Increasing consideration of ecologic consequences of industrial processes as well as legislation enforcing avoidance of environmental problems have caused a reorientation

of thinking & promoted projects for replacement of conventional technologies. Quality standards to be met by industrial wastewaters will certainly be raised in future that in turn causes unpredictable increases in costs, particularly thoseincurred by having to disposeofdyehouseeffluents. Dyeing process of fibers in supercritical carbon dioxide (scCO2) is an example of a clean process suitable for fulfilling many of requirements of sustainability Here, a recyclable process medium(CO2) is used together . with an efficient & minimum input of chemicals (only dyes, no auxiliaries) & energy (low dyeing times, fusion of processes, no drying) & with minimal emissions & waste production. Q lit f d d materialsis also very hi h i i t d ti Qualityof dyed t il i l high.

Supercritical Fluid Dyeing of Textiles Introduction

What is Supercritical Fluid?

Any gas above its critical temperature retains free mobility of gaseous state but with increasing pressure its density increases towards that of a liquid. Supercritical fluids are such high compressed gases & q p g p g as such they combine valuable properties of both liquid & gas. No distinction between gases & liquids. Properties intermediate between those of gases & liquids. Do not condense or evaporate to form a liquid or a gas. p q g Unit
Density Diffusion Coefficient Viscosities gm/cm2cm2 cm cm2cm/sec gm/cm2sec

Gas
1/1000 1/10 1/10000

Liquid
1 5/10000 1/100

Supercritical Fluid
0.6 1/1000 1/10000

Environmental Compatibility of CO2

No Smog Non-Toxic No Damage to Ozone Layer Non Carcinogenic Non-Carcinogenic Non-Flammable & Non-Corrosive Virtually Inexhaustible No Disposal Problem

345 ppm 315 ppm 1960 1990

380 ppm 2003

Physiochemical Properties of CO2 At critical point, temperature of CO2 is 31.1oC & pressure 73.8 bar. Below critical parameters two distinct phases of liquid & gaseous

CO2 are separated by phase boundary boundary. As temperature & pressure rise along vapourliquid coexistence line, liquid CO2 expands & the two phases become less distinct forming a so-called supercritical phase. Above critical point, vapourliquid line completely disappears. vapour liquid Viscosity of supercritical fluids is more gas-like.

Current SCF Dyeing Technologies

For significance of PET & cotton, development of supercritical fluid dyeing technologies worldwide is mainly focused on these fibers. Dyeing of PET works very well in scCO2, dyeing of polar fibers like cotton is still challenging when high fastness properties & color yields are required. Limitations of dyeing natural fibers in scCO2 arise from inability of CO2 to break hydrogen bonds the low degree of fiber swelling & low reactivity of OH-bonds in cellulose in slightly acidic CO2 medium. Furthermore, disperse dyes only show slight interactions with polar fibers, leading to unacceptably low fastness data.

Environmental aspects of PET Dyeing in CO2

It is evident that conventional water dyeing is an end-of-pipe process, whereas with scCO2 a quasi-closed loop process can be accomplished. After precipitation of spinning oils & excess dye in a separator, CO2 is recycled & can b reused. Q be d Quasi means extraction residues of d t ff & spinning oils i t ti id f dyestuffs i i il are not recyclable as well as about10% of CO2 released into atmosphere

Process Steps
Water Step:

scCO2 Step:

Dyeing Process

Process Flow
Extraction I represents partial extraction of spinning oils Extraction-II is started for removal of adhering dye from fabric surface by rinsing with fresh cold scCO2. Temperature in plant is decreased as fast as possible below Tg of polymer to avoid extraction of dye from the fiber bulk. Extracted dyes & spinning oils are precipitate d in a separator. separator

Dyeing:

Microscopic View of Dyed S Mi i Vi f D d Sample l

Standard Sublimation
Dye does not penetrate fibers but rather sits on top where it can easily h i il wear off. White fiber shows after cutting or needle penetration

Controlled Penetration

After treatment in an aqueous dye-bath & postdye washing, fibers show complete dye penetration. Colorfastness & adherence C l f t dh is low to moderate when exposed to cleaning agents.

Conventional Dyes

Complete Penetration.

Process Conditions

Time: For a dye uptake of 2%, a dyeing time of 40mins in Technical plant & 60mins in Industrial plant is needed.

Dye uptake of PET in scCO2 is equivalent to a minimum of 4% in water dyeing, when estimating an amount of auxiliaries in dye formulation of 50%.

Temperature & Pressure Programs

Total time is much less as compared to PET dyeing in water including rinsing/washing & drying (6-8hr.)

Energy Consumption
4.53 kWh /kg

Although treatment time in scCO2 is significantly lower compared with water dyeing process including drying, energy consumption of both processes seems to be similar.

Probable Reasons

Economization

Warm up before dyeing & cooling in Extraction Step-II of thicker steel Step II walls of scCO2 plant, need more energycompared with a waterdyeingplant. Electrical energy consumption in also include cooling energy for liquefaction of CO2 for recycling, was not considered for water-basedprocess. When considering minimal waste production as d Wh id i i i l t d ti demanded f d d for environmentally sound processes, scCO2 dyeing of PET is really a clean finishing process because only dyes are needed. For comparison, environmental impact of analogous water-based process is summarized. Based on significantly shorter process times, in scCO2 theoretically up to six process cycles could be accomplished per day.

Product Quality
Allshades as in water dyeing but also highcolor yields are obtained. No differences in reflectance spectra at inside, middle, & outside of fabric pack were found indicating a high levelness of dyeing dyeing. Alldyesapplied in thisprocess are approved by Oeko-Tex 100 Standard. Compared with water dyeing process on an industrial scale, wash fastness of PET when dyed in same shade is sometimes up oo eg a e g e . to one grade higher. Stressstrain & viscosmetric molecular weight measurements of scCO2 dyed PET show that no fiber damage takes place under optimum dyeing conditions

Other Application in Textiles

The UV stabilizer or even perfumes may be transferred to fiber. New classes of polymeric compounds have been developed with good solubility in liquid CO2. Thesecompounds are appliedfor non-aqueoussizing. Supercritical NH3 can be used for mercerization. High Investment Cost. High Pressure required for dye solubility. Impact of dyeing machine weight is related to circulation. Difficult to dye Natural Fibers.

Disadvantages

Textile dyes classification: Directs Reactive Acids/Basics Sulphur Vat Mordant Disperse Pigments

Not Dissolved in Sc- CO2

Disolved in Sc-CO2

Future Trends

Dyeing of supercritical fluid was limited to synthetic fibers but dyeing of natural fibers is under progress. Chemical modification of natural fabrics before dyeing is one of possible treatments. Reverse micelles provide a stable aqueous micro environment consisting of a water pool in non-aqueous medium. Cellulose material by impregnating with hydrogen bond breaking chemicals & or modification of cotton is done & afterwards pressure & temperature release dyestuff is trapped inside fiber.

Conclusion

Dyeing in scCO2 has been identified as one of the best alternatives to water-based dyeing. But, this favorable concept is waiting for its commercial implementation. Successful commercialization of above concept d fi it l i t definitely improves economics of d i i f dyeing b way of by f elimination of wastewater discharges.