of the directives relating to the textile fibers denomination and

their marking (96/74/EC and 96/73/EC) faced an acceleration after the new European Parliament

(EP) was nominated.

In October 2009 the Committee on the Internal Market and Consumer Protection (IMCO) of the EP

nominated Mr. Manders (NL-ALDE – Alliance of Liberals and Democrats for Europe) as

rapporteur. Since the starting it appeared that there was a fundamental misunderstanding regarding

the scope of the draft regulation. The EC Commission, the Member States, the industry and the

retailers want to keep the scope as narrow as possible while modernising and simplifying the

adoption of the new fibre names while, the rapporteur, as well as other members of the IMCO

committee took a completely different approach. In their views the Textile fibres names draft

regulation is the opportunity to clarify, complete and improve the labelling system for textile and

clothing products by “providing consumers with accurate, relevant, intelligible and comparable

information on the characteristics of textile products”.

The new marking and labelling requirements as proposed by the European Parliament. Textile and clothing products sold into the EU market should bear indications, were needed, of: The origin for textile products The inclusion of animal-derived materials in a textile product The care label based on an harmonised care labelling system The size label based on an EU-wide uniform size labelling system for clothing and footwear An ecological label relating to the environmental performance and sustainable production of textile products

A social label to inform consumers about the social conditions under which a textile product was produced

Warning labels with regard to the flammability performance of textile products, in particular high-fire-hazard clothing

Any potentially allergenic or hazardous substances used in the manufacture or processing of textile products

Any potential allergic reactions due to synthetic fibres, colourings, biocides, preservatives or nano-particles used in textile products

Moreover, the European Parliament would like to enable the consumer to easily understand the labels on textile and clothing products by favouring: electronic labelling, including Radio-Frequency Identification (RFID), the inclusion of an identification number on the label which shall be used to obtain additional on-demand information about the product, for instance via Internet,

the use of language-independent symbols for identifying the fibres used for the manufacture of a textile product



2.2. System thinking and green chemistry in textile industry: environmental impact The European Textile and Clothing industry, a leader in fashion, technology, quality and creativity,

is increasingly facing new challenges. Beside the so-called ‘traditional’ socio-economic challenges,

the industry is also facing others related to health and environment. Taking the fact that improving

environmental quality of production and products needs creativity and investments; the question

becomes not just one of morality but also of economic competition in a world market with different

aims and philosophies.

These challenges inevitably impact on the industry’s activities and overall performance and involve

heavy compliance socio-economic costs. Legislation is obviously the most common tool to achieve

the political agenda of the EU but at the same time it needs to meet the different and often divergent

interests to be effective enough to ensure development in the right direction enhancing therefore the

possibilities for the approach to become a real challenge and not a snare to the development of the

industry.

The European Textile and Clothing industry while taking into consideration these challenges insist

that all legislative measures should meet the criteria of being predictable, flexible, adaptable and

cost effective.

This general policy includes a range of measures to deliver more sustainable consumption and

production while improving economic competitiveness. It extends the Eco-design Directive to

energy related products and introduces benchmarks. Product labelling under the Energy Labelling

Directive and Eco-label Regulation will be developed; will establish a harmonised base for public

procurement and incentives. A range of other actions aimed at achieving smarter consumption will

also be undertaken. These objectives can however only be achieved if care is taken to avoid

increased costs and a further layer of regulation which will handicap the competitiveness of

European companies.

To achieve a successful implementation of the Action Plan, the full respect of better regulation and

sustainable principles is required. This means putting in place a coherent legislative framework

without overlapping and/or conflicting requirements; avoiding an increase of bureaucracy and

administrative burden, ensuring cost efficiency of measures, guaranteeing transparency and

involving stakeholders representing the supply chain actors from the very beginning, promoting

actions internationally to ensure sustainability measures are not used as barriers to trade; embracing

sustainability in its economic, environment and social dimensions; basing actions on sound

scientific evidence, applying life cycle thinking encompassing all relevant environmental aspects,

pursuing a voluntary approach to sustainable development wherever possible, permitting flexibility

in the way agreed policy goals are achieved; leveraging innovation as a source of process, product



and service solution; offering EU industries opportunities; and finally providing relevant

communication actions to shape consumer behaviour towards sustainable choices.

In this context BISCOL project aims to propose a new dyeing process as global alternative for the

bioconversion of raw materials into competitive eco-viable final products. To validate the new

process Life Cycle Assessment and toxicological tests will address the scale up of the new

technology.

As WP6 (on LCA) will start at M6, to optimize fiber selection, an analysis of environmental

impact of textile fibers has been carried out based on studies reported in litterature.

The environmental aspects of textiles are very complex and include production, processing,

transport, usage, and recycling. Textiles are made from a variety of materials and can contain a

large number of chemicals. Chemicals are used during production of fibres, for preservation and

colouring and they are released during normal wear and during washing.

Traditional natural clothing materials are animal furs and leather, and fibres from wool, cotton,

hemp, linen and silk. Fibres from traditional and alternative plants have been assessed for

environmental impact, showing that several alternatives were more environmental friendly than

cotton. Artificial fibres are made from cellulose (viscose, modal and acetate) and synthetic plastic

fibres made from plastic polymers. They all have a high molecular mass, and are therefore

biochemically inert and are not hazardous from a toxicity point of view. Nevertheless also inert

plastic fibres can affect biota as seen in marine animals affected by accidental ingestion of litter,

since the polymers are resistant to degradation. Toxicants of concern in plastics are the unreacted

residual monomers, polymer degradation products and additives.

The multitude of possible chemicals in textiles and their leachabilty from specific articles makes

risk assessments for textile articles complicated. Examples of chemicals that may occur in textiles

are alkylfenoxylates, azodyes and pigments, flame retardants, formaldehyde, phthalates,

chlorinatedorganics, metals, pentachlorophenol andPCBs. However, the additives have only been

studied one by one and not in direct relationship with their leachability from textile products.

In literature a comparative toxicity of leachates from 52 textiles was reported. Daphnia magna was

used to measure toxicity according to a standard protocol (International Organisation for

Standardization (ISO). Aspects of textile fibre type, printing and eco-labelling were considered in

the selection of textiles for testing and in the interpretation of test results.

The research brought out the fact that toxicity of textiles is not restricted to the factories but also to

the usage of the textile products. Nevertheless the high number of chemicals and amounts that are

used in textile production points to the need for information on the composition and content of

valuable as well as hazardous chemicals in articles. There is also a need for information on



chemicals in textiles because they can affect the user (human health), and they can contaminate the

environment through sewage (sludge and wastewater).

Regarding test results, it was not possible to detect any difference between fibre type and toxicity

(ANOVA), but a significantly higher toxicity was found for printed versus unprinted cotton and

cotton/linen textiles. Eco-labelled products were evenly distributed on a toxicity scale, which means

that eco-labelling in its present form does not necessarily protect users or the environment from

exposure to toxic chemicals. Therefore, the results from the present study suggest that bioassays and

toxicity tests should become an integrated part of textile environmental quality control programs.

BISCOL project is focused on dyeing process, using chemicals (dyes and auxiliaries) at low

environmental impact.

Recently a comparative environmental assessments (using LCA) between man-made cellulose

fibers, conventional cultivated natural fibers (e.g. cotton) and fossil fuel-based synthetic fibers has

been published. The analysis was carried out for the system of cradle-to-factory gate. The main

findings of this study are:

1 Based on all the mid-point results and three single scores, it was concluded that all man-made

cellulose fibres, except for Viscose (Asia), have better environmental profiles than PET, PP and

cotton; Tencel (2012) has the lowest impact of all. Viscose (Asia) has a lower impact than cotton;

it is comparable to PET, but less preferable than PP and other man-made cellulose fibres.

2 The environmental benefits of Viscose (Austria) and Modal are largely attributed to low fossil

energy requirements in the pulp and fibre production. This is a result of process integration, the

use of renewable energy and credits from by-products. Furthermore, Viscose (Austria) and Modal

have much lower process emissions (e.g. SO2 and NOx) compared to Viscose (Asia), leading to

low human toxicity, photochemical oxidant formation, acidification and eutrophication. The

environmental benefits of Tencel (2012) are the result of low energy consumption, low chemical

use, low CO2 emissions, low SO2 emissions and low water consumptions, leading to low impacts

on abiotic depletion, terrestrial ecotoxicity, photochemical oxidant formation and acidification.

3 Viscose (Asia) is less favourable than the other studied manmade cellulose fibres. The higher

impacts of Viscose (Asia) are primarily attributed to process energy, the use of market pulp and

local sourcing of chemicals while emissions from the viscose process are a minor contributor to

the overall impact.

4 Cotton is not an energy-intensive product; it has the lowest CED of all fibres studied. However,

cotton is ranked as the least favourable choice by Single scores II and III. The major

environmental issues of cotton include land use, water use, fresh water aquatic ecotoxicity,

terrestrial ecotoxicity and eutrophication. The use of pesticides in cotton cultivation causes most



of the ecotoxicity impacts. Furthermore, the use of fertilizer is the main cause of the

eutrophication impact.

5 Two alternative allocation methods were applied. Both lead to less favourable results for man-

made cellulose fibres compared to the default method, although the ranking of all fibres studied

does not change.

6 Based on the system of cradle to factory gate plus waste incineration with and without energy

recovery, all man-made cellulose fibres studied are better than PET and PP in terms of Net NREU.

2.3. Evaluation of textile fiber market

The production of textile materials has undergone dramatic changes in the last century. Prior to the

industrial revolution in the 19th century, natural materials, e.g. cotton, animal furs and silk, had been

used for thousands of years. In the first decades of the 20th century, cotton accounted for more than

70% of all textile raw materials in the world. It was not until the 1930s that man-made cellulose

fibres became one of the principle fibres. After World War II, the production of man-made

cellulosics kept increasing, until in the 1960s synthetic fibres “swept” the textile market (Fig. 2). In

the meantime, water and air pollution caused by toxic compounds darkened the image of the man-

made cellulosics.

Fig. 2. World fiber production 1920 – 2005

An approximation of the relative importance of individual fibres in Europe’s Textile/Clothing sector

is given in the following graph (Fig. 3). In terms of industrial consumption, man-made fibres

accounted for about 72% (in terms of volume), whilst cotton is the most important natural fiber.



Fig.3. Relative importance of textile fibres (source EURATEX)

BISCOL project aims to develop a new dyeing process which will lead to a concrete evoution of the

traditional colour industries towards high tech SMEs, which will become more competitive, more

innovative and develop sustainable process.

This modernisation will produce beneficial effects not only on environment but also on economic

profits of SMEs that will adopt the new process. This is very important to response to economic

crisis that affect european (and world) market. Results on textile indicators published on annual

2009 report of EURATEX show a negative trend for textile industry.



For most companies the year 2009 was characterised by a heightened focus on the immediate

business essentials to successfully navigate the challenges presented by the economic and financial

crisis. However also during these trying times the more strategic research, development and

innovation activities cannot and in most cases were not abandoned, as they are laying the

foundation for the sustainable competitiveness of the enterprise once the economy has returned to a

more normal situation. Indeed, if the crisis had one silver lining it was perhaps the realisation of

even more companies that business-as-usual is not an option going forward and that more radical

changes in products, processes, markets or business models may be required to achieve a better

market position, unlock additional growth drivers and ensure more sustainable profitability. Many

of these radical changes may indeed be based on increased research, development and innovation

efforts, either in-house or through collaborative efforts with value chain partners or other external

knowledge and service providers.

BISCOL aims to contribute to innovation of textile industry proposing a new dyeing process. The

first area selected for the introduction of the new process into market is Prato (Italy), one of the

most important textile manufacter area of Europe, specialised in the production of fabrics for



clothes, both for man and woman, in treating almost every kind of fiber, carded and combed wool,

cotton, linen, silk and synthetic fibers.

Textile operators 20,200 (of which 16,000 employees, the other entrepreneurs and self-employed workers)

Total operators (textile and clothing) 30,200 Source: Area studi Unione Industriale Pratese (2009) Textile companies 3,417 Knitwear and clothing companies 4,165 Total 7,582 (of which 44.5% industries and 55.5% self-

employments) Source: CCIAA of Prato (2009) Textile turnover 3,250 millions € Knitwear and clothing turnover 1,318 millions € Total 4,568 millions € Source: Area Studi UIP (2008) Textile export 1,646 millions € Knitwear and clothing turnover 592 millions € Total 2,238 millions € Source: Area Studi UIP (ISTAT 2008)

-20.00% -15.00% -10.00% -5.00% 0.00% 5.00% 10.00%

kn itted companies

confections

finishing

weaving

textile processing center

flock dye

carded spinning

textile production

specia l textiles

yarn production

home furniture

accessories

Fig. 4. Yearly growth rate of turnover



0.00% 1.00% 2.00% 3.00% 4.00% 5.00% 6.00% 7.00% 8.00% 9.00% 10.00%

yarn production

flock dye

finish ing

textile production

special textiles

home furniture

carded spinn ing

accessories

kn itted companies

textile processing center

confections

weaving

Fig. 5. Operating profitability

3. Conclusion

Selection of textile fibers is the starting point of BISCOL project and it could be deemed the basis,

together with dyes, for the success of the process. The second aspect to consider is the type of bio-

dye available in consortium. Actually two acid dyes have been synthetised. This class of dyes is

used to dye wool and some synthetic fibers.

As wool is one of the most used fiber in Prato district, and as its environmental impact is lower than

other fiber, we select wool as first fiber to be used in BISCOL project.

Although we have reported that modern man-made cellulose fibres have a clear potential in

reducing the environmental impacts over cotton and petrochemical synthetic fibres, we select

cotton as second fiber because it is the most important and used natural fiber, and because we want

to evaluate the toxicity of dyed cotton with the new process and compared the data with results

reported in litterature.

Finally we select also a man-made fiber, because it is reported that it has a loerw environmental

impact than cotton due to the lack of cultivation step. Besides they can be dyed with the same dyes

of wool and cotton.



Reference List - EURATEX, Annual report – Activities of the year 2009 - Moore, S.B., Ausley, L.W. (2004) J. Cleaner Production 12, 585-601 - Dave, G., Aspegren, P. (2010) Ecotoxicology and Environmental Safety 73, 1629-1632 - Shen, L., Worrell, E., Patel, M.K. (2010) Resources, Conservation and Recycling 55, 260-274 - Søndrgård, B., Hansen, O.E., Holm, J. (2004) J. Cleaner Production 12, 337-352 - McAdam, R., McClelland, J. (2002) Technovation 22, 113-121 - Allwood, J.M., Laursen, S.R., Russell, S.N., Malvido de Rodríguez, C., Bocken, N.M.P. (2008)

J. Cleaner Production 16, 1234-1246 - Nieminen, E., Linke, M., Tobler, M., Beke, B.V. (2007) J. Cleaner Production 15, 1259-1270 - Ren, X. (2000) J. Cleaner Production 8, 473-481



Appendix

A1. From trees to cellulosic fibers

Wood is the raw material used for producing manmade cellulose fibres. Viscose (Austria), Modal

and a part of Tencel are produced from pulp, which is made from European beech plantation. Half

of the beech wood is from Austria and most of the other half is from other European countries. The

wood is transported by rail or truck to the integrated pulp and fibre plant located in factory. Viscose

(Asia) and Tencel are produced from imported market pulp, which originates from eucalyptus

plantations in the southern hemisphere. The market pulp is transported by ship to the fibre

production sites in Asia and Europe. The beech and eucalyptus plantation used for the pulp

production have existed for more than 20 years. Based on the definition chosen by the IPCC and

PAS 2050, the GHG emissions from land use change are considered negligible. The European

beech is neither fertilized nor irrigated, and it is machine-harvested. The eucalyptus plantation is not

irrigated. Small amounts of nitrogen and phosphate fertilizers are applied. The harvested wood is

transported from the forest to the pulp mill by rail and road.

The pulp used to produce man-made cellulose fibres is so-called dissolving grade pulp. The

difference between dissolving grade pulp and paper grade pulp can be described as follows: in

paper grade pulp, lignin and resins are removed from wood and the pulp contains both cellulose and

hemicellulose; in contrast, dissolving pulp process removes not only lignin and resins, but also large

amounts of hemicellulose, resulting in a very high content (90–94%) of alpha cellulose. For

dissolving pulp production, the acid sulphite or the Kraft process is used.

Man-made cellulose fibres are produced by the regeneration of alpha cellulose. Two types of

technologies for cellulose regeneration, i.e. the viscose process and the lyocell process, are applied

to produce three types of man-made cellulose fibres, namely Viscose, Modal and Tencel. The two

technologies are illustrated in Fig. 6.



Fig. 6. The viscose process and the lyocell process

In the viscose process, pulp is first alkalized in caustic soda, then depolymerised and reacted with

carbon disulphide (CS2) to form cellulose xanthate, which is dissolved in caustic soda. After

filtration, degassing and ageing, the viscose solution is ready to be spun from a precipitation bath

containing sulphuric acid, sodium sulphate and zinc sulphate. Here, cellulose is regenerated in

filament form. Classic spinnable xanthate solution contains 7–10% cellulose, 5–7% sodium

hydroxide (caustic soda, NaOH), 25–35% CS2. The solution is spun into regular Viscose fibres in

an acid salt bath (80 g/l H2SO4, 150–300 g/l sodium sulphate (NaSO4), 10–20 g/l ZnSO4) at 45–

55°C. In Modal’s production, the xanthate solution contains 6–8% cellulose, 6.5–8.5% NaOH and

30–40% CS2; small amounts of modifier may also be added. Modal fibres are spun into filament in

a slightly acidic bath of low temperature and with a strong coagulating effect. The viscose process

requires a large amount of caustic soda (0.5–0.8 kg NaOH per kg fibre) and leads to sodium

sulphate (Na2SO4) as by-product. Nowadays up to 70% of the CS2 is directly recycled and reused.

Most of the remaining 30% is converted into sulphuric acid which is also recycled to the process.

The viscose process has been applied on industrial scale since the 1930s and nowadays the process

is used for the production of both Viscose and Modal fibres. Modal fibres are manufactured by a

modified viscose process with a higher degree of polymerization and modified precipitating baths.

This leads to fibres with improved properties such as higher wet strength and better washability.



The lyocell process represents a complete technology innovation. NMMO (N-methylmorpholine-N-

oxide) is used to dissolve pulp and regenerate cellulose. The process has a nearly closed solvent

cycle (see Fig. 6). This not only avoids the use of the highly toxic solvent CS2, but also reduces the

number of the process steps and total chemical use.

Fig. 7 shows the two different production systems: integrated (for Viscose (Austria) and Modal) and

separate production (for Viscose (Asia) and partially Tencel). In the case of integrated production,

process energy use has been highly optimized and only a small amount of fossil fuels is required.

Bark, thick liquor and soda extraction liquor from the pulping process are used fuel the pulp and

fibre production. The remaining heat requirements (about 40% of the total heat requirements) are

covered by externally purchased bark and a municipal solid waste incineration plant which is

located next to the integrated plant. The integrated production is self-sufficient in terms of

electricity use.

Fig. 7. System description of man-made cellulose fiber production: (a) integrate pulp-fiber plant and (b) separate pulp and fiber production.



The pulp produced from the integrated plant yields several wood-derived byproducts,i.e. xylose,

acetic acid, furfural and thick liquor4; it is not traded in the market. More commonly, pulp and fibre

are separately produced. Viscose (Asia) and part of the Tencel fibres are produced from market

pulp. For average market pulp, the pulping process yields lignosulphonate as the by-product (see

Fig. 7b). A substantial amount of the process heat and power is provided by combustion of thick

liquor. Additional process energy is provided by combustion of fossil fuels. Small amounts of

electricity are purchased from public grid.

In a fibre plant of the separate production system, fossil fuels are the main energy source. For

example, in the fibre plant of Viscose (Asia), over 99% of the process heat and power originate

from fossil fuels, which are mainly coal and oil; nearly half of the electricity is supplied from public

grid.

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