TEXTILE PRETREATMENT : RIGHT FIRST TIME

Wirote Sarakarnkosol

Why do Pretreatment is important?

Satisfactory preparation of the substrate before dyeing and finishing makes major contributions to consistent attainment of the desired end-product quality.

well prepared is half-dyed

Factor for Successful Preparation of Textile

Successful preparation depends on 4 factors the amounts of the various impurities present the purity of the water supply the chemicals used in the various preparation processes the machinery available for processing of the goods.

Troubleshoot in pretreatment :Factor to yellowing of textiles

Water Specification for textile wet processing

Average water consumption by fibre type

Water consumption by process

Preparation and Dyeing of Cotton

Cotton Impurities and Preparation Chemicals
Pectins are polygalacturonic acids and their calcium, magnesium and iron salts. The inorganic ash contains calcium, magnesium and potassium phosphates and carbonates. The spin finish and knitting oil contain mineral oil and surfactants applied to decrease friction on machinery parts. Sizing agents are film-forming polymers applied to warp yarns before fabric weaving in order to minimise yarn breakage. Metallic ion contamination, particularly iron and copper, is of serious concern during oxidative bleaching processes

Composition by mass of a typical cotton fibre

Important factors to select and use of surfactants in preparation

wetting agents used in the desizing stage must be compatible with the enzyme preparation detergents selected for scouring must be stable at the temperature and concentrations of alkali and electrolyte required surfactants added to bleach liquors must be stable to strongly oxidising conditions residual surfactants which retaining must not cause problems in subsequent printing or water-repellent finishing the cloud point of any nonionic surfactants used must be high enough to avoid impairing the wetting or detergency performance surfactants must be low-foaming to avoid risks of pump cavitation in circulating-liquor systems and loss of traction in conveyor or roller-bed steamers the viscosity of the surfactant solution should allow satisfactory performance in automatic dosing systems.

Sizing agents for different substrates

Desizing
Natural starch, starch ethers, cellulose ethers and polyacrylates are usually used as sizes. Economical starch-based formulations are effective for cotton yarns Poly(vinyl alcohol) is often preferred for sizing polyester/cotton blends
Waxy plasticisers may be added to the size mix.

Factors for Size removal

concentration and viscosity of the size formulation nature and amount of plasticiser present fabric construction ease of dissolution of the size washing-off procedure and temperature.

Enzymatic desizing
Amylase enzymes are highly effective catalysts for the hydrolysis of the amylose and amylopectin components of starch size. Normal type are applied for several hours at 65 to 70C Thermostable hydrolytic enzymes have been introduced, allowing brief dwell times at temperatures up to 120C. Common salt and calcium ions increase the rate of hydrolysis but amylase is deactivated by copper or zinc ions, as well as most anionic surfactants.
There is some interest in the use of pectinases as scouring agents and lignases to degrade the lignin in bast fibres, but as yet no commercial processes have been developed.

Scouring
is the hot alkaline process necessary to remove the non-cellulosic impurities. The main effects of this treatment are a 5 to 10% loss in mass and a dramatic improvement in wettability and absorbency. The change in mass results from degradation of protein to amino acids, conversion of pectin to soluble sodium salts, hydrolytic dissolution of hemicellulose and a limited amount of oxidative degradation of cellulose. Saponification of the cotton wax is incomplete but it has to become no longer capable of forming a continuous film over the fibre surface.

Oxidative desizing
reducing the number of fabric preparation stages, an important means of minimising the overall energy consumption. The oxidant can be added to the hot caustic scour liquor and little or no magnesium silicate or organic stabiliser is needed. Rapid desizing treatments require more critical control of alkali and oxidant concentrations. Increased oxidant above the minimum necessary for effective desizing and increasing the alkalinity for a given oxidant concentration both tend to increase the degree of chemical damage. Persulphates promote desizing rather than bleaching and require more critical control of concentration than does hydrogen peroxide.

Bioscouring
Bioscouring is a process in which an alkali-stable pectinase enzyme is applied to selectively remove pectin and waxes from cotton fibres. By hydrolysing the pectin material between the waxes and the fibre surface, the enzyme exposes the waxes to emulsification when the scouring bath temperature exceeds their melting range. Bioscouring does not eliminate motes (cottonseed fragments) or the natural colour of the cotton, which can be beneficial when scouring for a natural look

Hypochlorite Bleaching
Hypochlorite bleaches rapidly at ambient temperatures Less sensitive to transition-metal ions than peroxide but it does easily chlorinate organics present, it will turn to yellows on grey cotton by chlorinating the pectins and proteins. Cotton must be cleared of natural impurities by thorough scouring before bleaching. Must be followed by washing and an antichlor treatment with bisulphite. Prolonged, labour-intensive batchwise process with relatively low chemical costs but high water consumption. Chlorinated impurities are detected in effluent streams as absorbable organohalogens (AOX) and chloroform, which are environmentally unacceptable.
For these reasons, Hypochlorite bleaching will be abandoned

Advantages/disadvantages of bleaching with hypochlorite

Chlorite Bleaching
Sodium chlorite is used under acidic conditions Bleaching can be carried out on grey or desized cotton. Acidic conditions removes only a small proportion of the natural cotton wax, which can be advantageous in softening knitgoods and knitting yarns. Relatively unaffected by iron or copper contamination. Adequate fume extraction is essential, for ensuring protection against evolution of toxic chlorine dioxide gas from the acidic chlorite solution. The corrosive nature of this chemical demands exotic constructional materials such as titanium. The AOX generated by chlorite is much less than the amount generated by hypochlorite, but even this is more than twice that present after bleaching with hydrogen peroxide

Advantages/disadvantages of bleaching with chlorite

Hydrogen peroxide bleaching

Hydrogen peroxide is an extremely versatile bleaching agent, applicable over a wide range of temperatures (ambient to 130C) and times (minutes to days) by batchwise or continuous methods. Bleaching is carried out under alkaline conditions and this allows combined scour-bleach processes to be used. Bleaching with hydrogen peroxide is controlled by adding a stabiliser. Organic stabiliser including magnesium salts and
anionic polyelectrolytes such as silicates, polyacrylates protein degradation products sequestering agents to trap the transition-metal ions surfactants provide detergency during bleaching. Most of these products give adequate stabilisation in batchwise conditions but stabilisation in continuous pad-steam processes is more difficult.

Factors for hydrogen peroxide bleaching for cotton

exceptional versatility of application by batchwise or continuous methods a wide range of possible means of activation and stabilisation exceptionally innocuous to the environment, decomposing into oxygen and water.

Advantages/disadvantages of bleaching with hydrogen peroxide

AOX values for cotton bleached with various oxidising agents

Mercerisation
Mercerisation of cotton is achieved by saturation with cold caustic soda solution at about 25% w/w and containing a good wetting agent. Swelling of the fibres takes place, accompanied by shrinkage unless the fabric is held under tension. Mercerisation may be carried out on the grey, scoured or bleached substrate. Grey mercerising also fouls the liquor with size residues, causing instability and making caustic recovery for recycling difficult. Mercerisation enhances fabric lustre, smoothness, tensile strength, dyeability, dimensional stability and coverage of dead cotton.
influenced by alkali concentration, temperature and dwell time in alkali prior to washing-off

Preparation and Dyeing of Regenerated Cellulosic Fibres

Regenerated cellulosic fibres are desized by the same processes as for cotton. Care should be exercised with oxidative desizing in terms of both alkali and oxidant concentrations, which should be no more than half of those used for cotton. Most warps contain starch-based sizes and so enzyme desizing is customary. However, carboxymethylcellulose is sometimes used and in this case a cold swelling process followed by hot washing with a detergent is adequate

Tip for regenerated cellulosic fibres preparation

Viscose and other regenerated cellulosic fibres dissolve in caustic soda liquor at about 6.5% w/w (70 g/l), so causticisation rather than mercerisation is carried out using 3.3 to 5.5% w/w NaOH (35 to 60 g/l) to enhance wetting or dyeability. The addition of salt minimises the risk of damage. However, causticisation can cause uneven swelling of the fibres and lead to unlevel dyeing. Cellulase enzyme can widening of the voids in viscose fibres, making more internal surface available to alkali during swelling. A saving of 5 to 10 g/l caustic soda is attainable, as well as a more uniform and consistent swelling effect

Swelling action of regenerated cellulosic fibres in alkali

The swelling action of alkali on the strength and handle of viscose is less pronounced with more tightly spun yarns and woven fabrics. Better stabilisation is possible by fibre blending

Polynosic fibres are more resistant to alkali than regular viscose. Cotton/polynosic blends form an alkali-stable substrate that can be mercerised. The strong swelling of viscose results in an increase in the diameter of the fibre. Particular in the dyeing of cross-wound packages.
For this reason, packages of viscose staple yarn must be wound at a lower tension than cotton yarn

for example, viscose can be dyed with vat dyes without difficulty when blended with cotton or polyester.

Silk Degumming
Sericin forms the film outer covering of greige silk and is classified as a kind of scleroprotein or protective sheath. The sericin content of the filaments varies according to their position within the cocoon, those in the outermost layer having the highest content. Sericin is not a homogeneous protein but can be separated into four fractions on the basis of their differential solubilities in hot water Sericin and fibroin differ considerably in their chemical composition and accessibility, sericin being comparatively easily accessible to degumming chemicals

Various methods for degumming

aqueous extraction boiling-off in soap degumming with alkalis enzymes degumming in acidic solutions

Fully degummed silk, the degumming loss is 18 to 30%

Silk bleaching
normally carried out only for pale to medium dyeings or fabric sold as white. Reductive bleaching with hydrosulphite can be combined with alkaline degumming but it is more usual to give an oxidative bleach separately after degumming.

typical process would be for 2 to 4 hours at 70oC or 1 to 2 hours at 80 to 85oC, using 10 to 15 ml/l hydrogen peroxide (35% solution), 1 g/l EDTA (30% solution) and 3 g/l sodium pyrophosphate to pH 9, followed by thorough rinsing.

Traditional process sequence for polyester fabrics

Preparation of polyester
An aqueous scouring bath containing 1-2 g/l anionic detergent and 2 g/l sodium carbonate is satisfactory for most purposes Suitable detergents include fatty alcohol sulphates, alkylarylsulphonates and their mixtures with ethoxylated fatty alcohols. At the low liquor ratios applicable in scouring on the jig these concentrations should be increased threefold. The processing time and temperature may be adjusted according to substrate type, the degree of contamination and the available equipment. Woven or lightweight knitted fabrics prone to creasing should be treated in open width at 50 to 60C but many textured weftknit qualities can be scoured in rope form for a shorter time at the boil.
30 minutes at 60C is adequate in many cases

Preparation Preparation on blends of polyester with CEL

preparation sequence is determined by the quality and condition of the natural cellulosic fibre rather than the polyester component. If the grey goods contain starch size or other polymers not readily soluble or dispersible in water, it is necessary to extract or solubilise these contaminants before scouring. Even with the water-soluble size polymers it is often advisable to carry out an enzyme desizing process, because they may become difficult to solubilise after drying at temperatures above 100C.

Influence of preparation on disperse dyes

Disperse dyes are particularly sensitive to the influence of surfactants and polyelectrolytes, as regards both the quality and stability of the dispersion and the response of the dyes in exhaust dyeing systems. The dyeing of polyester at a temperature in the range 120 to 135C in circulating-liquor machines places severe demands on initial dispersion quality and subsequent stability under adverse conditions. The problem in the inherent instability of all dye dispersions, there being an overall tendency of fine particles to adhere together with formation of larger particles. It is this limited solubility that favours growth of particle size. The solubility of disperse dyes normally increases with temperature and dispersing agent concentration, although these effects vary greatly from agent to agent and from dye to dye.

Alkaline Pretreatment
Controlled alkaline hydrolysis of the surface layer of the fibres confers a limited degree of silk-like softness to conventional poly(ethylene terephthalate) materials. The resultant loss in mass is accompanied by an increase in surface polarity arising from the additional hydroxy and carboxyl groups formed by ester hydrolysis.

Influence of heat setting temperature

Influence of heat setting temperature on subsequent uptake of CI Disperse Red 1 by a polyester filament fabric

Oligomer : Cyclic tris(ethylene terephthalate)

Commercial samples of polyester fibres typically contain between 1.5 and 3.5% of the cyclic trimer

Variation of aqueous solubility of oligomer

Variation of aqueous solubility of cyclic tris(ethylene terephthalate) crystals with temperature

Cyclic tris(ethylene terephthalate) is a crystalline solid that melts at 314 to 319C. Although it can be hydrolysed by strongly alkaline solutions, the reaction is very slow because the cyclic trimer is almost insoluble in aqueous media

Sizing agents for different substrates

Degree of removal of residual sizing agent

Rapid scour-dye process for polyester

Weight reduction of polyester

Controlled alkaline hydrolysis of the surface layer of the fibres confers a limited degree of silk-like softness to conventional poly(ethylene terephthalate) materials. The resultant loss in mass is accompanied by an increase in surface polarity arising from the additional hydroxy and carboxyl groups formed by ester hydrolysis. additions of ethylenediamine to accelerate the hydrolysis by caustic alkali was examined in a rapid process for only 1 to 5 minutes at the boil.
Provide more hydrophilicity of polyester

Nylon Fibres
A heat setting treatment prior to dyeing normally prevents
Differences in the degree of swelling of nylon fibres arising from
the uneven absorption of moisture localised drying out of moist goods

It can result in unlevel shading faults

Whitening of nylon
Reductive bleaching with sodium dithionite under acidic or neutral conditions Oxidative bleaching with alkaline hydrogen peroxide, or with peracetic acid or sodium chlorite under acidic conditions Fluorescent brightening agents either alone or in the presence of a reducing agent

Why do nylon prefer reductive bleaching?

Oxidative bleaching treatments are the most effective in overcoming the yellowness of grey-set nylon but analysis reveals that some amino end-groups are oxidised and dye substantivity is lowered. This effect significantly impairs the resistance of the nylon to photodegradation and lowers the light fastness of dyeings and prints produced on the bleached substrate. The more drastic the oxidative bleaching treatment, the greater the sensitivity of the treated nylon to photodegradation. In most instances nylon is bleached under reducing conditions using sodium dithionite and a suitable fluorescent brightener under acidic conditions at pH 4 to 5.

Photodegradation of nylon
When nylon be in simultaneous contact with light, heat, air, water vapour, ozone and gas fumes. Can we solve with
UV absorber ? Or..

All these factors can catalyse or modify the fibre degradation reaction.

Factors that enhance the resistance of nylon to photodegradation (1)

Optimal purity of starting materials for polymerisation Minimal temperature of polymerisation, with exclusion of oxygen Inclusion of protective inorganic salts, particularly those of transition metals such as manganese (II) Inclusion of protective organic compounds as antioxidants

Factors that enhance the resistance of nylon to photodegradation (2)

Exclusion of fluorescent brighteners from the polymer Increased average molecular mass of the polymer Increased content of amino end-groups, as in deep-dye nylon variants Minimal temperature of the polymer melt, with exclusion of oxygen

Factors that enhance the resistance of nylon to photodegradation (3)

Minimal concentration of delustrant, using the optimal grade of titanium dioxide Selection of suitable spinning lubricants Draw ratio as high as possible to ensure maximum crystallinity, consistent with other commercial requirements Storage of grey fabric away from direct sunlight and away from heating systems

Factors that enhance the resistance of nylon to photodegradation (4)

Minimal temperature of heat setting in the grey state, consistent with the attainment of adequate set Treatment in a stenter designed for steam injection Alkaline rather than neutral or acidic conditions of scouring Oxidative bleaching should be avoided, but fluorescent brighteners can be applied under reducing conditions

Factors that enhance the resistance of nylon to photodegradation (5)

Dyes of high fastness to light (6-7) are preferred, with particular care in selecting suitable trichromatic combinations Certain metal-complex and milling acid dyes exert a protective effect on nylon, whereas others may catalyse photodegradation [15] Preferable to dye at or near pH 5, since more strongly acidic conditions can adversely affect antioxidants Inclusion of thiourea or hydroxylamine in the dyebath eliminates dissolved oxygen and minimises the risk of degradation in high-temperature dyeing