Non-surfactant auxilaries and applications

Wirote Sarakarnkosol

Non-surfactant auxiliaries : Classification

Electrolyte pH control Enzyme Reducing and Oxidising agents Sequestering agent Thickener and Migration inhibitor Hydrotropic agents Fastness improving agents

Electrolyte

Electrolyte

NaCl and Na2SO4 are commonly used.

Increase the adsorption of Reactive and Direct dyes on cellulose. (Also for leuco Vat and Sulphur dyes) Promote aggregation of soluble dyes. NaCl gave stronger effect than Na2SO4.

Electrolyte

Decrease the adsorption of Anionic dyes on PA and WO.

NaCl gave more decreasing the adsorption of anionic dyes on PA than Na2SO4 !!

Kosmotropes increase hydrophobic increase dye adsorption Chaotropes decrease hydrophobic decrease dye adsorption

Electrolyte:
: Equilibrium adsorption isotherm at 34oC and rate of dyeing at 40oC for CI Direct Blue 1 on viscose in the presence of electrolyte singly and binary mixture

Electrolyte:
: Fixation of CI Reactive Red 180 with various concentrations of Group IA chlorides

Electrolyte:
: Fixation of CI Reactive Red 180 with various concentrations of potassium salts of dicarboxylic acids
K oxalate

K tartrate

K phthalate

Electrolyte : Ecological approach

High salt loading is indesirable in wastewater. Na2SO4 causes corrosion of concrete pipes.

pH control :

pH control : 3 differents technique

1. Maintenance of a high degree of acidity or alkalinity 2. Control pH within fairly narrow tolerance mainly in the near-neutral region (pH 4-9) 3. Gradual shifting of the pH as dyeing proceeds

pH control : Maintenance of a high degree of acidity or alkalinity

Easy to control Acid region use in application of levelling acid and 1:1 metal complex dyes to PA and WO. Alkali region use in reactive, sulphur or vat dyes to CEL.

pH control:
Normality Material Hydrochloric acid HCl Sulphuric acid H2SO4 Formic acid HCOOH Lactic acid C3H6O3 Acetic acid CH3COOH g/l pH g/l pH g/l pH g/l pH g/l pH

pH value of some common acid in distilled water.

2N 92.0 1.61 180.0 1.78 120.0 2.18

1N 36.5 0.11 49.0 0.24 46.0 1.79 90.0 1.97 60.0 2.40

0.1 N 3.65 1.08 4.9 1.17 4.60 2.32 9.00 2.43 6.00 2.87

xN 1 g/l 1.61 1 g/l 1.79 1 g/l 2.76 1 g/l 2.94 1 g/l 3.27

0.01 N 0.37 2.00 0.49 2.05 0.46 2.85 0.90 2.95 0.60 3.37

0.001 N 0.037 3.00 0.049 3.00 0.046 3.42 0.090 3.50 0.060 3.89

pH control:
Normality Material T.S.P.P. Na4P4O7 Sodium carbonate Na2CO3 Ammonia NH4OH Sodium phosphate Na3PO4 Sodium hydroxide NaOH g/l pH g/l pH g/l pH g/l pH g/l pH

pH value of some common base with concentration.

2N 106.0 11.60 34.0 11.72 98.6 12.8 -

1N 83.0 10.50 53.0 11.50 17.0 11.59 49.3 12.30 40.0 13.93

0.1 N 8.30 10.15 5.30 11.00 1.70 11.16 4.93 11.40 4.00 12.98

xN 1 g/l 9.35 1 g/l 10.30 1 g/l 11.00 1 g/l 11.20 1 g/l 12.38

0.01 N 0.83 9.25 0.53 10.00 0.17 10.64 0.49 11.10 0.40 12.00

0.001 N 0.083 9.01 0.053 9.80 0.017 10.15 0.049 10.95 0.040 11.00

pH control : Near-neutral region (pH 4-9)

Very difficult to control. pH of pure water 7.47 at 0oC, 7.00 at 24oC and 6.13 at 100oC. Use in Milling acid and 1:2 metal complex dyes on PA and WO., Basic dyes on PAN and Disperse dyes on PES, PA, PAN. Precise control with buffer.

pH control : Buffer
Buffers are generally based on combinations of weak acid + its base salt or weak base + its acid salt Most common buffer is acetic acid/sodium acetate (pH range 3.8 5.8) Low cost

Buffer : Phosphate buffer

More cost than acetate buffer More resistant to temperature induced change Buffering region at pH 2.5-3.5, pH 6-8 and pH 10.5-11

Buffer : Others
Pyrophosphoric acid (H4P2O7) and its salts (pH 39) Orthoboric acid (H3BO3), sodium tetraborate (borax Na2B4O7) and sodium hydroxide (pH 8.110.1) Citric acid and sodium hydroxide (pH 2.16.4) Sodium carbonate and sodium bicarbonate (pH 9.311.3).

pH control : Shifting of the pH

Acid shift region use for non-migrating anionic dyes on WO or PA. Ammonium salts is the conventional system for acid shifting. Alkali shift region use for reactive dyes on CEL. Sodium salts of volatile acid is the conventional system for alkaline shifting.

Acid shifting : Ammonium salts

Ammonium sulfate generally used for dyeing milling acid dyes on PA and WO. Can be used only open system.

Volatile to atmosphere

Acid liberate

Acid shifting : Hydrolysable ester

Can be used alone or mix with alkali for higher starting pH. Can be used in closed system High cost Such as Ethylactate

Lactic acid

Acid shifting : Hydrolysable ester

Acid part Alcohol part Acid part Alcohol part

Diethyl tatrate

2-Hydroxyethyl chloroacetate

Acid shifting : Lactone

-butyrolactone

Alkaline shifting : Salt of weak acid

Sodium acetate

Alkali liberate

Sodium formate and Sodium bicarbonate are also used for reactive dyes on CEL printing.

Enzyme :

Enzyme :
Biocatalyst for accelerating the reaction -amylase use for desizing process Catalase for removing residual H2O2 after bleaching Cellulase for biofinishing of denim Etc.

Amylase enzyme for desizing

Convert starch to water-soluble product Non-ionic wetting agent should be combine used Temperature range cover 20 115oC :Prefer > 70oC (gelatinous point of starch) pH range cover 5.5 9 : Prefer pH 7 8 (condition for degraded product solubilisation) Salt and Hardness maybe require. Detect residual starch with Iodine solution

Amylase enzyme for desizing

Mode of action of enzymatic degradation : by SDC

Amylase enzyme for desizing

Optimum conditions for enzymatic desizing : by SDC

Amylase enzyme for desizing

Test for degree of desizing (TEGEWA scale) : by SDC

TEKEWA Rating 1

TEKEWA Rating 7

Catalase :
Remove residual H2O2 to water and oxygen. Activity range pH about 5-9 Activity range temperature 50-55oC Do not destroy the dye molecules.

Catalase :Hydrogenperoxide removal efficiency

Liquor condition 0.1 g/l 50% Hydrogenperoxide 0.1 g/l Organic stabilizing agent X g/l Product test Procedure : Keep the dye liquor at XC for 10 min. and follow dyeing with H2O2 sensitive reactive dyes Further dyeing : 1 % Sensitive Reactive Blue dye. 40 g/l Common salt 20 g/l Soda Ash 60 min at 60C LR 10:1 Material: knitted cotton

Cellulase

Can convert Cellulose to soluble product Partially or wholly replacement of Pumice stone abrasion on cotton denim fabric. Saving in time and labour, much less fabric abrasion and no debris. Devided to Neutral and Acid cellulase Contain endocellulase, exocellulase or betaglucanases

Cellulase :Dissolution of the cellulose

Cellulase : Denim finishing

Denim is cotton twill-weave fabric with a dyed warp with INDIGO and raw white weft. Acid cellulases (pH 4.55.5 ; 4555oC) give high aggressive action on cotton which use shorter time but backstaining. Neutral cellulases (pH 68 ; 5060oC)have less aggressive action but less or no backstaining. Terminated with inactivating, by raising the pH to 10 or by increasing the temperature to75oC for 1015 minutes.

Reducing agent & Oxidising agent

Reducing agent & Oxidising agent

Coloration assistance - Reducing agent for Vat & Sulphur dyes - Re-oxidising agent for Vat & Sulphur dyes

3 ACTIONS

Decoloration of material - Bleaching - Stripping

Redox inhibitor - Reduction inhibitor - Antioxidant

Reduction of Vat dyes

Reducing agent : Vat dyes assistant

Reduction potentials of various reducing agents measured as 5 g/l solutions in 15 ml/l caustic soda 38oB at 60oC

- Vat dyes have reduction potentials in aqueous media from 770 to 1000 mV the majority 900 to 950.

Reduction of Sulphur dyes

Sulphur dyes

Reducing agent : Sulphur dyes assistant

Reduction potentials of various reducing agents measured as 5 g/l solutions in 15 ml/l caustic soda 38oB at 50oC

Sulphur dyes have average only about 600 mV

Reduction clearing of Disperse azo dyes

Example
Cl O2N Cl N N N CH3 4H O2N Cl Cl NH2 + H2N N CH3 CH2CH2OH

CH2CH2OH

CI Disperse Orange 5

Reducing agent :
Fastness of black polyester dyeings after various reduction clearing treatments

Reducing agent : Sodium dithionite /Hydros/Sodium hydrosulphite

Most important reducing system for the batchwise application of vat dyes in a solution of sodium hydroxide. For sulphur dyes, the process is difficult to control and may be destroyed through OVER-REDUCTION. But effective with CI Solubilised Sulphur and sulphurised vat dyes. Reduction clearing for Disperse dyes.

Reducing agent : Sodium dithionite /Hydros/Sodium hydrosulphite

Reduction reaction of hydros with Vat dyes

Reduction reaction of hydros with atmosphere

Reducing agent : Sodium dithionite Environmental problems

Can produce sulphite and sulphate. Sulphite can be oxidised easily to sulphate High concentrations of sulphate can cause damage to unprotected concrete pipes.

Reducing agent : Sodium sulphide and Sodium hydrogen sulphide

Most widely used for Sulphur dyes At least 12 g/l sodium sulphide is required to dissolve the water-insoluble CI Sulphur dyes Sodium hydrogen sulphide is use 0.6 times of sodium sulphide but necessary to add alkali (10 g sodium hydroxide or 5 g sodium carbonate per 7 g sodium hydrogen sulphide)

Reducing agent : Sulphide Environmental problems.

Toxicity of hydrogen sulphide. Odour threshold being 0.035 0.14 mg/m3 Unpleasant odours (pH < 9) Neutralisation or acidification can occur gaseous hydrogen sulphide. Corrosion of the effluent drainage system. Damage to the treatment works and the often associated high pH.

Reducing agent :Thiourea dioxide/ Formamidine sulphinic acid

Powerful reducing agent for vat dyes. Lower MW than sodium dithionite. Lower sulphite and sulphate load. More stable than sodium dithionite. Cause over-reduction of indanthrone vat dyes. Glucose or sodium nitrite cant stabilise. Very good for reductive colorant stripping.

Reducing agent :Thiourea dioxide/ Formamidine sulphinic acid

Formamidine-sulphinate in alkaline media is more readily oxidised than dithionite. Low water solubility. Not suitable for continuous process.

Thiourea dioxide

Sodium formamidinesulphinate

Sodium hydrogen sulphoxylate

Reducing agent : Sodium formaldehyde-sulphoxylate

Know as Rongalite C or Formulsol G Produce from Sodium dithionite with formaldehyde More stable than dithionite at lower temperatures

Reducing agent : Sodium formaldehyde-sulphoxylate

Can be used to prepare stable pad liquors and print pastes. At higher temperatures, they are capable of rapid reduction of vat dyes. Used first in conventional steam fixation of vat prints.

Reducing agent : Other sulphoxylates

Sodium acetaldehyde is suitable for flash-ageing process. Zinc formaldehyde sulphoxylate : - Mono zinc : Water soluble - Di zinc : Water insoluble Calcium formaldehyde sulphoxylate is insoluble in water which low tendency to haloing

Sod. acetaldehyde sulfoxylate

Mono Zinc formaldehyde sulfoxylate

Calcium formaldehyde sulfoxylate

Reducing agent : Hydroxyacetone

Sulphur-free and biodegradable Used for vat, sulphur and indigo dyes with high concentrations of NaOH Does not over-reduction of indanthrone. Give different shades with carbazole dyes, compared with sodium dithionite

Reducing agent : Glucose

Characteristic odour preferable than odour of alkaline sulphide bath. High alkali concentration is required. Minimum dyeing temperature of 9095oC being necessary. High COD level in the effluent. A lot of by-product ; losing its reducing action. Should mix with Hydros for higher efficiency

Reducing agent : Dithionite/glucose system

Reducing agent : Dithionite/glucose system

Potential slightly lower than that of dithionite alone, although glucose has the lowest potential. Without the risk of over-reduction. Optimal colour yield and good reproducibility Other glucose binary systems, including hydroxy- acetone or sodium formaldehydesulphoxylate as stabiliser gave similar results.

Reducing agent : Others

2-Mercaptoethanol Sodium hydrogen sulphite Iron Triethanolamine complex Iron Gluconic acid complex etc.

Reducing agent : Summary of advantages and

disadvantages of the three most important types reducing agent for indigo, vat or sulphur dyeing Sodium dithionite Advantages (1) Sufficient reduction potential for vat, sulphur or indigo dyeing (2) Good stability of leuco vat dyebaths Disadvantages (1) Waste water loading; inhibits biological degradation and leads to a greater oxygen demand (2) Can cause over-reduction at higher temperatures (3) Special safe storage facility required

Reducing agent : Summary of advantages and

disadvantages of the three most important types reducing agent for indigo, vat or sulphur dyeing Sulphinic acid derivatives Advantages (1) Sufficient reduction potential for vat, sulphur or indigo dyeing. (2) Especially suitable for high-temperature dyeing methods. (3) Good resistance to oxidation by air. Disadvantages (1) As for dithionite disadvantage (1) (2) Potentially temperature-dependent.

Reducing agent : Summary of advantages and

disadvantages of the three most important types reducing agent for indigo, vat or sulphur dyeing Hydroxyacetone Advantages (1) Biologically degradable (2) Ease of dosing in liquid form (3) Very good stability to storage Disadvantages (1) Does not reach full reduction potential and thus mainly suitable for indigo and sulphur dyes (2) Persistent odour (3) Limited commercial production

Oxidising agents : H2O2

Use for bleaching on Cotton and other CELs. Can use as re-oxidising agent for vat dye and sulphur dyes (easy but low washing fastness) Environmentally friendly (Very low AOX values) Peroxide bath do not corrosive Can be used both exhaustion and continuous Give a good whiteness even without prior scouring

Oxidising agents : H2O2

Fiber damage (occur by free radical formation especially in the present iron or copper) Quality of whiteness (Less attractive tone) Cost-effectiveness (AOX-containing effuent are omitted)
- 2 times of hypochlorite bleaching in batchwise process - 6 times of hypochlorite bleaching in continuous process

Oxidising agent :
AOX values for cotton bleached with various oxidising agents

1.) AOX value of 0.5 mg/l must not be exceeded in waste water released 2.) Limit for drinking water of not more than 0.01 mg/l

Oxidising agents : H2O2 : Effect of pH in bleaching

Optimum

Oxidising agents for bleaching : H2O2 : Mechanism of bleaching and fibre damage

Oxidising agents : H2O2 : Effect of Fe(III) concentration on rate of decomposition

2.9 g/l H2O2, Sodium Silicate 5 g/l, Magnesium Sulphate 0.2 g/l 95oC, pH 12 (Absence of substrate)

Schematic diagram of catalytic damage occurrence

Oxidising agents : H2O2 : Desizing of PVA

Oxidising agent : Sodium hypochlorite

Most environmentally damaging of all bleaching agent with regard to AOX values. May even be banned in some countries. Bleached goods are prone to subsequent yellowing on storage. Substrate must be scoured before bleaching. Stock solutions of sodium hypochlorite are unstable and must always be chemically analysed before use. Hypochlorite bleaching can not combine with some FWAs and dyestuff.

Oxidising agent : Sodium hypochlorite

Economical attractiveness Lower risk of catalytic fibre damage, although some chemical damage can occur depending on temperature and pH Powerful bleaching action. High attractive whiteness (Bluish white)

Oxidising agent : Sodium hypochlorite

Effect of pH on the composition of sodium hypochlorite solutions

Oxidising agent : Sodium hypochlorite

After bleaching with hypochlorite it is always necessary to remove residual chlorine present call Antichlor Bisulphite and hydrogen peroxide are generally used for antichlor

Oxidising agent : Sodium chlorite

Lower AOX values than hypochlorite. Generally carried out under acidic conditions. (different from peroxide and hypochlorite) Risk of chemical damage is low. Minimal scouring action in acidic bleach results in lower weight losses hence good sewability Least sensitive to accelerated damage by metallic contamination useful for synthetic fibres and particularly important for acrylic fibres.

Oxidising agent : Sodium chlorite

Toxic and unpleasant chlorine dioxide vapour can be liberated. Highly corrosive. No rapid chlorite bleaching process is available. Bleached goods gave lower absorbency. Some dyes and FBAs are destroyed by chlorite bleaching

Oxidising agent : Sodium chlorite : Effect of pH on the composition of sodium chlorite solutions

Oxidising agent : Peracetic acid

Peracetic acids can be effective oxidative bleaching agents and, at least potentially, offer an alternative to the environmentally sensitive chlorine bleaches.

Oxidising agent : Dichromate and chromate salts.

Sodium and Potassium salts are generally used. Use combine with acetic acid (pH 4.5-5.5) for reoxidising sulphur dyes Gave the harsher handle and less hydrophilic of dyed fabric Can not use in yarn dyes because its decrease the winding property of yarn.

Oxidising agent : Dichromate and chromate salts.

If combine with Copper salt, Light fastness is improved Provide high washing and rubbing fastness. Environmental problem due to Cr3+ Low cost Sometimes use as antireduction for disperse dyes on T/C.

Oxidising agent : Iodate salts

Potassium iodate is generally used. For re-oxidise of sulphur dyes, no harsher handle and high rubbing fastness. Use combine with Lactic or Acetic acid (pH 3.5-5) Not Formic acid!! Very high cost. Maybe use as anti-reduction for disperse dyes on T/C.

Oxidising agent : Sodium m-nitrobenzene sulphonate

Use as anti-reduction for reactive, direct and acid dyes. Protect the reduction of azo group via heat or unfavorite condition. Can re-oxidise Vat and Sulphur dyes.

NO2 2H SO3Na SO3Na NH 2