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The environmental impact of Wet Processing & how to improve sustainability: Written for MADE-BY
Anne Moor International Fashion Management 2010
Wet Processing Thesis 9 November 2010 Final Thesis
Anne Moor, International Fasion Management Pagina 1 van 100
The environmental impact of Wet Processing & how to improve sustainability: Written for MADE-BY Anne Moor
Title Page
Name of author: Student No.: Full title: Anne Moor 233203 The environmental impact of Wet Processing & how to improve sustainability: Written for MADE-BY International Fashion Management Amsterdam Fashion Institute Hogeschool van Amsterdam Final Thesis Jan Piscaer Amsterdam, The Netherlands 09 November 2010
Name of degree course:
Type of report: Coach: Place: Date:
Executive Summary
MADE-BY is a non profit organisation that supports brands to improve sustainability in their supply chains. Brands can become a member of MADE-BY and receive supply chain support. MADE-BY has developed a social benchmark and a fibre benchmark. Both tools provide brands with a perspective for action to improve sustainabiltiy and can be used during sourcing activities.
The following research paper addresses how MADE-BY could inform their member
brands about the environmental impact of wet processing. Furthermore it has been researched how they can give their member brands a perspective for action to improve sustainability on wet processing practises. Subsequently, the main environmental impacts of wet processing ar water, energy and chemicals. The individual factors that pose a threat on the environment are water consumption, energy consumption, chemicals usage, which results into water scarcity, CO2 emissions, pollution to air, polluted waste water, acute toxicity to fish and plants. The main aspects of wet processing are pre-treatment, dyeing, and printing. Each of those processes consists of different treatments. As there are many variable factors all influencing a process and its effect is makes it very difficult.to measure impacts. Those variable factors are machines, substrates, blends, different dyestuff, auxiliary chemicals, levelling, and dyebath ingredients. Together with the technical aspect of wet processing comes the complexity aspect of wet processing. There are 180 ways to dye cotton; this depends on which dyeing methods, machine, dyeclass, dye stage the textile is dyed. Furthermore there is not a single standard procedure to dye textile, as this depends on substrate, whether is is a blend or not. Colour shade and colourfastness requirements affect the dyebath recipes which affect the environmental impact. Other influencing factors are fixation rates and azo compounds.The chapter provides a holistic overview and zooms in on 4 cases to demonstrate complexity and why it is difficult to impossible to measure environmental impact per dyeing process. In order to provide MADE-BY and its member brands a perspective for action, several sustainable alternatives are outlined. These alternatives are offered on three levels; input, process-integrated, output. The alternatives are, enzymes treatment, plasma treatment, natural dyes, solution dyed, CO2 dyeing, pigment+transfer printing, screen print optimisation, digital ink-jet print, Laser technique, substitution of chemicals, special dyeselection, process optimisation, dyebath replenishment, recovery auxiliary chemicals, and waste water treatment. However, as wet processing takes place in the bottom end of the chain and is hardly influenced by brands it causes extra difficulties. Moreover MADE-BY member brands know very little about the wet processes in their supply chain. Neither do they communicate with their dye houses nor do their agents.
Wet Processing Thesis 9 November 2010 Final Thesis Anne Moor, International Fasion Management Pagina 4 van 100
In the last chapter a step by step process or ladder has been developed to provide a more holistic approach in tackling sustainability in textile wet processing. The ladder describes 7 steps, which are transparency, measurements, impact calculation, process optimisation, output management, input management and review. In conclusion, wet processing is a complex area to approach with sustainability improvements. However with the presented sustainable altnernatives and the step by step process MADE-BY and its brands can start making a step in the right direction. MADE-BY member brands suppy chains should be analysed and further specified action plans should be developed. It is recommended that MADE-BY further developes and investigates the step by step process and starts collaborations with companies such as genencor and huntsman.
Table of Contents
Table of Contents ...................................................................................................................................... 6 1 Chapter 1......................................................................................................................................... 10 1.1 1.1.1 1.2 1.3 1.4 1.5 2 2.1 2.2 2.2.1 2.2.2 2.3 3 3.1 3.2 3.3 3.3.1 3.4 3.4.1 3.4.2 3.4.3 4 4.1 4.2 4.3 4.4 4.5 5 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 5.10 5.11 5.12 5.13 Introduction MADE-BY ........................................................................................................10 MADE-BY and benchmarks/scorecards ..........................................................................10 Problem definition...............................................................................................................12 Aim ......................................................................................................................................13 Research + Sub Questions ...................................................................................................13 Methodology .......................................................................................................................14 Water Consumption ............................................................................................................16 Use of Chemicals .................................................................................................................18 Pollution to air ................................................................................................................19 Water Pollution...............................................................................................................19 Energy consumption............................................................................................................22 Processing Methods ............................................................................................................25 Pre-treatment......................................................................................................................26 Dyeing..................................................................................................................................28 Examples.........................................................................................................................32 Printing ................................................................................................................................35 Methods of printing........................................................................................................37 Inks/Colours....................................................................................................................37 Ingredients print pastes..................................................................................................39 No Standard procedure .......................................................................................................45 Colour shade / Colourfastness (dye recipe) ........................................................................46 Fixation Rate........................................................................................................................47 Azo Compounds...................................................................................................................48 Conclusion ...........................................................................................................................49 Enzymes...............................................................................................................................50 Plasma application ..............................................................................................................51 Natural Dyes ........................................................................................................................52 Solution dyed.......................................................................................................................53 CO2 Dyeing ..........................................................................................................................53 Pigment + Transfer printing.................................................................................................54 Screen printing optimisation ...............................................................................................55 Digital Ink-jet printing..........................................................................................................55 Laser technique ...................................................................................................................55 Substitution of Chemicals....................................................................................................56 Special dye selection with supplier .....................................................................................57 Process optimisation ...........................................................................................................57 Dye bath replenishment......................................................................................................58
Chapter 2......................................................................................................................................... 15
Chapter 3......................................................................................................................................... 24
Chapter 4......................................................................................................................................... 42
Chapter 5......................................................................................................................................... 50
5.14 5.15 5.16 6 6.1 6.2 6.3 6.3.1 6.3.2 6.3.3 6.3.4 6.3.5 6.3.6 6.3.7 6.4 7 7.1 7.2 8 9
Recovery of auxiliary chemicals...........................................................................................59 Waste water treatment.......................................................................................................59 Chapter conclusion..............................................................................................................60 Power division Supply Chain................................................................................................62 Influence of Brands .............................................................................................................63 Step by Step process ...........................................................................................................66 Step 1 Transparency: ......................................................................................................68 Step 2 Measurements:....................................................................................................68 Step 3 Impact calculation: ..............................................................................................69 Step 4 Process Optimisation:..........................................................................................69 Step 5 Output: ................................................................................................................70 Step 6: Input: ..................................................................................................................70 Step 7 Review: ................................................................................................................70 Chapter Conclusion .............................................................................................................71 Conclusion ...........................................................................................................................72 Recommendations...............................................................................................................73
Chapter 6......................................................................................................................................... 62
Chapter7 ......................................................................................................................................... 72
Bibliography .................................................................................................................................... 74 APPENDICES .................................................................................................................................... 78 9.1 9.2 9.3 9.4 APPENDIX PRE-TREATMENT ................................................................................................78 APPENDIX DYEING ...............................................................................................................82 APPENDIX ALTERNATIVES SCHEMES ...................................................................................93 APPENDIX QUESTIONNAIRE RESULTS..................................................................................96
Table of Figures
Fig. 1 Scorecard Jackpot. Source: MADE-BY.com.............................................................................. 11 Fig. 2 Methodology, authors own .................................................................................................... 14 Fig. 3 Environmental Impact and Emissions, Authors own. .............................................................. 15 Fig. 4 WEC Use Dyeing Finishing. Source: Cotton incorporated 2010................................................ 16 Fig. 5 Water scarcity world. Source: Molden 2007........................................................................... 17 Fig. 6: Coloured streams. Source: flicr.com...................................................................................... 19 Fig. 7: Water effluent maximum levels. Source: (Multilateral Investment Guarantee Agency, 2007) ................................................................................................................................................. 21 Fig. 8: pH scale. Source: http://climatechange.wikispaces.com ....................................................... 22 Fig. 9: Textile Chain. Source: European Commission, 2003 .............................................................. 24 Fig. 10: Processing Methods. Source: Schonberger and Schafer, 2003.............................................. 25 Fig. 11: Liquor ratios machines. Source: Shukla, 2007 ...................................................................... 25 Fig. 12: Pre-treatment overview, Authors own. ............................................................................... 27 Fig. 13: Dyeing phases. Source: Cegarra, J., Puente, P., Valldeperas, J. 1992 .................................... 28 Fig. 14: Dyeclass overview, Authors own. ........................................................................................ 30 Fig. 15: Reactive dyeing ingredients. Source: European Commission 2003 ....................................... 33 Fig. 16: Acid Dyeing ingredients. Source: European Commission 2003............................................. 34 Fig. 17: Disperse dyeing ingredients. Source: European Commission 2003....................................... 35 Fig. 18: Printing Techniques. Sources: European Commission 2003 and Kilgus et al. 2008) .............. 36 Fig. 19: Print paste ingredients. Source: European Commission 2003............................................... 39 Fig. 20: Pollutants waste water printing. Source: European Commission 2003................................. 40 Fig. 21: Wet processing web, Authors own. ..................................................................................... 42 Fig. 22: Systematic Complexity demonstration ................................................................................ 43 Fig. 23: Waste water characteristics (different combinations of dyes, substrate, equipments) Source: Shukla 2007.............................................................................................................................. 45 Fig. 24: Fixation rate. Source: Van der Zee 2002.............................................................................. 48 Fig. 25: Molecule structure of Acid Red dye. Source: Smith 1986 ..................................................... 49 Fig. 26: Process comparison enzymes. Source: Hermse, 2010 .......................................................... 50 Fig. 27: Enzyme treatments. Source: European Commission 2003.................................................... 51 Fig. 28: Savings on solution dyeing. Source:hoyu.com.tw ................................................................ 53 Fig. 29: Phases of CO2 dyeing. Source: Dyecoo textile systems ........................................................ 54 Fig. 30: Printing processes comparision. Source: Schonberger and Schafer, 2003 ............................ 54 Fig. 31: Example Laser technique by Girbaud. Source. Girbaud.com ................................................ 55 Fig. 32: Different textile effluent treatments. Source: Das 2004....................................................... 59 Fig. 33: Supply Chain general overview, Authors own...................................................................... 62 Fig. 34: Different concerns and vision in supply chain. Source: Hermse, 2010 .................................. 63 Fig. 35: Overview Sustainable Alternative on different levels, Authors own. ................................... 65 Fig. 36: Ladder to tackle sustainable wet processing step by step, Authors own.............................. 67
Introduction
At the end of my six month internship at MADE-BY UK, London I moved back to Amsterdam and also started an additional non-obligatory internship at the MADE-BY office in The Netherlands. I was very keen on writing my thesis at MADE-BY, sustainability really interests me and is something I would like to continue working with in the future. MADE-BY was really keen on developing a document which could inform and help their member brands on textile wet processing as it is a very big polluting factor. MADE-BY has little information on wet processing as it is a very new subject for them. In addition, the subject is very specific, technical and is very textile focused. These aspects are what made this subject interesting for me but at the same time also very challenging. As wet processing had been on the agenda of MADE-BY I was more than happy to write my thesis about this. The main problem throughout this research was how brands out of their position can tackle wet processing issues in order to improve sustainability.
Chapter 1
What does MADE-BY do and what are their expectations? 1.1 Introduction MADE-BY MADE-BY is a non profit organisation that supports fashion brands in improving the transparency of their supply chains. By addressing social circumstances and environmental problems MADE-BY tries to establish supply chains which are kind for people and planet. Together with the member brands ado they work towards a better and brighter future. In order to guide and support the brands, MADE-BY has developed 2 benchmarks
1.1.1 MADE-BY and benchmarks/scorecards The social benchmark addresses the social circumstances in the supply chain (only focused on the garment manufacturing plants). By ranking 6 existing social standards for textile production a benchmark has been created which can improve guidance to brands. The benchmark can be used as a tool to expand their network of sustainable suppliers and to encourage their own supplier to obtain a certain social compliance. MADE-BY will always stimulate the adoption of codes with the highest social effectiveness and assists brands and suppliers in the implementation process. (MADE-BY, 2009) The second benchmark is the environmental benchmark for fibres. This benchmark has been created by Brown&Willmans in close collaboration with MADE-BY. 20 fibres have been ranked based on 6 parameters resulting into class A, B, C, D and E. The parameters take into account Green house gases, yield, and use of chemicals. This benchmark proves to be a valuable and actionable tool for brands in sourcing fabrics: I take the benchmark to fabric fairs and suppliers and tell them I only want fabrics from Class A and B (Buying Manager from Pure) The production data of the MADE-BY member brands will be translated into scorecards, which are based on the benchmark classes A, B, C, D, E, etc. The figure below shows an example of such a scorecard for the brand Jackpot:
Fig. 1 Scorecard Jackpot. Source: MADE-BY.com
As MADE-BY aim is to work on environmental problems, not only will do they focus on sustainable materials, they also want to address the wet processing of textiles. Wet processing of textiles involves the dyeing, printing and finishing of fibres, yarn, fabrics or garments. According to Kazakeviit (2004) is Textile wet processing (finishing) is a complex process. The same result can be achieved by applying some different technologies and with the use of some different kinds of chemical materials and machines. MADE-BY would like to inform their member brands about the impact of wet processing and help them make more sustainable decisions in their designing and sourcing practises.
1.2 Problem definition MADE-BY support their member brands in sourcing sustainable materials and becoming social compliant. More and more brands become interested in sustainability and are aware that wet processing is very damaging for the environment. To sketch the gravity of the situation: 55 million tonnes of textiles are dyed and this using worldwide 0,8 million tonnes of dyestuff. From this dyestuff approximately 5 to 10% of non-reactive dyes are lost in the waste water; this is even 50% for reactive dyes. The pollution lies around 450 l per kg texile, which gives a total amount of 25 billion m3 of waste water discharged annually. (Beke, 2009) Not only the environment suffers greatly, also the people working with the powerful chemicals develop diseases by handling the chemicals and breathing in the vapours. MADE-BY would like to support their brands in improving the wet processing practises and set out a policy document brands can follow. Tools that have been developed before are the fibre benchmark and social standards benchmark, these tools have proven to be very useful and offer brands a great perspective for action. However, wet processing is difficult to tackle for brands as garments/fabrics are dyed far from home and deep into their supply chain. Dyeing can be done at several stages, with several dyes, in different circumstances etc.. MADE-BY encourages transparency in the supply chain, but practise has proven it is difficult to get a complete overview of the chain, because there are many parties involved. It requires much additional time and effort and moreover it is an unknown world for most of the brands and it is not only up to brands to make a change as there are more parties involved. (Manufacturers, dye houses, mills) Taking all these issues into account this thesis will give more insight into the wet processing practises and demonstrate the complexity of the situation and look further into sustainable alternatives.
1.3 Aim The aim of this report is to provide MADE-BY and its member brands with stepping stone on how to approach sustainability in the wet processes in the production cycle. Brands should be able to use this document for information purpose and use as a guide to undertake wet processing in a sustainable way. Ultimately this document will offer MADE-BY and brands a perspective for action. In order to do so the research will document the technical/chemical aspects of wet processing, its impact on the environment, and the sustainable alternatives. Furthermore this report will focus on the brand perspective on this matter. By means of measuring water-, energy-, chemicals consumption and emissions per fibre/dyeclass, clarity and action perspectives will be provided. The research will take into account several aspects of wet processing; pre-treatment, dyeing, and printing will be finished by November 2010. Finishing processes are out of scope of this research. There will also be less focus on washing and rinsing processes.
1.4 Research + Sub Questions The main focus of the report is to answer the following question: How can MADE-BY effectively inform their member brands about the environmental impact of wet-processing and offer them a perspective for action to improve sustainability? In this context it is essential to investigate and distinct the following: The content (facts), behaviour (teaching the content) and strategy (point of view MADE-BY). What does MADE-BY do and what are their expectations? (Strategy) What are the environmental impacts of wet processing? (Content) What are the aspects of wet processing? (Content) What is the complexity of wet processing? (Behaviour) What are the sustainable alternatives? (Content, Behaviour) How can brands influence wet processing? (Behaviour, Strategy)
1.5 Methodology For this report primary and secondary research has been carried out. Desk research has been carried out and sources utilised are books, e-books, journals, e-journals, online publications, theses, internet articles, research reports. Questionnaires, visits to launches and textile experts have been used as field research.
Who MADE-BY member brands Dyecoo Anton Luiken Huntsman Genencor CREM Bijenkorf How Questionnaire Launch visit Meeting/Discussion Group discussion Group discussion Presentation Supply Chain Meeting What To test their knowledge about wet processing CO2 dyeing method Modint tool & tackling wet processing by brands Sustainable dye solutions Enzyme Treatments Waterfootprint To find out their knowledge and interest about wet processing Nomad Supply Chain Meeting To find out their knowledge and interests about wet processing Fig. 2 Methodology, authors own
Chapter 2
What are the environmental impacts of wet processing? Processes such as pre-treatment and dyeing require large amounts of water and highly toxic chemicals. The textile industry has a major impact not only on a nations economy but also on the economic and environmental quality of life in many communities. (Shukla, 2007) Moreover, the environment suffers greatly from textile processing and its waste. Textile processing generates various types of waste streams, including water-based effluent as well as air emissions, solid wastes and hazardous wastes. (Shukla, 2007) This chapter will look at the issues that pose threats towards the environment. The overview below gives a clear idea of the consumption and emissions that cause ecological concerns.
Water Consumption
Energy Consumption
Air emissions : VOC
CO2 emission
Chemical Consumption
Waste water emissions: BOD, COD, AOX
Solid emissions: sludge
Fig. 3 Environmental Impact and Emissions, Authors own.
The major impact on the environment from a wet processing perspective is the distribution of water (water consumption and the water pollution. According to Shukla (2007) in quantity, waste water generation is a major source of pollution from a textile processing factory as the treatments carried out on textile materials are essentially carried out through aqueous medium. As figure 4 outlines, the water usage for dyeing and finishing accounts for 85% of the total textile processing cycle, followed by energy (80%) and chemicals (65%) The impacts waste water has on the environment will be discussed under the chemical heading 2.2.
Fig. 4 WEC Use Dyeing Finishing. Source: Cotton incorporated 2010
2.1 Water Consumption Contributing to water use in textile wet processing is the general purpose of washing. Impurities need to be washed of the fabric before dyeing in order to obtain a good dyeing uniformity and non-fixed dyestuffs + auxiliary chemicals need to be washed off afterwards to prevent human beings from being exposed to toxic and hazardous chemicals. Additionally dyeing machines use tonnes of water. According to de Lange (2010) for one cotton t shirt (200gr) needs 2700 litre of water to be produced. Water used to be a plentiful and cheap resource for the textile industry, but this situation is changing.
The picture below demonstrates the economic and physical water scarcity in the world.
Fig. 5 Water scarcity world. Source: Molden 2007
Economic scarcity is caused by a lack of investment in water or a lack of human capacity to satisfy the demand for water. Much of the scarcity is due to how institutions function, favouring one group over another and not hearing the voices of various groups, especially women. (David Molden, 2007) For example in Africa, most of the continent suffers from economic water scarcity, this can be due to little infrastructure development, which means that people have trouble to get enough drinking water or for agriculture. Also because of the poverty, if infrastructure exists the distribution of water may be unequal. Physical scarcity occurs when there is not enough water to meet all demands, including environmental flows. Arid regions are most often associated with physical water scarcity, but water scarcity also appears where water is apparently abundant, when water resources are overcommitted to various users due to overdevelopment of hydraulic infrastructure, most often for irrigation. In such cases there simply is not enough water to meet both human demands and environmental flow needs. (David Molden, 2007) India is characterised by physical water scarcity or approaching physical water scarcity. In Tirupur (India) for example, nearly 3000 trucks with a capacity of 10.000 litres/ trip undertake 8-10 trips daily to feed the textile industry with water, leading to decreasing groundwater levels in neighbouring area. (Schouten, 2009) .
This has several socio economic issues. De Lange (2010) states that in 2025 1,8 million people will live in areas with several water scarcity and 46% of the household will not have a connection to the drink water net. Now and in the future, every year 3,3 million people die of water related diseases. Women in developing countries walk 6 kms on average for fresh drink water and this distance will only increase. The battle for water will be a future source for conflicts Furthermore, Biodiversity issues will occur because of drought.
2.2 Use of Chemicals There are more than 2000 chemicals used in the wet processing practises. Shukla (2007) states that in earlier days, the dyestuff selection, application and use was not given a major consideration with respect to their environmental impact. Until recently textile dyes had little access to the information concerning the environmental impact of the dyes they used, as of 1984, even the chemical composition of at least half of the dyes used in the industry was estimated to be unknown. Chemicals can cause severe damage to the environment as well as too human health. They can be carcinogenic, mutagenic, allergenic, and toxic; therefore there are more and more legislations to avoid them from ending up in the products consumers wear. For example, Formaldehyde, which is used in the synthesis of auxiliaries, such as dyefixing agent in direct and reactive dyes and printing or dispersing agents and vat dyeing, is a respiratory sensitizer and skin irritator and should be either totally eliminated or substantially reduced by substitution with non-formaldehyde-based products. (Shukla, 2007) However, as Easton (2009) says; It is workers in the dyeing factories, rather than Western consumers, who are most at risk. It should be just as important to reduce the exposure of dye house workers in China, India and other producer countries to carcinogenic dyes and chemicals as it is to reduce the exposure of cotton farmers in Africa to toxic pesticides. For example, the production of carcinogenic Benzedrine dyes were abandoned as it increased the levels of bladder cancer among the workers. Tragically, many of those dyes are still available today in major textile manufacturing plants. If there is no regard for health and safety in a workplace, working with those chemicals can have severe consequences for those workers. (Easton, 2009) As previously discussed chemicals used for dyeing can be very damaging when left in the waste water and dumped in rivers. Chemicals used for wet processing also contribute to air pollution and are endangering human health.
2.2.1 Pollution to air To identify these fumes the term VOCs Volatile Organic Compounds is often used. VOCs are very varied, countless and everywhere. They are not acutely toxic but have chronic effects, because concentrations are low, symptoms develop slowly. (European Commission, 2003) Especially emulsion thickeners for pigment printing generate large amounts of VOCs. Also drying processes and solvents use contribute to voc emissions. VOC concentrations vary from 10 milligrams of carbon per cubic meter (mg/m3) for the thermosol process to 350 mg carbon/m3 for drying and condensation process. (Multilateral Investment Guarantee Agency, 2007) 2.2.2 Water Pollution Waste water forms the biggest source of pollution from the textile industry. The components generally present in a textile dye bath are the dyestuff (colorant), solubilising chemicals, buffer system/pH controller, electrolyte (salt), specialty dyeing assistants (such as retarder/accelerant, levelling agent, lubricant, defoamer, surfactant/dispersant, sequesterant, etc) and water. Dyes itself contain heavy metals and hazardous pollutants. Moreover, not all dyestuff is absorbed by the fibre during the dyeing process and thus stays behind in the waste water. This results in coloured water, which is a threat for the biodiversity. Shukla (2007) states that highly colour effluent interferes with the transmission of light in receiving waters; high doses of colour in the waste water can interrupt photosynthesis and affect aquatic life. Some commercially important dyes have acute fish toxicity: 48 h toxicity to Daphnia maga and a 72h algal growth inhibition. (Shukla, 2007)
Fig. 6: Coloured streams. Source: flicr.com
In addition to dyestuff, the auxiliary chemicals used in a dye bath (they assist effectively the adsorption and fixation of the dyes into the fibre) are not consumed in the dyeing process. They will be washed off the fabric in the rinsing process and stay in the waste water. The spent dye bath contains varieties of such auxiliary chemicals including salt with each one having a different environmental impact. For example the heavy metals in dyes are only present as trace impurities. Due to the vast amounts of fabrics being dyed, this easily accumulates and forms a big threat to the environment. They are dangerous due their absolute resistance to
biodegrade and tendency to accumulate into higher concentrations, thereby increasing their toxicity to living beings. (Shukla, 2007) Metals such as copper are known to be toxic to aquatic organisms (Shukla, 2007) In additions to metal, salt also cause substantial environmental damage. Salt is used in dye processes such as reactive dyeing. In the worst case scenarios as much salt as 1 kg salt /1kg of fibre is required. According to Patterson (2009), salt formed dye baths is not rendered harmless by effluent treatment plants so it can pass straight through into rivers. If you image that 50% of the cotton production is dyed with reactive dyes, it is very unfavourable from an environmental point of view. It will cause salination and water can no longer be used for drinking or agriculture. Salination levels, also reffered to as Total Disolved Solid can go up to 12500 mg/l for reactive dyeing, whereas drinking water usually contains 100 300 mg/l and highly saline waters (oceans) 10.000 35.000 mg/l. (Shukla 2007, TDS 2008, Bergman 2001) Wood (2009) reports that textile printing and dyeing did most of its damage on Chinese soil. More accurately, on Chinese watercourses. As Chinas textile industry blossomed in the wake of the countrys entry into the WTO, doubling output in the decade after 1999, so has its production of hard-to-treat wastewater. Only about 10 percent of dye wastes are recycled, and about a third of the rest flows directly to the environment. In provinces like Xinjiang, this waste is a major contributor to industrial and municipal pollution so severe that nearly 1 in 4 of Chinas 1.3 billion people drink contaminated water every day.
The characteristics of waste water and its maximum value to be harmless to the environment are identified in figure 6 below: The most important parameters to measure waste water that are mentioned most of the time are the BOD, COD, pH, heavy metals and AOX. Essential is also the colour of the waste water as this is not aesthetical desired and moreover are dyes hardly biodegradable. The terms BOD and COD stand for biochemical oxygen demand and chemical oxygen demand. BOD measures the amount of oxygen that is necessary for micro organisms to decompose organic matter (plants, etc). If BOD levels are high, much oxygen is needed to biodegrade waste, which results in very low oxygen levels for fish and other aquatic organism to survive. COD does not differentiate between decomposition of organic matter and oxidation of inorganic chemicals. It is a measure of the total quantity of oxygen required to decompose /oxidise waste. (Northeast Georgia Regional Development Centre) BOD and COD are related to each other and often referred to as BOC/COD ratio. In most cases BOD/COD ratio of the composite textile wastewater is around 0.25 that implies that the wastewater contains large amount of non biodegradable organic matter. (Al-Kdasi et al., 2004)
Fig. 7: Water effluent maximum levels. Source: (Multilateral Investment Guarantee Agency, 2007)
Additionally, the pH level of the waste water is plays a great part in textile wet processing. Some dyes are applied in an alkaline (base) bath and other under more acidic conditions. pH scale ranges from 0 14 as the picture demonstrates. The pH range of water is neutral, which is 7 on the scale. As dye baths can be highly alkaline/acid they have to be neutralised before being discharged. It is known is that exposure to water with extreme pH levels (an acid of pH 2 or below, or a base of pH 10 or above) can cause damage to living things, including humans. Fish and plants have a relatively small pH range, near neutral, at which they can live. Typically, organisms thrive in environments with the pH between 6 and 9. As the environment becomes more acidic or basic the amount of diversity decreases and fewer organisms are able to survive. Changing the environment's natural pH affects the rate of corrosion, solubility of metals, mobility of chemical pollutants and types of micro organisms that are able to exist. (http://www.egr.msu.edu/tosc/alpena/factsheets/fs_pH/fs_pH1.shtml )
Fig. 8: pH scale. Source: http://climatechange.wikispaces.com
AOX is a measured value for organically bound chlorine, bromine and iodine in a given substance. (Roy Choudhury, 2006) Auxiliary chemicals, such as bleaching agent and wool anti-felting agent contain chlorine compounds; these are capable of reacting with organic compounds to form AOX. Bound halogen is also found in discharges of dye-concentrate (pad, kitchen) and non-exhausted dye baths that may still contain unreacted dyestuff. Absorbable organically bound halogens are mostly persistent in the environment, and accumulate in the food web. As these compounds are reactive they can be highly dangerous for human health. (Asplund, Grimvall, and Pettersson 2003)
2.3 Energy consumption Most of the energy consumption is because of the heating of the dye bath. In order for the dye to most effectively grab the fibre, cellulose fabrics are dyed at temperatures lower temperatures, whereas synthetic fibres, such as polyester are even died at a higher temperature, often 120 to 130 degrees. The temperature of the dye depends on whether you stock dye or piece dye, whether you use a direct dye or reactive dye, whether you dye cotton or acetate, whether you batch dye or dye continuously. Other important energy consumers are thermosol processes, stentering machines and drying machines. It takes much energy to keep the machines running. Additionally, Energy consumption rise due to redyeing when the correct shade has not been obtained. Sometimes an item requires to be redyed 2 to 3 times.
Moreover, old machines, or badly maintained machines with bad isolation of the pipes or malfunctions also cause energy consumption to rise. This translates into huge quantities of fossil fuels - both to create energy directly needed to power the mills, produce heat and steam, and power air conditioners, as well as indirectly to create the many chemicals used in production. In addition, the textile industry has one of the lowest efficiencies in energy utilization because it is largely antiquated. (O Ecotextiles, 2009) Those activities have a large carbon footprint, thus produce large amounts of greenhouse gases. As greenhouse gases produced by human activities accumulate and their concentration increases in the atmosphere, it causes global warming. (Domain-B, 2009) To conclude, the textile wet processing industry has several impacts on the environment.The main factors are water, energy and chemicals. They contribute to the greenhouse effect, loss in biodiversity, rising of sea level, abnormal climate change, ozone layer depletion and endangering of human health. In order to give a more thorough insight into which processes cause which environmental effect, the next chapter will explain more about the process itself and identify its impacts.
Chapter 3
What are the aspects of wet processing? In order to point out where the environmental concerns lie in wet processing, this chapter describes methods of application (machines), pre treatments, dyeing and finishing processes. For each method or process the cause for environmental impact will be identified. The figure below provides a clear overview of the supplier chain and shows at which stage wet processing practises can be applied and which factors are involved.
Note: FINISHING PROCESSES can also be applied at Garment stage. Fig. 9: Textile Chain. Source: European Commission, 2003
3.1 Processing Methods Pre-treatment and dyeing of fabrics can be done in batch, semi-continuous and continuous processes. Which application method is to be used depends on the different local situation, the substrate to be treated, production quantities, and the effect to be obtained. For example, processing of wool or wool blends require relatively high liquor ratios. Moreover, European Commission (2003, P. 62) states, One third of the dyes used for cellulose are reactive dyes. They are mostly applied according to the pad-batch and continuous processes for woven fabric, while batch processes are the most common for knitted fabric, loose stock and yarn. Figure 9 depicts the different processing methods. Batch/discontinuous/ exhaust techniques
Semi-continuous techniques
Continuous techniques
Fig. 10: Processing Methods. Source: Schonberger and Schafer, 2003
As outlined in figure 10 liquor ratios of dyeing machines vary greatly, thus environmental impact varies greatly. The liquor ratio characterizes the ratio of the textile weight (kg) to the liquor volume (l). Especially in batch dyeing, many different machines can be utilised for pre-treatment of dyeing. Dyeing machine/process Water consumption (l kg Liquor-to-goods ratio -1) Beam 167 10:1 Beck/Winch 234 17:1 Jet 200 15:1 Jig 100 5:1 Paddle 292 40:1 Skein/ hank 250 17:1 Stock 197 12:1 Pad-batch 17 Package 184 10:1 Continuous 167 1:1
Fig. 11: Liquor ratios machines. Source: Shukla, 2007
3.2 Pre-treatment The main environmental issues associated with cotton pre-treatment arise from water emissions. The characteristics of the emissions vary according to a number of factors: the make-up, the sequence adopted, the fact that some treatments are often combined in a single step, etc. The most relevant issues are highlighted below for the various operations involved in pre-treatment. The pre-treatment of textile is often necessary to remove impurities from the fibre. E.g. from wool and cotton, sand etc can still be attached to the fibre. The fabrics are prepared for dyeing, printing or finishing. Any processing aids, such as oils waxes, sizes, that have been applied during spinning, weaving and knitting have to be removed. Additionally fibres/fabrics are often bleached before dyeing to obtain the correct colour shade. Good preparation is a requirement for good results in dyeing and finishing. The absorption of dyes and textile auxiliaries increases. Tensions in textiles are minimised; the dimensional stability is improved Wet ability of the material is improved Mercerisation gives a change in crystallinity of the cellulose; lustre is improved Bleaching increases the whiteness of the substrates (Schonberger, Schafer, 2003) Figure 11 outlines the most common pre-treatments which can be used for the different substrates. The boxes which are coloured grey demonstrate that this pretreatment can be applied to that substrate. Moreover the environmental impacts are described. General information per process is explained in appendix. In order to get a better understanding of the processes and why they cause this impact, it is strongly advised to study the appendix.
Synthetic fibres
Pre-treatment Cotton/Linen
Cellulosic manmade fibres
Impacts
Wool
Desizing of woven fabric
Silk The liquors used for desizing contribute to a high COD load of a finishing mill. According to European Commission (2003) this can be up to 70% of the load in mills finishing woven fabrics and concentrations range from 3000 to 80000 mg O2/l. More problems are posed by the presence of substances that are difficult to emulsify and poorly biodegradable such as silicone oils. The surfactants and complexing agents are none readily biodegradable and the COD load is very high due to organic impurities removed from the fibres. COD-concentrations from 2000 to 6000 mg O2/l are typical. (European Commission 2003) Bleaching with hydrogen peroxide requires the use of stabilisers in order to inhibit the radical attack of bleach on the cellulose. However, stabilisers may contain complexing/sequestering agents (EDTA and DTPA) that have poor bio-eliminability and can pass straight through waste water treatment systems. Optical brightening has an impact on the water toxicity and the fluorescent agents have a low degree of bio elimination. The main ecological impact in mercerising is the high concentrated (varies from 20% - 30%) residual alkali which needs to neutralised.
X X X X X X X X X X X X X X X X X X X X
Scouring / removal of serecin in silk
Bleaching
Optical brightening Mercerising/ Causticizing Weighting Carbonising Fulling/crabbing thermo fixing Anti felting
Disadvantages of this procedure are the long processing time and the high water and energy consumption. The high amount of tin in the waste water is an environmentally undesirable effect of this process. The acid and the organic load (the by-products removed from the fibre) in the effluent cause the main environmental impact Ecological charges are caused by felting agents and by-products/impurities removed from the wool during the process This process is responsible for a relatively high AOX-load in the effluent. (in oxidizing techniques the chlorine generating agents are responsible) (e.g. dichloroisocyanurat)
Fig. 12: Pre-treatment overview, Authors own.
3.3 Dyeing Once the fibres/fabrics have been pre-treated they are ready to be dyed. Dyeing is the colouring of a substrate. The general principle of dyeing is that a dyestuff is added to an aqueous medium. The dyestuff holds on to the fabric and the fabric is coloured. However there is so much more about it then just dyestuff grabbing onto a fibre. Dyeing of textile is actually very scientific as it deals with molecule and different kinds of bonding. It is much more complex than the bare eye can see. This chapter will give a bit more insight into process of dyeing. Dyes exist in two forms, dyestuffs and pigments. Dyestuffs are soluble in water or are made soluble by an additive, called auxiliary chemicals. Moreover auxiliary chemicals are often added to the dye bath to control the migration of the dyes, the levelling of a dye, prevent foaming, etc. Pigments are attached to a fibre by the means of a binding agent. For textile dyeing often soluble dyestuffs are used. Dyeing is carried out in an aqueous medium which can be neutral, alkaline or acidic. In recent times it has been admitted by al that dyeing cannot be considered as a phenomenon of a simple nature, but that chemical and physical forces act simultaneously in such a way as to make it impossible to circumscribe in an absolute manner the respective spheres of influence. (Cegarra, J., Puente, P., Valldeperas, J. 1992, P. 8) There are many different dye processes, but in general a dye molecule passes through several phases. Each dye class has its own process and will be discussed later in the chapter.
Fig. 13: Dyeing phases. Source: Cegarra, J., Puente, P., Valldeperas, J. 1992
1: A movement within the liquid phase towards the fibre, known under the term diffusion of the dye in the dye bath. 2: Its passage from the liquid to the solid phase, known as absorption 3: A movement from the surface of the fibre towards the interior of the same which we can catalogue as diffusion through the fibre e and finally the formation of bonds between fibre and dye, which represents fixation. It is at this point that the molecule can be considered to be bonded to the fibre and therefore the dyeing process is finished. (Cegarra, J., Puente, P., Valldeperas, J. 1992, P. 8)
Cotton has different properties than polyester, as has wool. Therefore, a certain dye classes might perform better on cotton fibres than polyester and vice versa. Not only the physical structure of the fibre is important and can influence the dyeing process, also the chemical composition/structure of dyes should be taken into account. The chemical structure of a dye is fundamental for its fastness properties. So, even within the same family the more insoluble compounds have greater fastness to wet treatment, those which are found in a more oxidised state are more resistant to oxidants, those which contain chlorine atoms have greater fastness to bleaching treatment with hypo chlorites, etc. Dyeing is in fact chemical bonding, which is different for every dye class. Reactive dyes make use of covalent bonding, whereas direct dyes are ionic bonds and acid dyes hydrogen bonds. . Despite the importance of the reaction of the dye with the fibre, this is a very scientific story and this thesis will not be going into depth about this. It will, however, discuss the different dye classes and outline which aspects contribute to the impact on the environment. The most used dye classes are: reactive, direct, acid, metal complex, basic, disperse, vat, naphthol. Important to take into account when dyeing is the colourfastness of a dye, whether it is to washing, light, heat, hypochlorite, the affinity of the dye for the fibre, the levelling of a dye, the colour shade, the fixation of a dye. In order to control all of these aspects in the dyeing process one has to find the equilibrium between temperature, electrolyte, liquor ratio, pH and affinity for the fibre type. To facilitate this equilibrium several auxiliary chemicals are added to the dye bath. Each has their own function and results. Examples are levelling agents, retarding agents, dispersing agent, dye bath lubricants buffering agents, stripping agents/soaping agents, sequestering agents, reducing agent, de foaming agent, wetting agents. Although their function is to assist effectively the adsorption and fixation of the dyes into fibres, they are unlikely to be consumed completely during the dyeing process and hence may lead to pollution load on rinsing the dyed material using large amounts of water (Shukla, 2007) As explained before dyeing happens in several phases for each phase different chemicals can be used.
cotton, linen
Dyeclass
Colourfastness
Impacts Viscose Polyamide Polyester acetate Acrylic
Wool
Reactive
Very good fastness properties
X XX X X XX
X X X X
Silk More likely to have halogens in their molecules which can lead to AOX emission. Substantial amounts of salt and unfixed dye stay behind in the waste water. Moreover, the waste water is highly alkaline Salt, unfixed dye and non exhausted fixing agents contribute to COD load in waste water. The impact is worsened if substrate is treated with formaldehyde, which is highly carcinogenic. More likely to have halogens in their molecules which can lead to AOX emission. The reducing agent (sodium dithionite = hydrosulphite) used in application is an environmental burden. During the dyeing process sodium dithionite is converted into sulphite (toxic to fish and bacteria) and in some cases this is further oxidised into sulphate. The environmental concerns in Sulphur dyeing are the use of complex agents such as EDTA and the use of oxidising agents such as bromate, iodate and chlorite. Moreover the waste water contains high amount of unfixed dye. Sulphur dyes contain sulphide which is very poisonous. The ecological concern is the toxicity of the naphtol dyes. They are significantly carcinogenic, which means that it is directly involved to increase the severity of cancer. Naphthol dyes should be avoided at all times.
Direct (substantive)
Relatively poor fastness to light, washing and perspiration. Can be improved by after treatment. High fastness to washing, chlorine, boiling, light, weather, rubbing and perspiration.
Vat (reduced)
Sulphur (leuco sulphur Fast to washing, but not to light or or solubilised sulphur) chlorine. Dull colours.
X X XX X
Naphthol (azoic dyes Good fastness properties developed on the fibre)
Fig. 14: Dyeclass overview, Authors own.
cotton, linen
Dyeclass
Colourfastness
Impacts Viscose Polyamide Polyester acetate Acrylic
Wool
Acid (metal-free)
depends on the dye and the fibre type. Good fastness except for rubbing Good fastness properties due to large size and low solubility of the complex dye molecule Good fastness acrylics properties on
X X
X X X X
Silk Acid dyes are in general not toxic. However, two dyes (Acid orange 156 and Acid orange 165) have been classified as toxic by ETAD. The largest group of acid dyes are azo compounds, which are proven to be mutagenic and toxic. The main ecological concern is the potential release of chromium in waste water. Chromium is very harmful to the environment. The heavy metals in the dye molecule that leave behind in the waste water can cause severe damage to the environment as they are toxic to aquatic organisms. Moreover, they have the tendency to accumulate. Many basic dyes exhibit high aquatic toxicity classified by ETAD. More over, the retarders is used are represented by quaternary ammonium compounds which have by far the highest toxicity of all classes of surfactants More likely to have halogens in their molecules which can lead to AOX emission. The main ecological concerns are the carriers used in disperse dyeing. They are toxic to human and aquatic life, have high volatility and high odour intensity. In rinsing a significant amount of carriers are left behind in the waste water, which contaminates the water. Moreover during heat setting the fractions of carriers on the fibre contaminate the air.
Chrome (mordant) Metal complex
X X X X X X X X
X X
Basic (cationic)
Disperse
Good fastness properties
Fig. 14: Dyeclass overview, Authors own.
Please note that the scheme does not take into account all auxiliary chemicals, moreover the dyeing conditions and use of auxiliary chemicals vary greatly, depending on the substrate to dye, the chemical structure of dye itself (within dye class), the product requirements. Therefore, dye bath ingredients will be discussed per dye class specified by substrate. However, dye processes may deviate as process conditions of the mill could require more additives and dye from supplier A can differ with similar dye from supplier B. 3.3.1 Examples Reactive and disperse are applicable to most of the substrates and they will be discussed in greater detail. For other dyeing processes and dye bath ingredients please refer to appendix. The following texts about reactive dyeing, acid dyeing and disperse dyeing will illustrate as examples. The chemicals bonds, application technique and dye bath ingredients will be explained.
Reactive Dyeing Reactive dyes form covalent bonds with the fibre, which means that the dye becomes one molecule with the fibre molecule. Therefore wash fastness of reactive dyes is very good. Urea is sometimes used as dyeing solvent, it increases the solubility of the dye. However according to BAT, As early as 1992 the use of urea as dyeing solvent was already in decline. New highly soluble reactive dyes have been introduced in the market which do not need urea even for deep dyeing in highly concentrated dye liquor In order to improve dye bath exhaustion, salt is added. The salt makes the dye stick to the fibre. The concentration of the salt depends on the shade intensity and the substantivity of the dye. Higher concentrations are required for deep shades and low-affinity dyes. Alkaline is required to start the reactivity process after the fibre has absorbed the dye. After dyeing, the liquor is drained off and the material is rinsed and then washed off with the addition of auxiliaries Whether the dye, alkali and salt are added in one step to the dye bath depends on the dyeing method. For example in batch dyeing all the ingredients are added together, whereas in pad dyeing the ingredients are added in separate steps. The fixation % of reactive dyes is relatively low, around 50% of the dyestuff stays behind in the dye bath, this causes one of the environmental concerns. Typical reactive dye bath ingredients per substrate are outlined below: Cellulose (Cotton, Linen, Viscose) pH 9.5 - 11.5 by addition of sodium carbonate and/or sodium hydroxide - Salt is used to increase dye bath exhaustion: higher concentrations are used for low-affinity dyes and
Polyamide - in principle the reactive dyes used for wool are also suitable for PA - dyeing is conducted at near-boiling temperature in weakly
Protein (wool, silk) - pH 4.5 to 7 - formic or acetic acid - levelling agent - after-treatment with ammonia for highest fastness
for deep shades - Application temperatures vary from 40 C to 80 C depending on the class of the dyestuff - In padding processes urea or cyanoguanidine is usually added to the pad liquor (the Econtrol process described in Section 4.6.13 does not need urea) - After dyeing, the material is soaped and then washed off with addition of surfactants to remove unfixed dye Batch, Pad-Batch, Pad-Steam, Pad-dry
acidic conditions - after-treatment is performed at 95 C using a non-ionic surfactant and sodium bicarbonate or ammonia
batch
batch
Fig. 15: Reactive dyeing ingredients. Source: European Commission 2003 Acid dyes: Acids dyes dye protein fibres, such as wool and silk, but they also dye polyamide. The fabrics are dyed in acidic conditions, however, depending on the type of acid dye, the pH range varies. From chemical poiny of view they can be classified into three groups: azoics: most yellows, oranges, scarlets and greater parts of red come into this class, most browns as well. Reduced with sodium hydrosulphite and soldium sulphoxilate formaldehyde Anthraquinoes: blue dyes with good light fastness and some greens and violets: a leuce deritave is formed that oxidises again wgen it comes into contact with air. Triphenylmethanes: violets blues and greens with the most brilliant depths of all acid dyes However acid dyes can also be classified according to they way they are applied. Levelling acid dyes acid dyes with good levelling properties because the formic acid and sulphuric acid in the dye bath act as the levelling agents. Milling acid dyes acid dyes with medium levelling properties exhibit superior fastness properties to level-dyeing acid dyes, while retaining some of the migration properties. Application is from a moderately acidic dye bath (1 3 % acetic acid) in the presence of sodium sulphate (5 10 %) and levelling agent to assist migration. Super milling acid dyes - acid dyes with scarce levelling properties. (including 1:2 metal-complex dyes mentioned later) have good affinity for the fibre and do not migrate well at the boil. They are therefore applied at more neutral pH (5 - 7.5 with acetic acid) in the presence of sodium acetate (2g/l) or ammonium sulphate (4 %).
Optimal exhaustion and uniform dyeing can also be achieved by controlling the temperature profile. The wet-fastness of dyeing with acid dyes on polyamide fibres is often unsatisfactory. After treatment with syntans (synthetic tanning agents) is often necessary. The syntans are added to the exhausted bath or to fresh liquor at pH 4.5 by formic or acetic acid. The material is treated at 70 - 80 C and is then rinsed. Typical acid dye bath ingredients per substrate are outlined below: Polyamide - pH conditions from acid to neutral depending on the affinity of the dye - optimal bath exhaustion and level dyeing are achieved by either pH or temperature control methods (levelling agents are also used) - in the acidic range, electrolytes retard the exhaustion - with levelling dyes, wet-fastness is often unsatisfactory and aftertreatment with synthanes can be necessary batch Protein (Wool, Silk) - Strongly acidic conditions for equalising dyes (by formic acid) - Moderately acidic conditions for halfmilling dyes (by acetic acid) - More neutral conditions for milling dyes (by acetic acid and sodium acetate or ammonium sulphate) - Salt: sodium sulphate or ammonium sulphate - Levelling agents other than sulphate and formic acid are not necessary for level-dyeing colourants batch
Fig. 16: Acid Dyeing ingredients. Source: European Commission 2003 Disperse dyes Disperse dyes are used to dye polyester, polyamide, acetate and acrylic. The dyes have low solubility in water but in the presence of dispersing agent the dyes are ground into tiny particles and dispersed throughout the dye bath. However, their small size means that disperse dyes are quite volatile, and tend to sublime out of the polymer at sufficiently high temperatures. colour bleeding, staining, colour loss Disperse dyeing is executed under weak acidic conditions and a high dyeing temperature is required. The structure of a polymer is very crystalline in order to make it looser dyes should be applied under pressure at temperatures of 130C. The thermal agitation opens gaps in the polymers structure and makes it easier for the dye molecules to enter. In open baths where the temperature can not be raised over 100C, carriers are used to dye polyester. These carriers have low molecular weight, are quickly absorbed and accelerate the dyeing rate. Moreover they improve fibre swelling and migration. Phenols, amines, aromatic hydrocarbons and esters are examples of carriers. The main ecological concerns are the carriers used in disperse dyeing. They are toxic to human and aquatic life, have high volatility and high odour intensity. In rinsing a significant amount of carriers are left behind in the waste water, which contaminates the water. Moreover during heat setting the fractions of carriers on the fibre contaminate the air. Typical disperse dye bath ingredients per substrate are outlined below:
Polyamide
Polyester
Acrylic
Cellulose Acetate and Triacetate
- PH 5 by acetic acid -dispersing agents (sulphoaromat ic condensation products or nonionic surfactants) - dyeing is conducted at near-boiling temperature
- pH 4 - 5 by acetic acid - levelling agents (aliphatic carboxylic esters, ethoxylated products, combinations of alcohols, esters or ketones with emulsifying agents) - possible addition of complexing agents (EDTA) for dyes sensitive to heavy metals -> dyeing under pressure at 125 C. - this techniques requires the use of carriers unless modified polyester fibres are employed -> below 100 C - pH 4 - 5 by acetic acid - thickeners such as polyacrylates and alginates are added to the padding liquor in order to prevent migration of the dye during drying - after-treatment with a solution containing sodium hydrosulphite and sodium hydroxide (dispersing agents are added to the last washing bath) -> thermosol
- dyeing conditions correspond to those used for polyester - addition of carriers is not required
- dispersing agents weakly acidic conditions (pH 5 - 6). - presence of Levelling auxiliaries. -usually dyed at 120 C, but if these conditions are not possible a dyeing accelerant (based on butyl benzoate or butyl salicylate) is required
Batch
Batch + Thermosol
Batch + Thermosol
Batch +Thermosol
Fig. 17: Disperse dyeing ingredients. Source: European Commission 2003
In order to obtain a more technical knowledge about dyeing conditions per process (vat, sulphur, direct dyeing, etc) it is highly recommended to read the appendix. To conclude, dyeing is a very technical process and requires knowledge expertise to be executed. 3.4 Printing Printing can be described as the controlled placing of defined areas of colour onto a substrate. The colourants must first be brought to the fabric surface, usually in the
form of a printing paste. If it is a soluble dyestuff it must be diffused into the fibres. This process is similar to dyeing. Printing can be done with water-based ink, plastisol ink or pigments. Just like in dyeing, there are several techniques in which a printing ink can be applied.
Rotary Screen Printing: A combination of roller and screen printing in which a perforated cylindrical screen is used to apply colour. Colour is forced from the interior of the screen onto the cloth. (Kilgus et al, 2008) Screen Printing: A method of printing similar to using a stencil. The areas of the screen through which the colouring matter is not to pass are filled with a waterproof material. The printing paste which contains the dye is then forced through the untreated portions of the screen onto the fabric below. (Kilgus et al, 2008) Roller Printing: The application of designs to fabric, using a machine containing a series of engraved metal rollers positioned around a large padded cylinder. Print paste is fed to the rollers and a doctor blade scrapes the paste from the unengraved portion of the roller. Each roller supplies one colour to the finished design, and as the fabric passes between the roller and the padded cylinder, each colour in the design is applied. Most machines are equipped with eight rollers, although some have sixteen rollers. (Kilgus et al, 2008) Heat Transfer Printing: A method of printing fabric of polyester or other thermoplastic fibres with disperse dyes. The design is transferred from pre-printed paper onto the fabric by contact heat which causes the dye to sublime. Having no affinity for paper, the dyes are taken up by the fabric. The method is capable of producing welldefined, clear prints. (Kilgus et al, 2008) Fig. 18: Printing Techniques. Sources: European Commission 2003 and Kilgus et al. 2008)
3.4.1 Methods of printing Additionally to the different machinery and application techniques, there are different methods of printing. Direct printing Resist printing Discharge printing Direct Printing With this method the colour pattern is printed directly on the fabric, which can be white or dyed. Resist Printing A resist paste is printed onto the fabric in the desired printing pattern. The fabric is then dyed, the parts which were covered by the resist paste are not coloured. In this way a printed pattern is formed. Discharge Printing The fabric is first dyed in a specific colour then a discharge paste is printed onto the fabric. This discharge paste contains a reducing agent and removes the colour where applied. In this way a white print is created. If a coloured print is desired, a dyestuff is added to the discharge print and replaces the removed colour of the fabric. A fabric which is printed with a discharge paste requires thorough washing to remove the by-products. The discharge paste often contains formaldehyde which is a very toxic substance and is an ecological concern. 3.4.2 Inks/Colours Just like in the dyeing process, the type of ink has to be applicable to the type of substrate to be printed. Moreover, the type of ink used also depends on the desired print result. The industry has made a large choice of highly specialised compositions available. There are solvent inks, two component inks, UV inks, synthetic resin inks or enamel inks for ceramic prints. Metallic inks relief ink, ink with a mother of pearl effect, phosphorescent inks, shimmering, scented inks create special effects or inks which change their colour under the effect of heat. (Barth, 2009) The inks most used in the textile industry are plastisol ink and water-based ink. Plastisol is often the ink of choice for printing of finished goods such as T-shirts, sweatshirts, jackets, and tote bags. Water-based ink is the ink of choice for the printing of yard goods; either in piece form or on the roll. (Ukena, PNEAC) Plastisol Ink Plastisol inks are 100% solid, which means that they contain no solvent at all. They are made of PVC (polyvinyl chloride) and a plasticizer. In order to fix the ink on the fabric, it requires heat. The molecules of PVC and the plasticizers will cross-link under
a high temperature and solidify. Plastisol inks have to be disposed as hazardous waste. PVC and phthalates (plasticizers) cause ecological concern; they are prohibited by the GOTS standard. Not only in waste disposal but also during the curing process it releases Volatile organic compounds, which are damaging for health and environment. (Ukena, PNEAC) Water-based inks Dyes and pigments are used for water based inks. They utilize water as the main solvent. In order for a print to cure the water needs to evaporate. This is usually done in a drying tunnel. Dyes classes discussed in previous paragraph can be used in printing as well. For example reactive, acid, vat and disperse printing is often used. In reactive printing paste sometimes urea can be used to increase solubility and formation of condensate. Discharge of urea, but also ammonia and nitrate contributes to eutrophication and aquatic toxicity. Therefore urea used should be minimised at source. In order to develop a printing paste several additives are required: Ink, thickeners, binding agents, detergents, adhesives, dissolving agents, dispersing agents, fixation agents, reducing agents, oxidising agents. Pigments are not soluble in water and are fixed to the fabric by use of an adhesive and binders. As final stage in pigment printing, the printed fabric should be dried and fixed. This is done wit hot air. VOC are released one of the major sources is white spirit. White spirits is used for emulsion thickets. The final stages in pigment printing consist in drying and fixing the printed fabric with hot air. Hydrocarbons, which are found in synthetic thickeners, are also found in exhaust air. Additionally to thickeners, another ecological concern is the fixing agent used for pigment printing. Those auxiliaries are largely based on methylol compounds that give rise to formaldehyde and alcohols in exhaust air. Ammonia is used as additive in binders and is also a source of air pollution (European Commission, 2003) The tables below give an overview of typical ingredients for a print paste and demonstrate the difference between pastes of varies dyestuffs.
3.4.3 Ingredients print pastes Reactive dyestuffs (COD: ca 55000 g/kg

Component Reactive dyestuff liquid Alginate thickener Ludogol NaHCO3 Water Composition % 7 2 1 3 88
Vat dyes stuffs (COD: ca 160000 g/kg)

Component Vat dyestuff liquid Thickener Rongalit C K2CO3 Urea Sorbit De-arating agent Water Composition % 4.3 5.0 10.6 11 2 5 0,2 61.9
Disperse printing no COD available

Component Disperse dyestuff Tamarinds thickener Dispersing agents Monosodium phosphate Water Composition % 2.6 7.0 0.5 2.8 87.1
Pigment printing
Component Pigment dough Acrylate thinneker Emulsifier Binder Cross-linking agent Softening agent Water Composition % 4 3 1 12 1 1 78
Fig. 19: Print paste ingredients. Source: European Commission 2003
Whether plastisol inks or water-based inks are used, they are still chemical compounds and each of them poses threats to the environment and human health. Next to the hazardous chemical compounds which are used in printing, the cleaning of the printing machines and print paste waste also forms an ecological concern. Before a new colour will be used the equipments of the printing machine (screens, print paste feed, buckets) needs careful cleaning. Water consumption is very high and so is the use of detergents.
The European Commission (2003) created the table below, which describes pollutants that are likely to be encountered in waste water from printing processes.
Pollutant Organic dyestuff Unfixed dye
Source
Remarks The related environmental problems depend on the type of dyestuff concerned (these are discussed in Section 9) High level of nitrogen contribute to eutrophication High levels of nitrogen contribute to eutrophication Sulphites are toxic to aquatic life and sulphates may cause corrosion problems when concentration is > 500 mg/l High COD, but easily biodegradable Hardly biodegradable and hardly bio eliminable Hardly biodegradable, but ->70% bio eliminable (OEC D 302B test method)
Urea
Hydrotropic agent
Ammonia
In pigment printing pastes
Sulphates and Sulphites
Reducing agents by-products
Polysaccharides CMC derivatives Polyacrylates
Thickeners Thickeners Thickeners Binder in pigment printing
Glycerin and polyols
Anti-freeze additives in dye formulation Solubilising agents in printing pastes In discharge printing of vat dyes as oxidising agent. In direct printing with reactive dyes inhibits chemical reduction of the dyes Blanket adhesive Hardly biodegradable and watersoluble
m-nitrobenzene ulphonate and its corresponding animo derivative
Polyvinyl alcohol
Hardly biodegradable , but >90% bio eliminable (OEC D 302B test method) Hardly biodegradable and hardly bio eliminable Aliphatic alcohols and hydrocarbons are readily biodegradable. Aromatic hydrocarbons are hardly biodegradable and hardly bio eliminable
Multiple-substituted aromatic amines Mineral oils/aliphatic hydrocarbons
Reductive cleavage of azo dyestuff in discharge printing Printing paste thickeners (halfemulsion pigment printing pastes are still occasionally used)
Fig. 20: Pollutants waste water printing. Source: European Commission 2003
After dyeing, printing, the fabric will have to undergo a variety of other treatments, such as: Fixation/Curing: The colour may need to be durably bound (fixed) within the fibre. By using hot steam or thermosetting this fixation is achieved. Washing: Washing and rinsing is done at all stage and is used for the removal impurities, unfixed dyestuff, left over auxiliary chemicals, left over print pastes. Consequently these streams also carry heavy chemical loads. To conclude, wet processes are pre-treatment, dyeing and printing. Within this general process there are different treatments, such as desizing in pre-treatment and reactive dyeing in dyeing. As demonstrated Figure 12 and 14 not all treatments can be applied to all substrates, moreover each treatment has its environmental impact, such as high BOD/COD in waste water from desizing (see figure 12). Further, dyebath ingredients vary between dyeclasses; therefore each class has a slight different effect on environmental impact. Textiles can be treated at different stages, at stock (loose fibres), yarn, and piece and garment stage. The sort of dyeing machines being used depends on characteristics of the textile, quantities, colourfastness. Liqour-to-goods ratios of dyeing machines vary from 5:1 to 40:1. Printing can be done in different ways, direct, resist or discharge, depending on the design requirements. Plastisol and waterbased inks are often used, in addition to ink many other chemicals and additives are used to create the print paste. These additives, such as ammonia and sulphates are to found in waste water can cause environmental damange such as eutrophication and corrosion. In wet processing many aspects and many variable factors are involved, which make dyeing and printing complex processes.
Chapter 4
What is the complexity of wet processing? MADE-BY would like to give their member brand a better insight into wet processing practises and their environmental impact. More ideally they would like to offer them a perspective for action, which means that brands can make different choices to decrease the impact on the environment. The most convenient way would include all wet processes into a benchmark, similar to the fibre and social benchmarks discussed in chapter 1. However, wet processing is very complex and this raises the question whether a wet processing benchmark would be a valuable contribution and, moreover, trustworthy. To take textile dyeing as an example; In order to decide which dyestuff has the least environmental impact and which one has the most, so many variables to be taken into account that is it almost impossible. Dyeing is already a very complex process, there are no standard procedures and in addition to the dyestuffs, the auxiliary chemicals also pose a major threat on the environment. A different shade requires lower or higher amounts of dyestuffs and other auxiliary chemicals, etc. The map below shows the aspects which make dyeing such a complex process hence making it even more difficult to classify wet processes.
Different fibre groups
Dyeing at extrusion, fibre, yarn, piece garment
Dyeing Blends
Colour fastness
WET PROCESSING Colour shade Machines use Not one standard procedure Rinsing Continuous, Batch Fibres vs filaments Dyebath exaustion Influence of brands Washing Indigo
Dyebath Ingredients
Fig. 21: Wet processing web, Authors own.

Trying to find a systematic way of displaying and outlining all the possibilities to dye different substrates the flowchart below was developed. However, for this example only the possibilities for cotton were outlined, which was sufficient to support the argument being made. It provides a systematic overview of the possibilities to dye cotton. There are 5 x 3 x 12 = 180 ways to dye cotton, without taking into account aspects such as colour requirements and colour fastness requirements. Moreover, different characteristics of dye within their dye class are also not included in the scheme. This will be discussed later on in the chapter. More importantly, this scheme only demonstrates the possibilities to dye cotton, not polyester or wool. One can make a rough estimation of the total possibilities to dye all substrates (cotton, wool, polyester, silk, etc) by multiplying the fibre groups with 180. Take into account that most of the fibre groups can be dyed by average 4 to 5 dyeclasses. 180 x 20 (Fibre groups classified in MADE-BY fibre benchmark) = 3600. Note: this scheme does not take fabric blends into account, which will also increase dye possibilities, thus complexibility. When it comes to dyeclasses Naphtol dyes have gradually lost their market share. Reactive dyes have outmoded them, except from a few deep red and Bordeaux combinations shades which can not be obtained by any other dyeclass. (Broadbent, 2001) Whether textiles are dyed continuously or batch wise depends on production volumes and textile characteristics. Whereas continuous dyeing is often done with very large lots of a single colour, because it is the most economic, it creates problems with the constanty of the shade. Woven fabrics can be dyed continuously, but knitted fabrics are rarely dyed continuously because the tension on the textile causes to stretch. Considering dyeing machines, textile characteristics and stage of dyeing are determining factors. The stage of dyeing will add more posibilites to the overview as there is a choice between stock dyeing, yarn dyeing, piece dyeing, and garment dyeing. Whether textile is dyed in stock stage or in piece fluctuates as it is subjected to fashion and designs. According to Anton Luiken (2010) most used machines in piece dyeing are jet dyeing, beam dyeing and pad-batch or pad-steam dyeing.
Fig. 22: Systematic Complexity demonstration
One also has to take into account the Colour requirements, e.g. teint, brightness Reactive & Colourfastness requirements (to light, rubbing, washing etc.) Scale 1: 5 Both have their impact on the dye recipe and thus environmental impact
Semi-continuous Continuous Batch NB: See bottom
o o o o
Pad-batch Pad-Jig Pad-Roll Pad-Steam
o o o o o o o o
Stock 12:1 (STOCK) Hank 17:1 (YARN) Package 10:1 (YARN Beam 10: 1 (PIECE) Beck/winch 17:1 (P) Jet 12:1 (PIECE) Jig 5:1 (PIECE) Paddle 40:1(GARME
Semi-continuous Direct Continuous NB: See Batch
o o o o o o o o o o o o
Pad-batch Pad-Jig Pad-Roll Pad-Steam Stock 12:1 (STOCK) Hank 17:1 (YARN) Package 10:1 (YARN Beam 10: 1 (PIECE) Beck/winch 17:1 (P) Jet 12:1 (PIECE) Jig 5:1 (PIECE) Paddle 40:1(GARME
Semi-continuous
Cotton
VAT Continuous Batch
NB: See
Semi-continuous Sulphur Continuous Batch
NB: See
Semi-continuous Naphtol Continuous Batch NB: There are different groups within a dyestuff category, which are based on chemical structure or other characteristics and make the dyeing process each time slightly different. Moreover this scheme does not take into account the auxiliary chemicals added as this also varies per dye process, but do have a big impact on the environment. Wet Processing Thesis 9 November 2010 Final Thesis
o o o o
Pad-batch Pad-Jig Pad-Roll Pad-Steam
o o o o o o o o
Stock 12:1 (STOCK) Hank 17:1 (YARN) Package 10:1 (YARN Beam 10: 1 (PIECE) Beck/winch 17:1 (P) Jet 12:1 (PIECE) Jig 5:1 (PIECE) Paddle 40:1(GARME
In order to provide a better understanding of the twists and turns of wet processing, several scenarios will be explained in detail. Some are discussing an issue from a broader point of view, others are very specific. Combined these scenarios sketch the complexity of wet processing: 1. No standard procedure 2. Colour shade / colourfastness 3. Fixation % of dyestuff 4. Azo compounds 4.1 No Standard procedure As briefly explained in the previous chapter, there is not really a standard procedure in wet processing of fabrics. Especially when it comes to dyeing, e.g. obtaining the correct colour shade and level dyeing. The impacts on the environment vary greatly depending on which process step is chosen to be applied. For example, if one wants to dye a knitted woollen fabric, into a light pastel. The fabric will undergo a scouring treatment, a bleaching treatment; will be dyed by an acid dye and all these processes will be executed in an exhaust (batch) dyeing machine. However, the woollen fibres may be scoured before they are spun and woven instead of afterwards. The fabric can also be fibre, yarn, piece or garment dyed, depending on the design and requirements. Moreover the impact and water use of dye machines differ winch or soft flow? If the fabric is a blend different procedures would be carried out, which means that impacts would be different accordingly. Additionally, there are also the differences between blends; is one dyeing cotton/polyester or wool/acrylic? It may be clearly observed from figure 22 that depending on the dye substrate dyeing technique, the characteristic parameters of waste water differ widely.
Fig. 23: Waste water characteristics (different combinations of dyes, substrate, equipments) Source: Shukla 2007
A recurring theme in the efforts to become more environmentally responsible is one of the swings and roundabouts; a change made in one aspect of a dye application process for environmental reasons can often (negatively) impact another part of the process. (Bide, 2007) For example, exhaust dyeing of knitted goods is less polluting and the pad-batch option does not represent the best option for waste minimisation in cases where lower fixation is achieved in the pad-batch process and also as a result of the need to ensure that excess pad liquor is available to avoid running out of colour during the padding process. The pad-trough needs to have a minimal volume (minimal application techniques) and the distance from the feed tank must be very small to reduce the extra make up of dye liquor. (Shukla, 2007) Each of the factors below can considerably change the environmental impact: Process steps pre-treatment, dyeing, printing, Stage - Yarn, piece, garment Machinery, Fabric/blends, Knits or wovens. The textile industry is characterised by different kinds of substrates inclusive many bonds, different makeups, different main process types (continuous, semi & discontinuous) and different process steps (pre-treatment, dyeing printing, finishing) Thus there is a higher degree of diversity of process and process variation. (Kalliala and Talvenmaa 2000) 4.2 Colour shade / Colourfastness (dye recipe) In addition to all the variable factors included in wet processing, another factor which makes dyeing very complex is the desired colour shade and colour fastness, which has its implications on the make up of the dye recipe/print paste. Dyeing is an art and not a science (Old and Sold.com) This quote demonstrates the complexity of dyeing fairly well; of course dyeing is very much related and based on science. However, on the contrary, it is also a vague and more artistic process in order to obtain correct shades, depths, fastnesses, etc. According to Bide (2007) are dyes rarely completely reproducible, this consequently puts a higher pressure on dyers. Moreover the choice of dyes and the amount of each to be used (the recipe) is often based on trial and error. (BIDE, 2007) Several lab dips will go back and forth between buyer and supplier in order to determine the correct shade. Dyes are sold with concentration of the dyestuff ranging between 20 and 80%. They are sold as powders, granules, pastes, liquid dispersions and solutions. (Shukla, 2007) Undeniably the form the dyestuff is in; in addition to the concentration % have their influence on the make up of the dye recipe. In order to control the dyeing process, auxiliary chemicals are used on large scale. For example in controlling the colour shade of a fabric, an additive is often the first answer in solving the problem and correcting the shade. (Easton, 2009) Evidently, the more chemicals are added to the
dye bath, the more the system becomes, interaction increase, and new problems can occur and the more there is deviated from the original recipe (he recipe is taken out of its standard proportions.) Easton (2009) states that the inability to get the right colour at the right time, is one of the biggest sources of delay, and consequently increased cost in the apparel sectors current business processes. Certain products require a higher fastness to light, for example curtain, whereas bath towels and sportswear require a higher fastness to washing. Within the same dyeclass the more insoluble compounds have greater fastness to wet treatments; those which are found in a more oxidised state are more resistant to oxidants, those which contain chlorine atoms have greater fastness to bleaching. (Cegarra, J., Puente, P., Valldeperas, J. 1992) Dyes are specially selected to obtain a greater fastness. Moreover, process circumstances also have an impact on shade/fastness, by temperature, pH, and auxiliary chemicals. The aims of a dyer are therefore to achieve the correct shade and fastness properties on a substrate in a level of manner as efficiently and profitably as possible. (Easton, 2009) Some shade and substrate combinations are more difficult to dye than others and the dye house may consume large quantities of dyes, chemicals, water and energy trying to hit a difficult shade at the limits of achievability when a slight different shade may have presented a more easily achievable target. Colourfastness, colour shade, substrates contribute to the difficulty of dyeing. The aim of a dyer is therefore to achieve a level dyed fabric in the right colour shade and fastness as efficiently and profitably as possible. Taking into account the environmental factor of colouring fabric will even increase the complexity of this process. Selecting dyes that are considered more environmentally benign might be environmentally responsible, but reduced dye choice may make a level, fast or non metameric match harder to achieve under bulk application conditions. (Bide 2007) It is important to point out that the dyer does not exist in isolation. The customers requirements may force a dyer to carry out a process that is not environmentally responsible by insisting on tighter than necessary colour tolerances or fastness. (Bide 2007) Bide (2007) also states that life cycle analysis should be carried out in order to decide the environmental impact of the production of the item. However, the textile chain is long and complex, and weighting the balance of all the alternatives makes life cycle analyses for textile difficult, if not impossible. 4.3 Fixation Rate One of parameters dyestuff could be classified by is the fixation rate. In the dyeing process, once dyes are absorbed by the fibres they need to be fixed. The fixation of
dyes onto fibres makes sure that they are not washed off again during rinsing and washing procedures. Fixation can be done by oxidation or alkali washes, this depends on the dye class. The fixation percentage differs per dyestuff. The fixation % gives an indication of dyestuff that are fixed to the fibre, which means that the left over % stays in the dye bath. The table gives a clear overview of fixation rates per dye class.
Fig. 24: Fixation rate. Source: Van der Zee 2002
As demonstrated in the table, reactive dyeing has the lowest fixation rate, much of the dyestuff is left behind in the dye bath ie the waste water consist of large amount of non biodegradable dyestuff. One could argue that therefore reactive dyeing is the worst option, however, the fixation rate does not take into account, the chemical composition of the dyes and more importantly it does not include the auxiliary chemicals added to the dye bath. Chrome dyeing may have a better fixation rate, the chromium applied cause significant environmental concerns. 4.4 Azo Compounds Dye classes can be, within their class, divided into 2/3 groups. Those groups are formed based on their chemical structure. For example, acid dyes can be divided into 3 groups, azoic, anthraquinone, triarylmethanes and similar are vat dyes, which can be divided into 2 groups. According to Van der Zee (2002) the vast majority (60-70%) of the more than 10,000 dyes applied in textile-processing industries are azo compounds and represent the largest class of organic colorants listed in the Colour Index. Their relative share among reactive, acid and direct dyes is even higher, it can be expected that they make up the vast majority of the dyes discharged by textile-processing industries. Anthraquinone dyes are second largest class (~15% of the entries in the Colour Index), followed by triarylmethanes (~3%) and phthalocyanines (~2%). For example Acid Red 26 is carcinogenic azo dyes.
Fig. 25: Molecule structure of Acid Red dye. Source: Smith 1986
Azo dyes are banned because they are proven to be mutagenic, carcinogenic to humans and toxic to aquatic life (anaerobic azo dyes reduction). They will stay behind as unfixed dyes in waste water and their discharged is undesirable, for those reasons azo dyes need to be avoided. Considering this, it means that within dye classes, certain dyes are very hazardous. Therefore it is also difficult to classify the impact of a dye class. One could say, hypothetically, that acid dyes are friendlier to the environment than metal-complex dyes. However, most of the acid dyes are azo compounds, which makes calculating their total impact difficult.
4.5 Conclusion To conclude, calculating or weighting the environmental impact of wet processing activities, such as pre-treatment, dyeing, printing are complex. When it comes to dyeing textiles there are 3600 and more possibilities. This calculation takes into account dyeclass, methods, and machines. A more detailed view on complexibily is the effect of colourshade and colourfastness requirements, fixation rate of dyestuffs, and azo compounds in dyes. The variables and alternatives are too extensive to discuss and classify them into this thesis and would require more in depth research by an expert. Therefore creating a wet processing benchmark would not be a comprehensive approach to support MADE-BYs member brands.
Chapter 5
What are the sustainable alternatives of wet processing? The previous chapters gave the MADE-BY member brands a better insight into wet process and outlined the complexity. This demonstrated that creating a benchmark to give them a perspective for action is very difficult to achieve. Therefore, in order to give the MDE-BY member brands an alternative to the benchmark but still offer them a perspective for action, several sustainable alternatives will be discussed. 5.1 Enzymes Another alternative in wet processing is the use of enzymes. Enzymes can be used for pre treatment processes such as desizing and bio polishing. This has been proven more environmentally friendly by a Life cycle analysis study by Genencor (2010). This study contucted a life cycle assesement and compare conventional bleach and Gentle Power Bleach The use of enzymes saves many liters of water and increases the chemical load in waste water. An example calculation by Rene Hermse, Tanatex (2010):
Fig. 26: Process comparison enzymes. Source: Hermse, 2010
Enzymes are proteins and produced by living organisms. They can be used as catalysts and are biodegradable (Hermse 2010). Genencor (2010) claims the life cycle assessment of elemental textiles indicates the possible savings of 70000 litres of water and 1100 kilos of CO2 per ton knitted fabric. It also said to show reduced processing times of between 20-35% The process included stages of bio scouring to remove pectin and impurities followed by low temperature bleaching, dyeing in a combined process with bioblasting and finally bio soaping to do the final rinses. (Patterson, 2010) Processes were enzymes can be used are:
Fibre Cotton Treatment Desizing Scouring ` Scouring Enzymatic mixture Enzymes Amylases, amyglucosidases Pectinases Cotton fibre adjacent material Cotton fibre adjacent material
Substrate Starch
Degree of development State of the art Available Emerging
Bleaching Degradation of residual H2O2, after bleaming Bio-polishing Bio-stoning Wool Silk Flax Jute Scouring Anti-felting Degumming Softening Bleaching, softening
Laccases, glucoseosidases Peroxidases
Lignin, dyestuffs, glucose H2O2
Emerging Available
Cellulases Celluloses Lipases Special enzymes Sericinases Pectinestearases Cellulase, xylanases
Cellulose Cellulose Lanolin Sericin Flax fibre adjacent material Jute fibre adjacent material
Available Available Emerging Emerging Emerging Emerging Emerging
Fig. 27: Enzyme treatments. Source: European Commission 2003
Environmental savings are according to Genecor (2010) when comparing standard bleach with Gentle Power Bleach; 50% improvement of cotton loss in the process, water use is dimished from 40L to 30 L per kg for the total process, and process temperatures decreased with 30%. This results in decreased water consumption and decreased energy consumption. Genercor states that there is a benefit ranging from 10% to 30% for Gentle Power Bleach. The use of enzymes has several drawbacks, which hinder the industy from implementation. Enzymes are only applicable to desize, scour, bio-polish cotton, it therefore is limited in its utility. Additionally techniques to apply enzymes on other substrates are emerging but not yet commercially available.
5.2 Plasma application Plasma can be described as a mixture of partially ionised gases. Atoms, radicals and electrons can be found in the plasma. The electrons in low temperature plasmas are able to cleave covalent chemical bonds, thereby producing physical and chemical modifications of the surface of the treated substrate. (European Commission 2003) Advantages of plasma treatments are that it is a dry process, extremely short treatment times, and fewer chemicals are required in the textile sector. According to Radetic et al. (2007), the multi functionality of plasma processing is reflected in the possibility of using one system for modification of different kinds of fibres (natural protein and cellulose, synthetic) and textile forms with highly flexible product functional design. Plasma treatment can be used to achieve pre-treatment effects, such as wool degreasing, desizing, increase wet ability, improve hydrophilicity/hydrophobicity, improve dye levelling, and anti-felting finish. By choosing the appropriate gas (O2, N2, H2, air, Ar, He, NH3, hydrocarbons, fluorocarbons) and control of the plasma process conditions, such as treatment time, power, pressure, and gas flow the mentioned pre-treatment effects can be carried out. Drawbacks: Plasma application can not replace all pre-treatments in addition to that it requires capital investment, time and effort.
5.3 Natural Dyes The most obvious alternative form a brands perspective would be the use of natural dyes. Natural dyes can be divided into three categories, dyes derived from: 1: Animals 2: Plants 3: Minerals Natural dyes are biodegradable, this has a significant effect on the waste water, whereas non fixed conventional dyes stay behind in the waste water, natural dyes do not form any threat to the environment. However, natural dyes are low concentrated thus require high amounts to colour a substrate and often require a mordant to fixate the dyestuff and improve fastness. These mordants are heavy metals, such as copper, alum. As discussed earlier, heavy metals are very damaging to the environment. Tinctoria (Van Hengel 2008) uses only alum and state it is not harmful to the environment. According Lenntech (2009) alum is the least toxic. Aluminium is one of the most widely used metals and also one of the most frequently found compounds in the earth's crust. Due to these facts, aluminium is commonly known as an innocent compound. Nowadays most natural dyers use chemical mordants such as alum, copper sulphate, iron or chrome (however, in relation to environmental impact heavy metals such as chrome and copper are restricted). Mordants are prepared in solution, often with the addition of an assistant which improves the fixing of the mordant to the yarn or fibre. The most commonly used mordant is alum, which is usually used with cream of tartar as an additive or assistant. Other mordants are: Iron (ferrous sulphate) - Iron is used as a saddener and is used to darken colours. Tin (stannous chloride) - Tin brightens colours. Chrome (bichromate of potash) - Chrome is good for obtaining yellows. Copper sulphate - Copper sulphate also darkens but can give shades which are otherwise very difficult to obtain. Tannic acid, used traditionally with other mordants, will add brilliancy. Oxalic acid is good for extracting blues from berries. (Thesmarttime.com 2008) The company Rubia Pigmenta Naturalia manufacture a vegetable dye pigment from the roots of the madder plants, Rubia Red. Rubia states that the dyes can be applied in a similar way to conventional dyes and that they are exceptionally stable with extremely high colourfastness. (Ecotextile News 2010) At the moment Rubia Red covers around 40% of the colour spectrum, when used with different application methods. They are, however, striving to bring more vegetable dyes on the market in order to cover the total spectrum of colours. Drawbacks: Natural dyes are suitable for wool, silk and cotton, but often only applied to small production amounts. With conventional dyeing it is already very difficult to obtain the similar colour for several lots, in natural dyeing this is even more complex. Moreover, not the complete colour spectrum is covered which limits brands and suppliers to compete with the market.
5.4 Solution dyed A Taiwanese company HO YU haven proven that solution dyed yarn is more environmentally friendly. It reduces pollution and saves more energy, water consumption is reduced as well as the CO2 emission, and the process requires less dyestuff than piece-dyeing processes. HO YU produce recycle polyester fabrics and when PET is melted pure concentrations of dyestuff are added to the solution and are then extruded. According to HO YU, The fabrics have much better UV resistance and colourfastness to light washing. However, brands will have less flexibility with colours and can not adapt to colour quickly/easily. As the table demonstrates, a solution dyed fabric saves around 40-60% of water, fuel and electricity consumption. Moreover CO2 emissions were reduced by 60%.
Fig. 28: Savings on solution dyeing. Source:hoyu.com.tw
Drawbacks: However, many brands and suppliers prefer to dye the textile as late as possible to be able to rapidly response to market demand and trends.Consequently, more often textiles are dyed in piece or even in garment stage. Solution dying limits brands and suppliers in their flexibility towards market changes. 5.5 CO2 Dyeing Another interesting alternative is the possibility of CO2 dyeing. Dyecoo has developed a dyeing machine which dyes fabrics with CO2 under supercritical conditions. The first machine was launched on the 16th of June 2010. Up until now only the polyester fibres can be dyed, however Dyecoo is researching and developing possibilities to dye cotton. The main environmental benefit of CO2 dyeing is the lack of water and auxiliary chemicals. In order to dye with carbon dioxide it will be heated to 120 and pressurised to 250 bar (Dyecoo Textile Systems). Characteristic of a supercritical fluid is a high (liquidlike) density that enables dissolution of compounds. The graph below demonstrates the phases of carbon dioxide when heated and pressurised. The CO2 will become a supercritical liquid and acts as a swelling agent; moreover it allows the dye to penetrate the fibres. The process of scouring, dyeing, rinsing, drying and removing the excess dye can be carried out in the same batch.
Drawbacks: CO2dyeing is a very new development and costs will be high and availability low. At this moment, only polyester fabrics can be dyed and they still require pre-treatment process and heat setting processes. Moreover only one machine is commercially available. According to Noorderlicht nieuws (2008), Dyecoo is researching the possibility to dye cotton within 1 -3 years.
Fig. 29: Phases of CO2 dyeing. Source: Dyecoo textile systems
5.6 Pigment + Transfer printing In order to reduce the amount of processing water used for dyeing, pigment dyeing/printing would be a good alternative. Little pigment particles are glued to the surface by chemical binders and do not require water. According to Patterson (2009), the prints only need a simple heat treatment as a final process and since no steaming or washing is required it is much cheaper and lower environmental impact process than dyeing/printing with dyes. The thickener and the fixation agent do, however, contribute to volatile organic compounds. In pigment printing emissions to air (ammonia, formaldehyde, VOC) can be observed in drying and curing. (Schonberger and Schafer 2003) Those specific chemicals will have to be substituted and will be discussed further in this chapter. As the overview demonstrates below the Printing Pigment Transfer process of transfer printer does not with printing printing require washing procedures either.
dyestuffs
Pigment and transfer printing do have environmental benefits concerning water consumption, nevertheless the, chemical use, the VOC emission and energy consumption (curing, drying) still cause concerns. Drawbacks: pigment and transfer prints are printed on top of the fabric and do not penetrate into the fibre. The binder holds the pigments on the fabric and the printed areas are mostly stiffened. This has little effect on small designs, however with all over prints; the fabric will lose its flexibility.
Fig. 30: Printing processes comparision. Source: Schonberger and Schafer, 2003
5.7 Screen printing optimisation As Phil Patterson (2009) states in his article a simple solution to reduce water consumption, print paste waste, screen mesh would be to minimise the use of screens. I.e. create a less complex print and minimise the colours. In order to print a design with a screen printing method, the design has to be split up into its component colours. For each colour a individual screen mesh will be made. The numbers of colours in a design determines the number of screens that are used and this can be anywhere from 1 to 18 colours depending on the complexity of deisgn and the cost a customer is prepared to pay. (Patterson, 2009) Designers should look into the development of their prints and consider the impact last minute changes to print designs have. Drawback: Designers are limited in their flexibility and creativity. 5.8 Digital Ink-jet printing Compared to screen printing, digital ink-jet printing is a much easier process. The complete print is developed on the computer and is printed similar to paper. There is no need for separate screens and preparation of print pastes. Digitally printed fabric still has to go through the same sequence of bleaching, drying, printing, drying, fixing, washing off and drying so the digital printing only improves a solitary part of a long, convoluted process (Patterson, 2009) Drawbacks: The European Commission (2003) reports that production speeds are low and therefore are not replaced by the analogue printing techniques. Nevertheless, digital printing saves much time and effort in screen making, especially when changing designs. Moreover, there will be less wasted fabric from the design changes and avoid printing paste residues at the end of each run. 5.9 Laser technique Marite + Francois Girbaud (www.girbaud.com) have used laser techniques to give their denims finish treatments. By using the laser denims get a worn look or a nice pattern without using stones, chemicals or any water. This method is marketed as the WATT wash TM as it relates to an environmentally safe, water-free method for colour fading and producing patterns. By replacing regular denim treatments with laser technology, water and chemical can be saved. Consequently, energy consumption will rise. Drawbacks: Laser technique does not replace coloured printing and is therefore very limited in its use.
Fig. 31: Example Laser technique by Girbaud. Source. Girbaud.com

5.10 Substitution of Chemicals Less specific, but also of high importance, is the substations of process chemicals as an alternative. Most of the option mentioned earlier are limited to specific substrates and are not (yet) widely available. Substitution of chemicals is also a very important step in pollution prevention. It is however very broad and require intensive knowledge of techniques, chemicals, impacts. To list all chemicals and process substitutions would be too extensive and out of scope for this research. There are, however, very useful sources which list hazardous chemicals and their substitutes. In order to conduct a chemical substation study, it is crucial to obtain the Material Safety Data Sheet of a chemical. This document contains the chemicals nature, chemical and physical specialties, ecological data and hazards of the chemicals. (Ozturk et al. 2007) On the ecological side, a textile chemical should have high biodegradability / bio eliminability and less toxicity, nitrogen (N) and phosphorus (P) content. Ozturk et al. (2007) studied the problematic chemicals used in one specific mill and tested the effect of their substitution. For this particular mill, the environmental impacts of complexing agents, dispersants and sulphur dyes were discussed in depth. It was highlighted that for any substitution, a careful evaluation should be made to ascertain that one pollution problem is not being substituted for another. Whether substitution can be applied depends on the processes, the end product requirements, raw materials and the process conditions (water, machines). The possibilities and opportunities for chemical substitution vary greatly from one mill to another and require extensive study per mill. Nevertheless, there are lists and reference documents that provide an overall picture and offer solutions. The American Apparel and Footwear Association (AAFA) (2010, 7th release) created such a list The Restricted Substances list. The RSL was created based on substances, materials and chemicals forbidden by regulation or law in several countries around the world, for example, Germany, The Netherlands, Denmark, Japan, EU, China. The RSL identifies substances that can be found in the end product, not substances used in production processes. Many brands start developing their own Restricted Substance List, often in cooperation with the dyestuff supplier. For example, Levis created a RSL with CIBA, S. Oliver with Dyestar. Bestseller, on the other hand, created a chemical restrictions list which should be studied in depth and signed by all their suppliers. In this way they try to control the chemical uses which can pose risk to human health and environment. A more detailed and technical approach is offered by the European Commission that wrote a reference document on best available techniques in the textile industry. The document extensively discusses processes, dyes, auxiliary chemicals and also identifies the best available techniques to decrease environmental impact. Complexing agents, anti foaming agents, sulphur dyes, reactive dyes, A regulation on chemicals was developed by the European Commission:
REACH has been introduced as a means to more effectively monitor and control the import of chemicals into the EU. It aims to ensure that all manufactures and importers of chemicals identify the substances that they are bringing in, and that this is effectively managed to identify and manage the risks that these chemicals may pose to human health and the environment. Drawbacks: Substition of chemicals is detailed and requires expertise knowledge, time, and investment. It requires dyers to reassess their complete day-to-day business. 5.11 Special dye selection with supplier In order to be able to create a wide spectrum of colours and its shades and depths, but reduce the impact on the environment. Brands could team up with the dye supplier and their dye house. The report from Cotton incorporated (2009) claims that specially selected dyes, such as pre-reduced liquid dyes and high fixation reactive dyes, will cause less ecological damage. Several dye suppliers offer now more environmentally sound ranges and solutions, such as Dyestars Econfidence Program (2009), which classifies its products by red, amber and green. Huntsman have implemented sustainability in their business model: Product Stewardship is an integrated business process for identifying, managing and minimizing environmental, health and safety (EHS) impacts at every stage of a products life cycle. Product Stewardship has been a way of life at Textile Effects for as long as anyone can remember and provides the solid foundation for all our products and processes. Drawbacks: The choice of dye selection is limited when taking into account all the environmental impacts. It requires knowledge, time, effort, close collaboration and investment from the brand, the dyehouse and dyestuff supplier. Browngart and McDonough write about the chemical selection for the company DesignTex which selected environmentally sound dyeswith chemical company CIBA. Among 8000 chemicals commenly used in the textile industry, 38 were considered not harmful to environmental and human health. (Braungarth, McDonough 2003) 5.12 Process optimisation Options that will reduce the water, energy, and chemical consumption are process optimisations in the dye house itself. Cotton incorporated (2009), outlines several technologies which would reduce environmental impact. For example; Cold pad batch prep and dyeing, Continuous processing of knits, Two stage preparation of wovens, Combined scour and bleach for yarns and knits, Foam dyeing, finishing and coating, Pad/dry vs. pad/dry/pad/steam, Right first time dyeing. These are all technologies brands have little influence on, yet in order to successfully decrease impact it is very important suppliers adopt new technologies. More process optimisation technologies are discussed in the reference document for best available techniques in textile industry. This document is publicly accessible and considers techniques such as,
One-step continuous vat dyeing in pastel to pale shades Minimisation of dye liquor losses in pad dyeing techniques Enzymatic after-soaping in reactive dyeing Silicate-free fixation method for cold pad batch dyeing Alternative process for continuous (and semi continuous) dyeing Of cellulosic fabric with reactive dyes pH-controlled dyeing techniques Equipment optimisation applied to winch beck dyeing machines Reduction of water consumption in cleaning operations Water & energy conservation in continuous washing and rinsing Low-liquor-ratio jet dyeing machines Low-liquor-ratio package dyeing Insulation of dyeing, drying and stenter machines Solar heating of water
Drawbacks: These process optimisations require capital investments, expertise knowledge and complete turn around of automatic processes. Up until now only process-integrated alternatives were discussed. Conversely, there are also END OF PIPE SOLUTIONS in order to reduce pollution from the output streams of textile wet processing.
5.13 Dye bath replenishment Shukla (2007) reports the dye bath constituents should be analysed after exhaustion onto the textile and then replenished for subsequent use for dyeing another batch. A single processing bath can be reused for a number of times before being discharged as effluent. Dye baths or direct dyes, acid dyes, disperse dyes are manageable to replenish, as there are relatively few auxiliary chemicals present, thus few chemical changes occurred during the process. Shukla does state however that difficulty will be arise because of high temperature of water and problems with shade matching and metamerism can occur. The process of replenishing the dye bath, by adding the require amount of dyestuff and chemicals, does decrease the environmental concerns with regard to water use. A more appropriate approach would be to use the partially exhausted dye bath to obtain a lower depth of dyeing. This process will reduce the colour content of the bath and it presumably does not require addingtion of salt and auxiliaries, as they are not exhausted in a dye bath. In most cases, it is conceivable that the dye bath after second dyeing and, exceptionally third dyeing, will be almost colourless, thereby, decreasing the pollution load drastically. (Shukla, 2007) Drawbacks: From a dye house perspective there are many factors that are likely to hinder implementation of dye bath replenishment. From a brand perspective desired colour shades will be difficult to obtain.
5.14 Recovery of auxiliary chemicals In line with dye bath replenishment, is the recycle, reuse and recovery idea described byHendrickx and Boardman (1995). For example, an exhausted dye bath still contains a large amount of auxiliary chemicals like acetate/acetone. In other cases, sodium hydroxide, synthetic sizes or heat can be recovered. Drawbacks: These processes require capital investments, expertise knowledge and complete turn around of automatic processes. 5.15 Waste water treatment Effluents treatment plants are the most widely accepted approaches towards achieving environmental safety. But, unfortunately, no single treatment methodology is suitable or universally adoptable for any kind of effluent treatment. (Das, 2004) Textile effluent treatment can be executed through different methods:
Classification of waste water treatment process Treatment Primary Operations Screening Sedimentation Equalization Neutralisation Mechanical flocculation & Chemical coagulation Secondary Aerated lagoon Trickling filtration Activated sludge process Oxidation ditch & pound Anaerobic digestion Tertiary Oxidation technique Electrolitic precipitation & Foam fractionation Membrane technologies Electrochemical processes Ion exchange method Photo catalytic degradation Adsorbtion (Activated carrbon etc) Termal evaporation Fig. 32: Different textile effluent treatments. Source: Das 2004
Resulting from waste water treatment is a substance which is a concentration of pollutants, called sludge. Sludge should be disposed safely. Sludge therefore becomes unstable, putrescible and pathogenic. Sludge must therefore be treated before disposal or reuse in order to remediate our environment. (Asia, Oladoja and Bamuza-Pemu, 2006)
5.16
Chapter conclusion
The sustainable alternatives vary from specific pretreatments to process optimisations Most of the sustainable alternatives mentioned are available or emerging. In order to make a difference and actually reduce environmental impact, alternatives should be executed simultaneously. For example, if the dye house does not make use of waste water treatment then it does not make any sense for brands to invest in natural or low-impact dyes. To conclude, concrete solutions for each wet process are not widely available, many solutions replace a part of a wet processing aspect. Time, effort, knowledge, investment are required to implement most of the solutions.
Chapter 6
How can brands influence wet processing practises in their supply chain? As explained and demonstrated in the previous chapters, wet processing in textiles is very complex and has a major impact on the environment. Moreover, sustainables alternatives for wet processing are emerging, hardly available or incomplete. Furthermore, textile supply chains are very scattered and complex, which makes it even more difficult for brands to put their feet on the ground and start producing in a sustainable way.
6.1 Power division Supply Chain One of the major obstacles for brands to start dyeing sustainably is the power division in their supply chain. The example below demonstrate a simple supply chain which shows that brands do not communicate directly with their dyehouse, they often do not even communicate directly with their C.M.T., this happens through an agents. Additionaly, dyeshouses and CMTS have of course their own suppliers, which all have their influences on the chain and environment.
Brand
C.M.T.
Dyehouse
Weaver
Spinner
Farmer
Agent
Business/ Communication Supply Chain

Fig. 33: Supply Chain general overview, Authors own.
In order to get a grip on the wet processing situation and to improve sustainability, brands would have to communicate directly with their dyehouses. However the questionnaire carried out among MADE-BY brands confirmed that brand know very little about the wet processes in their supply chain. Neither do they communicate with their dye houses nor do their agents. One of the first steps to gain improvement would be a direct relationship between brand and dye house. Difficulties are often that brands communicate with the sales person and that person is not responsible for the chemical purchase and daily routine of production processes. Hermse (2010) also brought this up in his presentation about enzymes and demonstrated this issue with the model below.
Fig. 34: Different concerns and vision in supply chain. Source: Hermse, 2010
Within a company there are different concerns and visions. The sales person in keen on getting as many as customers as possible and would like to offer them sustainable solutions etc. However, the department manager who is responsible for the purchase of chemicals has to stay within his budget and sustainable alternatives are most of the time more expensive or require different methods. Therefore, Hermse (2010) also states, it is really important that everyone is involved and sees the benefit in order to improve wet processing.
6.2 Influence of Brands Another obstacle will be the influences brands have on its supplier (and their suppliers). Small brands have less buying power than big brands. A small brand could set up a wish list of requirements for sustainable production. However id the amounts that this brand buys are only 10% of the total production capacity of this supplier, it is very questionable whether this list will be executed and implement. The table below provides some overview of actions that can be taken by brands design or sourcing department. However, many of the sustainable alternatives are often only executable by supply chain commitment, communication and collaboration.
Alternatives Pre-treatment Enzymes Plasma application
Design
Sourcing
Supply Chain Commitment
Why Brands could decide to use enzymes, if a supplier is equipped for it. Brands could decide to use enzymes, if a supplier is equipped for it. Decision that can be made in design/sourcing process
X X X X
X X
Dyeing
Natural dyes
Solution dyed
X X X X X X X X X X X X X
Brands can not influence processes without engaging and collaborating with suppliers Brands can not influence processes without engaging and collaborating with suppliers Brands could decide to use CO2 dyeing, if a supplier is capable of it. Brands can not influence processes without engaging and collaborating with suppliers Decision that can be made in design/sourcing process Decision that can be made in design/sourcing process Decision that can be made in design/sourcing process Decision that can be made in design process Decision that can be made in design process
Special dye selection CO2 dyed
Dye bath recycling
Printing
Pigment printing Transfer printing Digital Ink-jet screen print optimisation Laser technique
X X
Alternatives
Design
Sourcing
Supply Chain Commitment
Why Brands can not influence processes without engaging and collaborating with suppliers
Over- all Management
Substitution of chemicals
Restricted Substances List
X X
X X X X X X
Brands can not influence processes without engaging and collaborating with suppliers Brands can not influence processes without engaging and collaborating with suppliers Brands can not influence processes without engaging and collaborating with suppliers Brands can not influence processes without engaging and collaborating with suppliers Brands can not influence processes without engaging and collaborating with suppliers Brands can not influence processes without engaging and collaborating with suppliers
REACH legislation
Process optimisation
Recovery auxiliary chemicals
Dye bath replenishing
Waste water treatment Fig. 35: Overview Sustainable Alternative on different levels, Authors own.
One can conclude from this scheme that brands have little influence on most of the sustainable alternatives as most of them are focused on process optimisation and end of pipe treatments. This is out of reach for brands to change according to their wishes as dye houses are responsible. This means that brand will have to collaborate and communicate with their suppliers. There are some choices which can be made solely by the brand, which are decisions on design and sourcing level. For example, a brand can choose to work with non-toxic natural dyes or they can work with enzymes. However, working both with natural dyes and enzymes only allows treatment of certain substrates and obtaining of a small spectrum of colours. It is fair to say that brand have to take many things into consideration when solely focusing on decisions they can make. Availability of techniques and costs will play a big part in this, but a more important aspect is flexibility. Brand will have to give in on their flexibility to adapt to market demand and consumer behaviour. Especially when making colour choices, setting colourfastness standards and deciding the stage of dyeing (Fibre, yarn, piece). If all fabrics are solution dyes, the flexibility to adjust colour last moment is gone.
6.3
Step by Step process
From my own investigations, conversations with textile expert Anton Luiken and dyestuff experts from Huntsman, brand really have to dive into their supply chains to find out which processes are being used and which can lead to improvement. In an industry where supply chains are fragmented and scattered across the globe, supply chain transparency is crucial in order to improve. Therefore a more holistic approach is developed. It shows brands steps that have to be taking in order to improve the sustainability of their dye processes and provides them a starting point. The Step by Step Process or Ladder on the next page outlines the several steps brands would have to take.
Wet Processing Thesis 19 October 2010 Draft Version
Fig. 36: Ladder to tackle sustainable wet processing step by step, Authors own.
6.3.1 Step 1 Transparency: The first step towards more sustainable wet processing practises is an insight in and overview of the supply chain. As most of the MADE-BY brands know little of their own supplier, transparency is the starting point. In order to get a better understanding of wet processing practises, brands should investigate who is doing what in their chains. I.E. who is the manufacturer, where do they produce, where is their dye house, etc. Once the complete supply chain is transparent and suppliers and dye houses are identified further steps can be taken. MADE-BY support transparency in the supply chain and should motivate its brands to dig deeper into the bottom of their chains. They have already developed a template for transparency up to CMT (garment manufacturer) level and could extend this. Important to get a better picture is to know what is happening in the dye houses. E.g. what methods are being used, what are the machines, dyestuffs, is there any waste water treatment, and are their any certifications? MADE-BY could develop a template which asks for specific information such as; Name of dye house Location Certifications Machines Processes Dyestuffs To start with, brands could choose a certain product or product groups and trace back its supplier and dye house. Then they should figure out which treatments are applied, which processes and machines are used.
6.3.2 Step 2 Measurements: Once MADE-BY and its member brands have obtained a complete picture of their dye houses and dye processes further steps can be taken to develop an improvement plan. To set specific objectives factory input and emissions should be measured. A lifecycle analysis tool develop for Modint by Anton Luiken and CU Delft measures the water usage, energy usage, CO2 emissions, Chemicals and then gives an indication of the
total impact in specified by process (fibre manufacturing, fibre processing, garment manufacturing) Other examples are the carbon footprint and the water footprint CREM has developed, which measure the CO2 emission and water consumption. In order to get more knowledge and expertise in this field, MADE-BY should collaborate with experts such as Anton Luiken and CREM to measure factory emissions. There can be looked at: Liquor ratios of machines Waste water emission in total Toxicity of waste water Energy consumption CO2 emission
6.3.3 Step 3 Impact calculation: Once all measurements are taken, the impact calculation can be made. Which means that on overview can be created that sums up impacts of a brands collection or perhaps just a product group of one specific product (jeans). By using the Modint tool, Carbon footprint or Water footprint, an overview of water energy, CO2 can be calculated and provide a starting point with a carefully chosen approach. For example, the minimising water usage in pre-treatment processes.
6.3.4 Step 4 Process Optimisation: The fourth step is a more direct or concrete approach to tackle environmental pollution/impact. By optimising processes in dye houses the environmental impact can be considerably reduced. As mentioned in the previous chapter there are many process optimising solutions. The European Commission reference document for Best Available Techniques provides extensive knowledge and explanation. MADE-BY and its member brands should collaborate with experts in the field to implement these optimisation by dye houses. Tackling process optimisation allows the factory emissions, such as waste water and energy to diminish. Moreover, it could enable less chemical input requirements. It, therefore cover a large scale of impact reduction possibilities.
6.3.5 Step 5 Output: Secondly, to avoid any pollution steams to end up into the environment, output (emission) management should be improved or in some cases implemented. Different methods of waste water treatments have been developed and can be implemented. There should be looked at careful sludge disposal, as well as dyestuff disposal and other chemicals disposal. Moreover should be looked at greenhouse gases emissions. The Best Available Techniques reference document and certifications could provide guidance into this matter. However, also in this case MADE-BY should work with experts in the field and suppliers to work on a solution.
6.3.6 Step 6: Input: Lastly, input management should be undertaken. This step is very complex and will require time, effort and very specific research. Brands could look, in collaboration with chemical experts, at the chemical requirements for their collections. Thus, which chemicals are applied to these jeans and to this top specifically? They should identify each chemical, dye used for their collection and then find a substitute which will cause the environment impact to diminish. Additionally, they could explore the dosage of dyestuff, perhaps it could be halved and still obtain the same results. REACH, Restricted Substances Lists, and Material Safety Data Sheets will provide more information on chemical substance, however without help of chemical experts this step will be nearly impossible. Organisations MADE-BY could collaborate with: Huntsman dye stuff manufacturer Genencor (enzyme treatments) Chemists
6.3.7 Step 7 Review: Once improvements have been made they should be reviewed, examined, and assessed, thus start over at step 1. Creating a more sustainable supply chain and more sustainable processes will be a continuous process as the industry will be developing new technologies, solution, findings at all times. Therefore, it is important, results and processes are assessed over and over again.
6.4 Chapter Conclusion The ladder in this chapter caters as a starting point and encouragement to investigate further the circumstances in supply chains. As it is difficult for brands to implement sustainable alternatives, the possibilities lie in supply chain transparency, measuring, impact calculation. Furthermore they should investigate their own collections and supply chains to identify the room for improvement. In order to work towards a more sustainable dyeing process brands will have to collaborate with suppliers and textile chemical experts. By means of collaboration, production processes can be optimised, in and output can be managed. The conclusion is transparency and supply chain collaboration is the way forward.
Chapter7
7.1 Conclusion This final chapter will reflect back on the aim and findings of this report and will answer the research question. How can MADE-BY effectively inform their member brands about the environmental impact of wet processing and offer them a perspective for action to improve sustainability? MADE-BY can inform its members on the wet processing aspects; with the technical and chemical information provided in chapter 2, 3, and 4. In chapter 5 and 6 are alternatives and action plans to improve sustainability outlined. Both will be explained below. MADE-BY strives to develop a wet processing benchmark, which in their opinion enables their member brands to tackle the textile wet processing environmental issues. Researching the wet processing aspects showed that, whereas reactive dyes have low fixation rates, thus waste water is highly coloured and not biodegradable, are metal complex dyes hazardous due to presence of heavy metals in their molecules. Moreover, liquor ratios vary per machine; jet machines are less water consuming than winch dyeing machines. Unfortunately not all processes can be carried out in jet machines and not all substrates can be dyed with one dyestuff. Not to forget are the auxiliary chemicals, which are versatile and applied for many reasons. Consequently, chemical usage and effluent loads very per process. The systematic analysis (Fig. 22 page 42) shows that for cotton alone there are +/180 possibilities to dye cotton. This results in +/- 3600 possibilities to dye all substrates. (Substrates x dye class x methods x machines). To reflect back on one of the initial objectives of the research, which was to inform by measuring, it had not been specified what had to be measured. This resulted in a diversity of variable factors and lead to that a wet processing benchmark has not been achieved in this study. Nevertheless, a ladder to tackle sustainability step by step has been developed in this research. Step 1 is Transparency and requires knowledge about suppliers, methods, machines, dyestuff. In order to move forward brands have to know or find out which processes are being used and make their supply chain transparent. Only as soon as complete supply chain transparency has been obtained, one can start measuring processes (Inputs, emissions, consumptions). Measuring processes requires expertise and information. With those measurements environmental impacts can be calculated. Absolute figures and knowledge about water
consumption, energy consumption, and chemical consumption will help MADE-BY and its member brands to make purposeful decisions and develop concrete action plans. In this thesis are the following alternatives researched; enzyme treatment, plasma application, natural dyes, solution dyed, CO2 dyeing, Pigment + Transfer printing, Screen print optimisation, Digital Ink-jet printing, Laser Technique, Substitution of chemicals, special dye selection, process optimisations, dye bath replenishment, auxiliary chemicals recovery, and waste water treatment. However, the research has revealed that brands will not be able to implement sustainable alternatives on their own, as often decision making is beyond the influence of brands (Chapter 6). Whereas designers can optimise prints by considerate design, implementation of low-liquor-ratio package dyeing requires capital investment, knowledge and collaboration with the dye house. Therefore, under controlled and transparent circumstances in combination with supply chain collaboration, sustainable alternatives can be executed. By means of the ladder MADE-BY and member brands are offered a stepping stone and can start working on improving sustainability, which means decreasing water, energy, and chemical consumption.
7.2
Recommendations Each of the steps in the step by step process should be developed further into action plans and clear aims and objectives. In order to develop those action plans MADE-BY should create alliances and collaborations with several organisations, such as Huntsman, Genencor, CREM and other industry experts. MADE-BY have already developed an internal document on wet processing standards and certifications and should also use that document to educate and inform their member brands.
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9
9.1
APPENDICES
APPENDIX PRE-TREATMENT
Desizing
Process: Size is a substance that is applied to the yarn before weaving, it enhances the weaving effiecieny. These sizes, which can be watersoluble or waterinsolube, have to be removed before the fabric is dyed, called desizing. The following methods are commonly used (depending on the size type): - enzymatic desizing processes; starch - oxidative desizing (e.g. persulfate); all size types - washing (with/without detergents); water soluble sizing agents. Impact: The liquors used for desizing contribute to a high COD load of a finishing mill. According to European Commission (2003) this can be up to 70% of the load in mills finishing woven fabrics and concentrations range from 3000 to 80000 mg O2/l. Neither enzymatic nor oxidative desizing allows size recovery, while for some synthetic sizing agents size recovery is technically feasible, but difficult to apply for commission companies. More problems are posed by the presence of substances that are difficult to emulsify and poorly biodegradable such as silicone oils, which are found in elastane blends with cotton or polyamide.
Scouring
Process: Scouring is used to remove natural impurities from cotton fabrics and blends/ In order to remove waxes pectines, proteins and metals salt the fabrics are treated with hot alkali (sodium hydroxide), complexing agents and surfactants. Scouring of silk (removal of serecin) can be done under alkaline/neutral/acidic conditions depending on the desired result. Temperature is also an important factor in achieve the desired result. The scouring process of silk can be divided into 3 groups: unscoured silk, souple silk, degummed silk. Impact: The surfactants and complexing agents are non readily biodegradable and the COD load is very high due to organic impurities removed from the fibres. COD-concentrations from 2000 to 6000 mg O2/l are typical. (European Commission 2003) Silk scouring baths Scouring baths present a high total organic charge; the concentration of nitrogen organic components in particular is high.
Bleaching
Process: Bleaching is used to increase the whiteness of a fabric and enhance dyeing and printing properties. Fabrics are almost always bleached, except when a fibre is to be dyed to a deep shade with a dark colour. As bleaching agent, hydrogen peroxide,
sodium hypochlorite and sodium chlorite are used. Which technology or agent is used depends on the substrate. Impact: Bleaching with hydrogen peroxide requires the use of stabilisers in order to inhibit the radical attack of bleach on the cellulose. However, stabilisers may contain complexing/sequestering agents (EDTA and DTPA) that have poor bio-eliminiability and can pass straight through waste water treatment systems. Their ability to form very stable complexes with metal makes the problem even more serious because they can mobilise heavy metals present in the effluent and release them in the receiving water (BREF2003) It has been reported ([77, EURATEX, 2000]) that, depending on concentration, pH, time and temperature, effluents containing inorganic chlorides (e.g. NaCl from dyeing and printing, MgCl2 from finishing) can be oxidised to their chlorites/hypochlorites when they are mixed with hydrogen peroxide bleach waste water. In this way AOX may be found in waste water When bleaching with hypochlorite, chlorine air emissions occur and causes secondary reactions that for organic halogen compounds (quantified as AOX) Sodium chlorite bleaching may also be responsible for AOX generation in the waste water. (bref 2003) Moreover, handling and storage of sodium chlorite need particular attention because of toxicity and corrosion risks. When subjected to heat, friction or impact, sodium chlorite mixtures with reducing agent can cause an explosion hazard. Sodium chlorite decomposition produces oxygen, which supports ignition
Mercerising/Causticizing
Process: The cotton is treated under tension with a strong akali (solution of caustic soda or ammonia). Mercerizing causes the fibres to swell, which improves dystuff absorption and increases strength and lustre. Causticzing is similar to mercerising but is applied to man-made synthetics and done without tension stress at low temperatures. (http://www.thesmarttime.com/processing/mercerisation.htm) Impact: The main ecological impact in mercerising/causticising is the high concentrated (varies from 20% - 30%) residual alkali which needs to neutralised.
Causticizing (alkali treatment)
Process: Causticzing is similar to mercerising except, caustixing is done without tension stress and at low temperatures (between 10 C and 15 C. ) The process induce shrinking of the textiles. Ecological impacts in causticizing can be compared to mercerising. (http://www.thesmarttime.com/processing/mercerisation.htm )
Optical bleaching/brightening
Process: optical brightening is achieved by dyeingthe fibre with fluorescent chemicals (stilben and imidazol derivatives). Those chemicals absorb ultraviolet light and hide the yellowish colour of the by-products and give a bluish light to the textiles
(Schonberger, Schafer 2003). Optical brightening is used to achieve a very high degree of whiteness/brightness and can be classified as direct dyes. It can be carried out in a single step process, simultaneously with bleaching or during finishing. Impact: Optical bleaching has an impact on the water toxity and the fluourescent agents have a low degree of bio elimination. The intense exchange of information in the textile chain is very important to adjust the appropriate washing conditions (kind and quantity of surfactants, pH, temperature, dwell time, liquor exchange, etc.) to achieve good quality and to minimize ecological loads.
Carbonising
Process: carbonising is a process applied to wool and used to destroy cellulose impurities, such as hay and straw, in the fibre/fabric. The fabric is treated with sulphuric acid and with compressed air the degraded cellulose is blown out. Impact: The acid and the organic load (the by-products removed from the fibre) in the effluent cause the main environmental impact. Wool pretreatment gives rise mainly to water emissions, although there are also specific operations (e.g. carbonising with the Carbosol system and dry cleaning) where halogenated (mainly perchloroethylene) solvents are employed. The use of halogenated organic solvents solvents can produce not only emissions to air, but also contamination of soil and groundwater if their handling and storage is not done using the necessary precautions. Preventive and end-ofpipe measures include closed-loop equipment and in-loop destruction of the pollutants by means of advanced oxidation processes The process also involves the generation of exhausted active carbon from the solvent recovery system. This solid waste has to be handled separately from other waste material and disposed of as hazardous waste or sent to specialised companies for regeneration. (European Commission 2003)
Crabbing
Process: crabbing is carried out on wool in order to fix the material and reduce/prevent creasing + felting, and to wash out by-products. The wool is treated under tension (wounded) with hot water and chilled afterwards. Felting/fulling: Is similar to crabbing and induces shrinkage of the textiles and improves the handle of the fabric. Alkaline or acidic liquor and felting agents are used to start the felting process. Impact: App. 20% of textiles made of pure wool are felted. Ecological charges are caused by felting agents and by-products/impurities removed from the wool during the process.
Anti-felting
Process: Sometimes felting is done on purpose, however often felting is an undesirable effect, which can be caused by wet processing activities (dyeing, washing). Anti-felting minisimes this effect by coating polymers and/or oxidizing techniques. Impact: This process is responsible for a relatively high AOX-load in the effluent. (in oxidizing techniques the chlorine generating agents are responsible) (e.g. dichloroisocyanurat)
9.2
APPENDIX DYEING
Direct dyes:
Direct dyes are water soluble, although with some require the presence of sodium carbonates (salt) to become soluble and dissolve. Direct dyes dye cellulosic fibres without a mordant, thus there is no need for an extra substance to fix the dyestuff to the fibre. Direct dyes are also quite important in cellulose fibres dyeing: 75 % of the total consumption of these colourants is used, in fact, to dye cotton or viscose substrates (European Commission 2003) They dye the fibre without being removed by a subsequent washing, therefore there also called substantive dyes. Direct dyes belong to two chemical classes: azoic dyes (azo groups); thiazole dyes ( can form azoic compounds). With direct dyes there is no need for mordant, but still need for salt (to become soluble), levelling agent and reducing agents, retarding agent etc. Celluloses can be dyed in neutral bath and slightly alkaline bath. The auxiliary agents ensure a thorough wetting and dispersing effect Within the direct dyes family you can recognise: Self levelling dyes dyed in neutral bath; Dyes with average levelling or salt controllable dyes dyed in slightly alkali bath; Dyes with poor levelling which are controllable through temperature; Dyed in slightly alkali bath. In continuous dying with direct dyes, urea can be added for very intense shades. To increase the solubility of the dye wetting agents, anti foaming agents, reducing agents etc can be added. This all depends on the characteristics of the dyes, of the fabric to pad as well as the system used to fix the dye. Direct dyes do not require a mordant to fix the fibre, however, in order to improve wash fastness metallic salts and formaldehyde treatments can be carried out. According to BAT Environmental concerns arise when after-treating with formaldehyde condensation products or metal salts. The method using fixative cationic agents is, therefore, the most frequently applied. However, quaternary ammonium compounds are often non-biodegradable, fish-toxic and contain nitrogen. Also the use of urea contributites to the environmental impact.
Cellulose - Salt is used to increase bath exhaustion - Mixtures of non-ionic and anionic surfactants are used as wetting/dispersing agents - After-treatment is usually necessary to improve wet-fastness (possible use of fixative cationic agents, formaldehyde condensation products) Batch, Pad-Steam, pad batch, pad jig
Source: European Commission 2003
Sulphur dyes
Process: suplhur dyes are in many aspects similar to direct (substantive) dyes and in other aspects to vat dyes. Cellulosic fibres are dyed directly when reduced and link with basic dyes to produce a insoluble laquer. The quantity of dye absorbed by the fibre isinfluenced by the presence of salt, the temperature and the concentration of the dye. This is all very similar to direct dyes. However, sulphur dyes are insoluble in water or slightly soluble like vat dyes. In order to make them soluble the presence of sodium sulphite (acts as reducing agent) is required and alkaline conditions. When exposed to air (oxidisation) the dyes get back to their insoluble form and are fixed to the fibre. Sulphur dyes have very low exhaustion rates, much fo the dystuff gets left behind in the dyebath.he reducing agent, salts, alkali (caustic soda) and unfixed dye are finally removed from the fibre by rinsing and washing. The environmental concerns in Sulphur dyeing are the use of complex agents such as EDTA and the use of oxidising agents such as bromate, iodate and chlorite, which contribute to AOX emission. Moreover the waste water contains high amount of unfixed dye. Sulphur dyes contain sulphide which is very poisonous. Warning: Solution is highly alkaline Contains hydrogen sulfide, a highly toxic gas. Eye contact will cause marked eye irritation and possibly severe corneal damage. Skin contact will result in irritation and possible corrosion of the skin. Ingestion will irritate/burn mouth, throat and gastrointestinal tract. Contact with stomach acid will cause hydrogen sulfide vapors to be released. Heating or acid will cause hydrogen sulfide gas to evolve. Dilution of NaHS with water will also cause increased evolution of hydrogen sulfide. (http://tdc-home.com/downloads/MSDS/MSDS_Sodium_Hydrosulfide.pdf)
Cellulose - Reducing agents (Na2S, NaHS, glucose-based combination of reducing agents) and alkali are applied to convert the dye into soluble form, unless ready-for-use dyes are used - Dispersants and complexing (EDTA or polyphosphates) agents are used in batch dyeing - In batch dyeing, the dye generally absorbs at 60 - 110 C, while in the pad-steam process the material is padded at 20 - 30 C and then subjected to steaming at 102 - 105 C - Oxidation is carried out mainly with hydrogen peroxide, bromate and iodate (which are halogen-containing compounds) Batch, Pad Steam, Pad-Dry
Vat dyes
Process: vat dyes are insoluble in water. In order to make them soluble and substantive for textile fibres the dyes should be reduced by alkaline solutions. Although vat dyes are similar to sulphur dyes, the reducers (alkaline solutions) used and dyeing methods are very different. Once the dyes are converted to their leuco form, they immerse into the fibre and are then converted back into insoluble form by oxidation. Vat dyes can be recognised in two groups: Dyes derived from indigo; Dyes derived from anhtraquinone (most of them in this group). The washing fastness for vat dyes in deep shades is good, but in case of light shape not. The dye method plays an important part in wash fastness; when dyed with vat dyes in flock the best results are obtained, the worst results are in piece dyeing. Vat dyes are very wash-fast, but have the opposite reputation due to ring-dyeing The difference in method of dyeing with indigo and that of dyeing with other vat dyes us that with indigo the fibre is immersed and oxidised by the leuco several times until the required shade is obtained because of the low affinity of indigo for cotton. However, other vat dyes are absorbed just in one phase. Different type of reducers: Vat with lime and iron sulphate Vat lime and zinc Hydrosulphide vat In order to achieve uniformity in dyeing, levelling agents are added, temperature is increased or a pre-pigmentation process can be used. Oxidation and after-treatment follow in all cases. The after-treatment is washing the material in a hot/boiling alkaline bath with a detergent
Cellulose - Alkali and reducing agents (sodium dithionite, sulphoxylic acid Batch derivatives, thiourea dioxide, and other organic reducing agents) are applied to convert the dye to the sodium leuco form - Poorly degradable dispersants are present in the dye formulation and are further added in other steps of the process - Levelling agents are sometimes necessary - Temperature and the amount of salt and alkali required vary according to the nature of the dye (IK, IW, IN) - Dye is fixed to the fibre by oxidation, generally using hydrogen peroxide, but halogen-containing oxidising agents can also be used - After-treatment takes place in a weakly alkaline detergent liquor at boiling temperature - In continuous processes, anti-migration and wetting agents are used Batch, Pad Steam

Reactive
Reactive dyes form covalent bonds with the fibre, which means that the dye becomes one molecule with the fibre molecule. Therefore wash fastness of reactive dyes is very good. Urea is sometimes used as dyeing solvent; it increases the solubility of the dye. However according to European Commission 2003, as early as 1992 the use of urea as dyeing solvent was already in decline. New highly soluble reactive dyes have been introduced in the market which do not need urea even for deep dyeing in highly concentrated dye liquor In order to improve dyebath exhaustion, salt is added. The salt makes the dye stick to the fibre. The concentration of the salt depends on the shade intensity and the substanticity of the dye. Higher concentrations are required for deep shades and low-affinity dyes. Alkaline is required to start the reactivity process after the fibre has absorbed the dye. After dyeing, the liquor is drained off and the material is rinsed and then washed off with the addition of auxiliaries Whether the dye, alkali and salt are added in one step to the dyebath depends on the dyeing method. For example in batch dyeing all the ingredients are added together, whereas in pad dyeing the ingredients are added in separate steps. The fixation % of reactive dyes is relatively low, around 50% of the dyestuff stays behind in the dyebath, this cause one of the environmental concerns. Different circumstances different substrates Reactive Dyeing Chemicals and Auxiliaries
Cellulose (Cotton, Linen, Viscose) pH 9.5 - 11.5 by addition of sodium carbonate and/or sodium hydroxide - Salt is used to increase dye bath exhaustion: higher concentrations are used for low-affinity dyes and for deep shades - Application temperatures vary from 40 C to 80 C depending on the class of the dyestuff - In padding processes urea or cyanoguanidine is usually added to the pad liquor (the Econtrol process described in Section 4.6.13 does not need urea) - After dyeing, the material is soaped and then washed off with addition of surfactants to remove unfixed dye Batch, Pad-Batch, Pad-Steam, Pad-dry Source: European Commission 2003 batch batch Polyamide - in principle the reactive dyes used for wool are also suitable for PA - dyeing is conducted at nearboiling temperature in weakly acidic conditions - after-treatment is performed at 95 C using a non-ionic surfactant and sodium bicarbonate or ammonia Protein (wool, silk) - pH 4.5 to 7 - formic or acetic acid - levelling agent - after-treatment with ammonia for highest fastness
Acid dyes
Acids dyes dye protein fibres, such as wool and silk, but they also dye polyamide. The fabrics are dyed in acidic conditions, however, depending on the type of acid dye, the pH range varies. From chemical poiny of view they can be classified into three groups: azoics: most yellows, oranges, scarlets and greater parts of red come into this class, most browns as well. Reduced with sodium hydrosulphite and soldium sulphoxilate formaldehyde Anthraquinoes: blue dyes with good light fastness and some greens and violets: a leuce deritave is formed that oxidises again wgen it comes into contact with air Triphenylmethanes: violets blues and greesn with the most brilliant depths of all acid dyes. However acid dyes can also be classified according to they way they are applied. Levelling acid dyes acid dyes with good levelling properties because the formic acid and sulphuric acid in the dyebath act athe the levelling agents. Milling acid dyes Acid dyes with medium levelling properties exhibit superior fastness properties to level-dyeing acid dyes, while retaining some of the migration properties. Application is from a moderately acidic dye bath (1 3 % acetic acid) in the presence of sodium sulphate (5 10 %) and levelling agent to assist migration. Super milling acid dyes - acid dyes with scarce levelling properties. (including 1:2 metal-complex dyes mentioned later) have good affinity for the fibre and do not migrate well at the boil. They are therefore applied at more neutral pH (5 - 7.5 with acetic acid) in the presence of sodium acetate (2g/l) or ammonium sulphate (4 %). Optimal exhaustion and uniform dyeing can also be achieved by controlling the temperature profile. The wet-fastness of dyeing with acid dyes on polyamide fibres is often unsatisfactory. Aftertreatment with syntans (synthetic tanning agents) is often necessary. The syntans are added to the exhausted bath or to fresh liquor at pH 4.5 by formic or acetic acid. The material is treated at 70 - 80 C and is then rinsed.
Polyamide - pH conditions from acid to neutral depending on the affinity of the dye - optimal bath exhaustion and level dyeing are achieved by either pH or temperature control methods (levelling agents are also used) - in the acidic range, electrolytes retard the exhaustion
Protein (Wool, Silk) - Strongly acidic conditions for equalising dyes (by formic acid) - Moderately acidic conditions for half-milling dyes (by acetic acid) - More neutral conditions for milling dyes (by acetic acid and sodium acetate or ammonium sulphate) - Salt: sodium sulphate or ammonium sulphate - Levelling agents other than sulphate and
- with levelling dyes, wet-fastness is often unsatisfactory and aftertreatment with synthanes can be necessary batch Source: European Commission 2003 Natphtol dyes
formic acid are not necessary for level-dyeing colourants batch
Naphthol dyes are insoluble azoic compounds and are dyed under highly alkaline conditions (12-14 pH). If natpholds are combined on the fabric with a range of diazo salts it will result in the formation of a water insoluble dye. However this will typicallty be a very different colour than either of the two components. Various combinations result in different colours. Therefore, dyeing with Naphthol dyes is a very complex process; especially the preparation of the colour requires a number of delicate steps. In order to creat the naphtholate solution, the naphtol is dissolved by boiling with caustic soda (alkaline). In cold processes alchohol, cellolsolve, caustics soda and cold water are required to solubilsed the natphol. In some case, the addition of fomaldehyde is necessary to prevent formation of free naphtol (BAT). The napholota is appkied to the substrate by batch or padding techniques and afterwards the fabric is treated in a bath with diazotized base. This base is a mixture of sodium nitrite and hydrochloric acid. Buffering agents are required to control the pH and increase coupling capacity. The ecological concern is the toxitiy of the naphtol dyes. They are signifcalty carcinogenic, which means that it is directly involved to increase the severity of cancer.
Cellulose - Preparation of the naphtholate (caustic soda and, in some cases, addition Batch of formaldehyde is required to stabilise the naphthol on the fibre) - Impregnation of the naphtholate by exhaustion or padding processes - Preparation of the diazotised base (with NaNO2 and HCl) - Developing stage (the textile is passed through the cold developing bath or the developing solution is circulated through the stationary textile in the dyeing machine) Batch, padding methods Source: European Commission 2003 Chrome dyes
Chrome dyes are soluble, have an affinity for silk, wool and polyamides and are often used for dark shades such as greens, blues and blacks. They do require a mordant to
attach the dye to the fibre. Chromium acts as a bridge between the dye and the fibre and the fastness properties are excellent due to this very strong ionic bond. The dyes are applied from an acidic bath, often sulphuric acid, together with the presence of the mordant dye and potassium dichromate (chromium ion) they form a complex which is insoluble in water.
There are three application methods of chrome dyes:
Chrome Mordant method; Meta chrome method; After chrome method. In this process the potassium dichromate (chrome)s added first together with sulphuric or formic acid (to make the bath acidic). When the fibre has taken up the chromium, the fabric is taken out of the bath and placed in a bath with the mordant dye. relies on chroming the fibre prior to dyeing with a chromable dye Meta Chrome process In this process the subtrate is treated simultaneously with the mordant dye, the potassium dichromate (chrome) and ammonium sulphate (acid). Then the bath is heated and the ammonium converts into ammonia and sulphuric acid. The bath is now strongly acid and the potassium dichromate reacts with the dye molecules and forms a strong complex.
After chrome method
With this technique the substrate is first dyed in the presence of an acid. Once the dye reached its exhaustion rate the potassium dichromate is added and forms the insoluble complex. According to BAT the other to processes have ben largely superseded by the afterchrome process, because the technique utilises the exhausted dye bath and thus conserves water. The main ecological concern is the potential release of chromium in waste water. Chromium is very harmful to the environment.
Wool - pH 3 to 4.5 - sodium sulphate - organic acids: acetic and formic acid (tartaric and lactic acids can also be used) - reducing agent: sodium thiosulphate - after-chrome with Na or K dichromate Batch dyeing (After-chrome method)
Source: European Commission 2003 http://www.dyes.co.uk/chemicals.html http://www.ecotintes.com/en

http://www2.dystar.com/highlights/deepshades.cfm?CFID=421760&CFTOKEN=7284 5548 http://www.scribd.com/doc/28010401/Textile-auxiliaries-Non-Surfactant-auxiliaries01

Metal-complex dyes
Metal complex dyes contain of a metallic atom and one or more dye molecules. This molecule is often chromium and has an affinity for protein and polyamide fibres. From a dyeing point of view they are actually concidred as acid dyes. Metal complex dyes have vert strong wet fastness Metal complex dyeing recognise two groups of which the first one is 1.1 metal complext dyes that dye in strong acid liquour (pH 1.8 -2.5) with use of sulphyric acid or formic acid, it also requires the presences of sodium sulphate + levelling agents. The other group are the 1.2 metal complex dyes.They dye in neutral- moderate acidic liquors with ammonium acetate for moderate acidic and ammonium sulphate for weakly acidic. If the pH value of the bath decreases the absorption of the dye increases, which means that high affinity dyes require a pH dye bath: They also require the presence of a levelling agent
Wool 1:1 metal complex: - pH 1.8 to 2.5 (pH 2.5 in the presence of auxiliary agents such as alkanolethoxylates) - sulphuric or formic acid - salt: sodium sulphate - ammonia or sodium acetate can be added to the last rinsing bath 1:2 metal complex: - pH 4.5 to 7 - ammonium sulphate or acetate - levelling agents (non-ionic, ionic and amphoteric surfactants) Batch Source: European Commission 2003 Disperse dyes 1:2 metal complex: - dyes containing sulphonic groups are preferred because they are more water-soluble and produce better wetfastness - to improve absorption of low-affinity dyes (especially for disulphonic) dyeing is carried out in weakly acidic conditions using acetic acid - high-affinity dyes are applied in neutral or weakly alkaline medium using amphoteric or non-ionic levelling agents Batch Polyamide
Disperse dyes are used to dye polyester, polyamide, acetate and acrylic. The dyes have low solubility in water but in the presence of dispersing agent the dyes are ground into tiny particles and dispersed throughout the dye bath. However, their small size means that disperse dyes are quite volatile, and tend to sublime out of the polymer at sufficiently high temperatures. colour bleeding, staining, colour loss Disperse dyeing is executed under weak acidic conditions and a high dyeing temperature is required. The structure of a polymer is very crystalline in order to
make it looser dyes should be applied under pressure at temperatures of 130C. The thermal agitation opens gaps in the polymers structure and makes it easier for the dye molecules to enter. In open baths where the temperature can not be raised over 100C, carriers are used to dye polyester. These carriers have low molecular weight, are quickly absorbed and accelerate the dyeing rate. Moreover they improve fibre swelling and migration. Phenols, amines, aromatic hydrocarbons and esters are examples of carriers. The main ecological concerns are the carriers used in disperse dyeing. They are toxic to human and aquatic life, have high volatility and high odour intensity. In rinsing a significant amount of carriers are left behind in the waste water, which contaminates the water. Moreover during heat setting the fractions of carriers on the fibre contaminate the air.
Polyamide - PH 5 by acetic acid - dispersing agents (sulphoaromatic condensation products or nonionic surfactants) - dyeing is conducted at near-boiling temperature Polyester - pH 4 - 5 by acetic acid - levelling agents (aliphatic carboxylic esters, ethoxylated products, combinations of alcohols, esters or ketones with emulsifying agents) - possible addition of complexing agents (EDTA) for dyes sensitive to heavy metals -> dyeing under pressure at 125 C. - this techniques requires the use of carriers unless modified polyester fibres are employed -> below 100 C - pH 4 - 5 by acetic acid - thickeners such as polyacrylates and alginates are added to the padding liquor in order to prevent migration of the dye during drying - after-treatment with a solution containing sodium hydrosulphite
Acrylic - dyeing conditions correspond to those used for polyester - addition of carriers is not required
Cellulose Acetate and Triacetate - dispersing agents weakly acidic conditions (pH 5 - 6). - presence of Levelling auxiliaries. -usually dyed at 120 C, but if these conditions are not possible a dyeing accelerant (based on butyl benzoate or butyl salicylate) is required
and sodium hydroxide (dispersing agents are added to the last washing bath) -> thermosol Batch Batch + Thermosol Source: European Commission 2003 Cationic dyes Batch +Thermosol
Dyes consist of molecules, which can ionic, cationic, or anionic. The difference is in the way they are electrically charged. Ionic atoms are cationic or anionic, in which cationic is a positively charged ion and anionic is a negatively charged ion. Typical recipes used in batch dyeing include an electrolyte (sodium acetate or sodium sulphate), acetic acid, a non-ionic dispersant and a retarding agent. Dyeing is conducted by controlling the temperature in the optimum range for the treated fibre. Finally the bath is cooled down and thematerial is rinsed and submitted to aftertreatment. Continuous processes commonly applied are: pad-steam process (fixation with pressurised steam at more than 100 C); this process has the advantage of reducing fixing time. Pad liquor typically contains a steam-resistant cationic dye, acetic acid and a dye solvent; pad-steam process (fixation with saturated steam at 100 - 102 C); this process requires a longer fixing time. Rapidly diffusing cationic dyes and dye solvents, which exhibit a carrier effect, are required. When dyeing with basic dyes, special levelling agents (also called retarding agents) are widely used to control the absorption rate of the colourant on the fibre, thus improving level dyeing. Cationic dyes are slightly soluble in water, while they show higher solubility in acetic acid,ethanol, ether and other organic solvents. In dyeing processes, they are applied in weak acidconditions. Basic dyes are strongly bound to the fibre and do not migrate easily. In order toachieve level dyeing, specific levelling auxiliaries, (also called retarders) are normallyemployed (unless a pH controlled absorption process is used). The most important group ofretarders is represented by quaternary ammonium compounds with long alkyl side-chains(cationic retarders). Electrolytes and anionic condensation products between formaldehyde and naphthalenesulphonic acid may also be found.
Environmental issues
Many basic dyes exhibit high aquatic toxicity but, when applied properly, they show fixation degrees close to 100 %. Problems are more often attributable to improper handling procedures, spill clean-up and other upsets The following dyestuffs have been classified as toxic by ETAD:
Basic Blue 3, 7, 81 Basic Red 12 Basic Violet 16 Basic Yellow 21

Acrylic - Acetic acid (pH 3.6 - 4.5) - Salt (sodium sulphate or sodium acetate) - Retardant auxiliaries (usually cationic agents) - Non-ionic dispersing agents - Acetic acid (pH 4.5) - Dye solvent - Steam-resistant, readily-soluble dyes (usually liquid) are required - Dye solvent - Rapidly diffusing dyes are required Batch Pad-steam process with pressurised steam Pad-steam process with saturated steam Source: European Commission 2003
Since the dye fixing to the fibre does not depends on its molecular weight, it is possible to use small molecules obtaining very bright dyes, whereas the covalent bond that is formed between the fibre and the dye ensures the fastness to washing. Before reactive dyeing: cellulosic fibre dyeing was carried out almost exlculsively with dyes having affinity for the fibre after being dissolved in the dye bath; this menat the dyes used were directly soluble or soluble inr educed form and were absorbed by the fibre and united to it by secondary bonds, or by internal depositing of the insoluble dye that remained trapped in the macrmolecular reticle of the fibre and sometimes undited by secondary bonds. With soluble type dyes there was the problem of an imcompatibility between dye brightness and washing fastness, as to have the former, chromopshore with small molecular weight are necessary, which giv e low washing fastness it being only possible to esthablish a few secondary bonds between the fibr and the dye molecule.
9.3
APPENDIX ALTERNATIVES SCHEMES
Process Desizing of woven fabric Scouring / removal of serecin in silk Bleaching
Enzymes Enzymes Enzymes
Plasma application
Process optimisation Process optimisation Process optimisation Process optimisation Process optimisation Process optimisation Process optimisation Process optimisation Process optimisation
Waste water treatment Waste water treatment Waste water treatment Waste water treatment Waste water treatment Waste water treatment Waste water treatment Waste water treatment Waste water treatment
Substitution of chemicals Substitution of chemicals Substitution of chemicals Substitution of chemicals Substitution of chemicals Substitution of chemicals Substitution of chemicals Substitution of chemicals Substitution of chemicals
Optical brightening Mercerising/ causticizing Weighting Carbonising Plasma application Fulling/crabbing thermo fixing Anti felting Plasma application Reactive Special dye selection (low salt high fixation) Dye bath replenishing Special dye selection (prereduced) Special dye selection (predreduced) Avoid use of naphthol Dye bath replenishing natural dyes (without use of heavy metals) Avoid use of naphthol
Plasma application
Direct (substantive) Vat (reduced)
Process optimisation Process optimisation Process optimisation Process optimisation Avoid use of naphthol Process optimisation Process optimisation Process optimisation Process optimisation Process optimisation
Waste water treatment Waste water treatment Waste water treatment Waste water treatment Avoid use of naphthol Waste water treatment Waste water treatment Waste water treatment Waste water treatment Waste water treatment
Substitution of chemicals Substitution of chemicals Substitution of chemicals Substitution of chemicals Avoid use of naphthol Chemical Subsitution Substitution of chemicals Substitution of chemicals Substitution of chemicals Substitution of chemicals
Sulphur (leuco sulphur or solubilised sulphur) Napthol (azoic dyes developed on the fibre) Acid (metal-free) Chrome (mordant)
Metal complex Basic (cationic) Disperse Dye bath replenishing CO2 dyed solution dyed.
Water based (reactive, vat, disperse) Pigments Plastisol
screen print optimisation screen print optimisation screen print optimisation
Digital Ink-jet Digital Ink-jet
Process optimisation Process optimisation Process optimisation
Waste water treatment Waste water treatment Waste water treatment
Substitution of chemicals Substitution of chemicals Substitution of chemicals
Reactive Direct (substantive) Vat (reduced)

Sulphur (leuco sulphur or solubilised sulphur) Napthol (azoic dyes developed on the fibre) Acid (metal-free) Chrome (mordant) Metal complex Basic (cationic) Disperse Natural dyes CO2 dyeing Plastisols (print paste) Desizing of woven fabric Scouring / removal of serecin in silk Bleaching Optical brightening Mercerising/ causticizing Weighting Carbonising Fulling/crabbing thermo fixing Anti felting Enzyme bleaching Enzyme desizing Enzyme scouring
CO2 dyeing
Natural dyes
Reactive Direct Vat Sulphur Acid Basic Disperse
Naphthol Metal-complex
Pigment printing Transfer printing
Plastisol print paste Discharge print paste resist print paste
Enzyme bleach Enzyme desizing Enzyme scouring
Mercerising Weighting Carbonising Fulling Anti felting
desizing scouring bleaching optical brightening
THIS CHART DOES NOT TAKE INTO ACCOUNT ANY AUXILIARY CHEMICALS, PROCESS CONDITIONS, MACHINE USE, WASTE TREATMENT AND IS THEREFORE INCOMPLEET AND NOT VALUABLE. IT IS BASED ON EMPERICAL RESEARCH, NO PARAMETERS WERE SET (SEE CHAPT 4 COMPLEXITY) AND PURELY BASED ON WRITTEN INFORMATION, THUS NO STATISTICS.
9.4
APPENDIX QUESTIONNAIRE RESULTS
Wet Processing Questionnaire In order to find out and create a useful WP benchmark/framework I am trying to figure out how much knowledge there is about wet processes used for the production of your collections. Therefore these questions are quite detailed. I would be grateful if you could give me as much information as possible, but if you do not have the answer please also state why not. (eg, communicated through agents or decisions are made by dyehouse). Decisions made about dyes&prints: 1. Do you (as a company) make decisions about dyes and prints in the design phase? If yes, what kind of decisions/choices? Yes, together with the styling department we decide on design and colour.
2. Do you make decisions about dyes and prints in the sourcing phase? If yes, what kind of decisions/choices? Yes, the decisions on design and colour are linked to the decision on where and from which factory to source. 3. Do you make decisions about dyes and prints in the production phase? If yes, what kind of decisions/choices? Yes, based on the order that was appointed to the supplier in question. Dyes: 4. Could you name the dyestuffs most used for your collections? (eg, reactive dyes, direct dyes, acid dyes, etc..) Acid dyes (not for Pure), direct dyes for Pure. We do not yet work with reactive dyes. 5. Do you use natural dyes? Which ones? Mud Jeans, supplier of the denim articles for Pure, work with natural dyes. 6. Could you name the dyeing stage most used for your collections? (eg, yarn dyeing, piece dyeing, garment dyeing, etc..) Yarn dyeing. 7. Could you name the dye methods most used for your collections? (eg, batch dyeing, continuous dyeing, pad-batch dyeing) We dont know as we only source at CMT level. Prints: 8. Could you name the prints most used for your collections? (eg, direct print, discharge print, plastisol print, flock print, etc) Most used print is direct print (allover print & placement printing). 9. Could you name the inks most used for your collections? No, we cannot. 10. Could you name the print methods most used for your collections? (eg, roller printing, screen printing, digital printing etc.)
Screen printing and digital printing. Finishes: 9. Could you name the wet finishes most used for your collections? Wet finishes applied to denim items for Pure (finish unknown, but can be checked with denim supplier Mud Jeans). We apply the regular finishes. Communication: 10. Do you directly communicate with the dyehouse? NO If yes, about what? (related to dyes/prints) If no, would it be possible to communicate with the dyehouse or is it too far away in the supply chain? Unfortunately it is too far away in the supply chain. 11. Do your agents communicate with the dyehouse? 12. Does your CMT communicate with the dyehouse? NO YES
Focus of the tool: 13. Could you rank the word below, from most important (1) to least important (5): Energy reduction _5_ _1_ No hazardous chemicals No pollution _2_ Waste water treatment _3_ _4_ Water use reduction -. __ 14. In your opinion, what would be a useful tool and offer you a perspective for action? A. An overview with hazardous chemical ranked B. An overview with dyestuffs ranked? C. An overview with dye methods ranked? D. An overview with type of prints ranked? E. All of the above? F. Any other suggestions? A benchmark on wet finishes in general would be very useful. 15. Could you give some feedback about the fibre benchmark? Do you think it is a useful tool? And why? Have you used it as a guideline while sourcing fabrics? The benchmark is a very useful too. We use it as a guideline for our sustainable sourcing decisions for Pure and any other sustainable textile items we source. An update on the benchmark (if applicable) would be very much appreciated. Thank you very much for answering this questionnaire. Your input is very much appreciated. Kind Regards, Anne Moor anne.moor@made-by.nl 0031(0)20-5230664
Wet Processing Questionnaire In order to find out and create an useful WP benchmark/framework I am trying to figure out how much knowledge there is about wet processes used for the production of your collections. Therefore these questions are quite detailed. I would be grateful if you could give me as much information as possible, but if you do not have the answer please also state why not. (eg, communicated through agents or decisions are made by dyehouse). Decisions made about dyes&prints: 1. Do you (as a company) make decisions about dyes and prints in the design phase? If yes, what kind of decisions/choices? Yes, we define what kind of print and dye we need in terms of Discharge/reactive printing, and pigment dye or reactive dye.
2. Do you make decisions about dyes and prints in the sourcing phase? If yes, what kind of decisions/choices? Normally instructions from design phase is followed, but do some extend we have some discussions if we face problems To follow initial instructions
3. Do you make decisions about dyes and prints in the production phase? If yes, what kind of decisions/choices? Same as above
Dyes: 4. Could you name the dyestuffs most used for your collections? (eg, reactive dyes, direct dyes, acid dyes, etc..) Reactive dye, pigment dye 5. Do you use natural dyes? Which ones? We have used vegi dye on some jeans some seasons ago
6. Could you name the dyeing stage most used for your collections? (eg, yarn dyeing, piece dyeing, garment dyeing, etc..) Garment dye, piece dye, yarn dye is mostly used.
7. Could you name the dye methods most used for your collections? (eg, batch dyeing, continuous dyeing, pad-batch dyeing) I do not know this.
Prints:
8. Could you name the prints most used for your collections? (eg, direct print, discharge print, plastisol print, flock print, etc) Reactive printing and discharge printing. 9. Could you name the inks most used for your collections? I do not know. 10. Could you name the print methods most used for your collections? (eg, roller printing, screen printing, digital printing etc.) Roller prints and screen prints.
Finishes: 9. Could you name the wet finishes most used for your collections? Garment wash, enzyme wash, silicone wash, stone wash, sand wash
Communication: 10. Do you directly communicate with the dyehouse? YES/NO If yes, about what? (related to dyes/prints) NO 11. Do your agents communicate with the dyehouse? 12. Does your CMT communicate with the dyehouse? YES/NO - NO YES/NO - YES
Focus of the tool: 13. Could you rank the word below, from most important (1) to least important (5): Energy reduction _4_ No hazardous chemicals _2_ No pollution _5_ Waste water treatment _1_ Water use reduction _3_ -. __
14. In your opinion, what would be a useful tool and offer you a perspective for action? A. An overview with hazardous chemical ranked we have this in our Standard Operation Procedure B. An overview with dyestuffs ranked? XXXX C. An overview with dye methods ranked? XXXX D. An overview with type of prints ranked? XXXX E. All of the above? F. Any other suggestions? Overview of finishings ranked.
15. Could you give some feedback about the fibre benchmark? Do you think it is a useful tool? And why? Have you used it as a guideline while sourcing fabrics? It is very very usefull and we use it a lot in our department
Thank you very much for answering this questionnaire. Your input is very much appreciated. Kind Regards, Anne Moor anne.moor@made-by.nl 0031(0)20-5230664

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The environmental impact of Wet Processing & how to improve sustainability: Written for MADE-BY

Anne Moor International Fashion Management 2010

Wet Processing Thesis 9 November 2010 Final Thesis

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Name of degree course:

Type of report: Coach: Place: Date:

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Fig. 1 Scorecard Jackpot. Source: MADE-BY.com

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Waste water emissions: BOD, COD, AOX

Solid emissions: sludge

Fig. 3 Environmental Impact and Emissions, Authors own.

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Fig. 4 WEC Use Dyeing Finishing. Source: Cotton incorporated 2010

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Fig. 5 Water scarcity world. Source: Molden 2007

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Fig. 6: Coloured streams. Source: flicr.com

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Fig. 8: pH scale. Source: http://climatechange.wikispaces.com

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Fig. 10: Processing Methods. Source: Schonberger and Schafer, 2003

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