The Dyehouse Doctor

STANDARD DYEHOUSE LABORATORY MANUAL

ARTHUR C WELHAM

The Dyehouse Doctor Ltd Bluebell Cottage, Brearley Old Hall, Luddendenfoot, Halifax, West Yorkshire, HX2 6HS, UK www.dyehousedoctor.com enquiries: arthurwelham@gmail.com

CONTENTS
1.
1.1.

INTRODUCTION
HEALTH AND SAFETY

3
3

2.
2.1. 2.2.

FABRIC IDENTIFICATION
BURNING TEST CHEMICAL
IDENTIFICATION

3
3 4

3.
3.1. 3.2. 3.3. 3.4.

TESTING OF MATERIALS
FABRIC WATER SALT AND ALKALIS DYES

5
5 5 6 6

4.
4.1. 4.1.1. 4.1.2. 4.1.3. 4.2. 4.2.1. 4.2.2.

PREPARATION OF SOLUTIONS
DYES W EIGHING STORAGE AND HANDLING OF DYES IN THE LABORATORY DISSOLVING PROCEDURES OF DYES IN THE LABORATORY CHEMICALS SODIUM CARBONATE SODIUM HYDROXIDE

7
7 7 8 10 11 11 11

5. 6.
6.1.

PREPARATION OF FABRIC SAMPLES LABORATORY DYEING

FIXATION STAGE

12 12
13

7.
7.1.

AFTERTREATMENT
WASH-OFF
PROCESS

15
15

8.

FASTNESS TESTING

16

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8.1. 8.2.

FASTNESS TO WASHING LIGHT FASTNESS

16 17

9.
9.1. 9.2. 9.3.

INSTRUMENTAL COLOUR MEASUREMENT

COLOUR COLOUR
CO-ORDINATES STRENGTH

18
18 18 19

THE REFLECTANCE SPECTROPHOTOMETER

10. 11.
11.1.

LABORATORY APPARATUS LAB-TO-BULK RECIPE TRANSFER

INSTRUMENTAL APPROACH

20 20
20

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1. INTRODUCTION One of the most important aspects of an Adastra Project is the successful transfer and correlation of the dyeing recipes from the laboratory to production. In fact this is one of the most important issues that any dyehouse is concerned with on a day-to-day basis. Unfortunately, there is no clear and practical guidebook which, when followed to the letter, is guaranteed to give the desired results. Therefore, the purpose of this manual is to give guidelines and information that will prove helpful in the quest for the ultimate goal to understand the relationship between laboratory and production wet processing of textile materials and to be able to predict or control correlation between these two very different situations. 1.1. Health and Safety The importance of taking all necessary precautions prior to any work involving the handling of chemicals cannot be stressed enough. The lab personnel should always wear protective clothing (lab coat) and suitable footwear as well as gloves and goggles where appropriate. It is equally important to carefully study the relevant supplier information (safety data sheets and related literature) of each chemical product before using either in isolation or combination with other chemicals.

2. FABRIC IDENTIFICATION This is an important, though frequently overlooked, issue. It is of special import in the case of commission dyeing plants. Although vertical units may be expected to have a very good knowledge of the nature of the fabrics processed, this cannot be guaranteed in the case of a commission dyehouse. Most dyers have encountered initially inexplicable dyeing problems during their career which, after a lot of painstaking research are found to be due to the composition of the fabric as stated by the knitter, weaver or merchant converter being incorrect. Although it might be considered a luxury by most dyehouse and laboratory managers, it is always wise to check the fabric composition before going to production. The following are practical and quick check tests which may be used. 2.1. Burning test This test does not require time or expensive apparatus, only need a lighter or match and experience. The material to be tested is prepared in the form of a strand of fibres from the component yarn, which are twisted together. The behaviour of the fibres is noted as follows: as they approach the flame inside the flame after they are removed from the flame the nature of the burnt leftover odour

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These observations are then compared with those of Table 2.1 from which the yarn can be identified. This test is applicable to single-fibre yarns and not blends. In the case of different yarn types blended in the same fabric, different tests should be carried out for each type. Special care should be taken when performing the burning tests so that there are not any inflammable substances in the vicinity and the testers hands are protected with special gloves. Table 2.1 Burning test data
Fibre Cotton Polyester Nylon Viscose Wool Acrylic Modal Silk Acetate Linen Approaching the Flame It does not shrink away Backs away and shrinks Backs away and shrinks It does not shrink away Backs away and curls Backs away Backs away Backs away and curls Backs away It does not shrink away Inside the Flame Burns without melting Burns slowly and melts Burns slowly and melts Burns without melting Burns slowly partially melting Melts Burns very slowly and melts Burns slowly partially melting Melts Burns without melting Removed from the Flame Continues to burn without melting Usually stops burning Usually stops burning Continues to burn without melting Burns very slowly (sometimes stops) Continues to burn with melting Stops burning Burns very slowly (sometimes stops) Continues to burn with melting Continues to burn without melting Nature of burnt residue Ashes Hard, black, round Hard, brownishyellow, round Thin Ashes Black Ashes Hard, black, non-uniform Hard, black, non-uniform Black Ashes Brittle, black, non-uniform Ashes Smell Burnt paper Aromatic Celery Burnt paper Burnt hair Acidic

Burnt hair Acidic Burnt paper

2.2. Chemical identification A more sophisticated way of fibre identification involves the use of chemical reagents. The correct combination of reagents to be used is selected from the information given in Table 2.2. For example, if we know the material is an unknown cellulosic, hydrochloric acid can be used; if the material dissolves, then it is rayon (cotton does not dissolve). If it is synthetic (polyester, nylon or acrylic) then we can use concentrated hydrochloric acid, sulphuric acid and m-cresol. Another way to easily identify fabrics of unknown composition, is to use specially developed dyes (e.g. Shirlastain E), which, when applied, impart different shades according to each fibre type.

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Table 2.2 Chemical identification

Reagent Acetic acid Hydrochloric acid Sodium hypochlorite D.M.F. Sulphuric acid M-Cresol Conc. 100% 20% 5% active Cl 100% 80% 100% Temp (C) 25 25 25 Polyester Does not dissolve Does not dissolve Does not dissolve Does not dissolve Does not dissolve Dissolves Cotton Does not dissolve (yellow) Dissolves quickly Does not dissolve Nylon Does not dissolve Dissolves Does not dissolve Dissolves Dissolves Dissolves Linen Does not dissolve (yellow) Dissolves slowly Does not dissolve Acrylic Does not dissolve Does not dissolve Does not dissolve Does not dissolve Does not dissolve Does not dissolve Wool Dissolves Acetate Dissolves Does not dissolve Does not dissolve Dissolves Dissolves Dissolves Silk Dissolves Cotton Does not dissolve Does not dissolve Does not dissolve Dissolves Dissolves Does not dissolve Jute Does not dissolve (brown) Dissolves Does not dissolve Wool/Silk Does not dissolve Does not dissolve Dissolves

95 25 95

Does not dissolve Dissolves Does not dissolve

Sodium hydroxide Sulphuric acid Sulphuric acid

50%

25

80% 60%

25 25

Does not dissolve Does not dissolve

Dissolves Dissolves

3. TESTING OF MATERIALS The physical-chemical process of dyeing usually involves a lot of different reagents that need to be controlled in order to achieve a repeatable and acceptable result. 3.1. Fabric The fabric (apart from fibre identification as above) should be dimensionally measured and weighed as well as physically inspected in order to appreciate its condition (degree of cleanliness, excessive oil stains, etc). 3.2. Water Since the processes are almost always taking place in an aqueous medium it is, consequently, very important to have the best possible knowledge of the water quality. Apart from the comprehensive water analysis that should be conducted periodically, a day-to-day check of its pH and hardness should be done at the dyehouse lab. It should be stressed here that there water supply in the lab must be the same water as that of the production if at all possible. The presence of sodium bicarbonate, especially in base exchange softened water, should also be checked by heating up to 60C and then checking the pH. If it is higher than that of a cold solution, this is a clear indication of bicarbonate presence.
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3.3. Salt and Alkalis These are almost always used in dyeing cellulosics and their quality should be known as they can seriously affect the dyeing process. The pH of a 60 g/l solution of salt should be equal to that of process water, i.e. 6-8. The hardness of a 60 g/l solution should be 3-4 odH (good quality common salt), or 1-2 odH (good quality sodium sulphate). If the concentration of the caustic soda is not known it can be determined with the following way: Fill 1 Lt. of the unknown solution and weigh it at ambient temperature Weight [g] % Caustic soda B 3.4. Peroxide Every delivery of hydrogen peroxide should be tested for activity by titration as should any peroxide which has been on site for a significant time. Peroxide quantities should be corrected in the light of the results of these activity tests if necessary. 3.5. Dyes Each new batch of dyes should be checked, as it is not very unusual to have varied results using the same recipe. This is due to inexact standardization of dyes by the manufacturer giving strength variation and changes in manufacturing or raw materials causing a change in exact shade compared to the type standard. The testing of the dye strength can be carried out either by absorption measurements of dye solutions or by carrying out standard dyeings of routine recipes and then comparing them with previous ones, instrumentally and optically. Ideally, testing should be by a combination of these. Solution strength alone is not an adequate test for fibre reactive dyes as the small proportion of hyrolysed dye in every case can vary. Strength tests by dyeing should be carried out as binary combinations with a dye of contrasting hue as well as single dye applications as strength differences can be more easily discerned (visually or instrumentally). If, as ought to be the case nowadays, the assessment of shade and strength is made instrumentally then we have to remember that using delta E single number shade difference equations requires a very low tolerance as any difference will be magnified in combination dyeings (especially with dyes which are also varying in strength and shade from the type standard. Typically the major European dye manufacturers will guarantee a strength difference of <2% compared to type with identical shade (ie dE<0.2 in standard depth to the CMC 2.1 colour difference equation. Dyehouses purchasing dyes from non-traditional suppliers must insist on similar standards or pay the price of poor reproducibility, a high level of reprocessing and rejection (for shade or for fabric damage, resulting from excessive processing (and reprocessing) times). For specially critical applications (for example in automotive textiles), major dye companies will not only guarantee tolerance limits for shade and strength but will also give an accurate report of actual shade and strength with every delivery or batch change. 1220 20 26 1330 30 36 1430 40 44 1530 50 50

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4. PREPARATION OF SOLUTIONS The correct preparation and storage of chemicals stock solutions should be carefully taken into account, since many problems in repeatable lab results could be traced back to badly preserved or prepared solutions. It is very important to use the correct pipette sizes (as close to the desired volume as possible) as the measuring errors can increase dramatically otherwise. Accurate electronic pipette fillers, although expensive, are essential in minimising measuring errors if automated preparation and dispensing of dye solutions is not available. The balance used should be calibrated and of adequate accuracy. The glassware should be of Grade B. Nowadays the use of mouth pipettes must not be allowed on health and safety grounds. Automated lab solution preparation and dispensing systems (e.g. Robolab XPN, Dosarama, Datacolor Autolab TF, etc.) are used increasingly in dyehouses throughout the world. Such systems can be very helpful in the accuracy and repeatability of lab dyeing processes as well as increasing the productivity of laboratory staff. Also, they permit infallible retention of the history of dyebath preparations allowing investigation into any anomalous dyeings. The use of automated systems is discussed in section 4.3 but the general principles apply with both manual and automated dye preparation and dispensing. 4.1. Dyes All dyes are slightly hygroscopic and subject to changes in strength due to the uptake of water from humid atmospheric conditions. Powder reactive dyestuffs are especially sensitive to humidity and temperature as they can react chemically with water. Reactive dyes should be carefully handled and preferably stored in a refrigerator and never in areas which are not air conditioned. It is also very important to prepare fresh solutions of reactive dyes every day since they are prone to water hydrolysis (especially at elevated temperature). The usable life of stock solutions of other dye classes varies considerably and can be from a few hours to several weeks (experience and advice from suppliers is essential). The following instructions are of a practical and general nature. It is advisable always to read carefully the manufacturers colour card for each individual dyestuff. 4.1.1. Weighing The quantity of dyestuff to be weighed depends upon: 1. The desired stock solution concentration, taking into consideration the capacity of the volumetric flask and the required quantities. 2. The solubility limit of the specific dyestuff, stated in the manufacturers colour card. 3. The depth of the shade. E.g. if the depth is 5-6 % the concentration has to be as high as possible in order for the metered quantities not to be higher than the required LR inside the dyepot (again without exceeding the solubility limits). The importance of accurate weighing as well as having fresh solutions is paramount. There are not any specific rules to follow, since each individual dyestuff behaves differently. Solutions of different dyestuffs even at 1g/l can last from several weeks down to a few hours! An example of stock solutions calculations and preparation is given in Scheme 4.1 and Table 4.1. The concentration of dye in a stock solution should be as low as practically possible (max 1gr of dye in 100-200ml).

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4.1.2. Storage and handling of dyes in the laboratory It is suggested to keep powder dyes in quantities of 30-50 grams in safely closed appropriate bottles or boxes. They should be replaced very often with new ones with the following procedure: 1. Pour away the old dyestuff from the sample box, with a final shake, making sure that no residuals are left. 2. With a very clean and dry spoon or scoop, fill it again from: either a new sealed box, with adequate quantity e.g. 20-50 grams, or from the box which is already in use, but taking the amount not from the surface which might have been contaminated during bulk weighing or contain moisture from the atmosphere, but from a deeper position which is dry and pure. It should be noted that just a tiny trace of contamination from a different dyestuff which is negligible in bulk production, could create serious problems in the laboratory. Apart from the name of the dyestuff, the date of sampling and even the drum number should be also noted on the label.

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Y-A
1%
Solution (10.00 gr Dyestuff in 1000 ml of water)

Y-B
0.1%
Solution (1.00 gr Dyestuff in 1000 ml of water)

Y-C
0.01%
Solution (0.10 gr Dyestuff in 1000 ml of water)

With Pipettes of -100 ml -10 ml 100 ml 10 ml

R-A
1%
Solution (10.00 gr Dyestuff in 1000 ml of water)

R-B
0.1%
Solution (1.00 gr Dyestuff in 1000 ml of water)

R-C
0.01%
Solution (0.10 gr Dyestuff in 1000 ml of water)

100 ml

With Pipettes of -100 ml -10 ml

10 ml

B-A
1%
Solution (10.00 gr Dyestuff in 1000 ml of water)

B-B
0.1%
Solution (1.00 gr Dyestuff in 1000 ml of water)

B-C
0,01%
Solution (0.10 gr Dyestuff in 1000 ml of water) With Pipettes of -100 ml -10 ml

100 ml 10 ml

Scheme 4.1 Preparation of stock solutions

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Table 4.1 Calculations of chemicals EXAMPLES OF PREPARATIONS (10gr of fabric for final LR 1:8 = 80 ml)
Light Shade % ml 0.003% 3 0.02% 20 0.004% 4 5 48 80 Bottle Y-C R-C B-C Medium Shade % ml 0.7% 7 0.1% 10 0.4% 4 7 52 80 Bottle Y-A R-B B-A Dark Shade % ml 2 20 1 10 3 30 7 13 80 Bottle Y-A R-A B-A

Yellow Red Blue Various Chemicals Water Final

From each dyestuff, a small quantity (e.g. 100g) should be kept separately, noting the date and batch number, in a dry dark place safely closed, to be used as standard in order to check new deliveries from the suppliers. Alternatively it may be possible to obtain a type standard from the manufacturer. The literature accompanying the dyestuffs-auxiliaries used, should be carefully studied. In case that the dyestuff, after weighing, is to be dissolved hours later or the next day, it should be placed in a covered dry beaker to avoid moisture contamination from the environment. 4.1.3. Dissolving procedures of dyes in the laboratory The dyestuffs should be dissolved according to the manufacturers instructions. Depending on the dyestuffs nature, they can generally be categorised as follows: A. (Direct, Reactive, Acid) 1. The dyestuff is poured inside a dry glass beaker. Cold water is then added, equivalent to the dyestuff amount and a paste is created using a glass rod. Warm water (up to 60C) is then added (at least 50-100 times the amount of the dyestuff) inside the beaker while stirring with the rod. Stirring is continued until the liquor does not deposit any non-dissolved residual on the beakers side. The stirring of dyes and chemicals in a modern lab is done with the aid of magnetic stirrers/heating plates. 2. The dissolved dyestuff, with the aid of a proper glass funnel, is then poured in a narrow neck calibrated flask and filled with cold water until the line, which indicates the volume. The flask is closed with its lid and put inside a basin with cold water until the temperature of the dissolved liquor is less than 20C. Normally the volume will drop below the flask line. Water is added until the line and the contents are poured inside a proper wide neck dark bottle of equivalent size. After a few shakes, it is placed in a dark place. B. (Disperse) As above, but the temperature of water should not exceed 60C while a 2g/l of a dispersing agent in the water is helpful. Keep in mind that, given the nature of these dyes, they are not true solutions but fine dispersions which generally have lower stability and consequent solution life than ionic dye classes. C. (Cationic or Basic) The dyestuffs are pasted inside a beaker with an equivalent amount of acetic acid and then proceed as in paragraph A.
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4.2. Chemicals It is imperative that before handling any of the chemicals in the laboratory, their respective safety data sheets (or MSDS) and literature are studied and understood. Special care should be given in their aqueous solubility and compatibility properties when mixed with other chemicals. The grade of the chemicals used in the lab should be the same as that of the production and manufacturers samples should only be used for initial lab evaluation of new products not for production lab work. 4.2.1. Sodium carbonate Fresh soda solutions should be prepared often and kept in a cool, dark place. It is recommended to make solutions up to 50g/l as at higher concentrations (80-100g/l) their solution becomes saturated and unstable. 4.2.2. Sodium hydroxide Special care should be given when dissolving caustic soda as it is a highly corrosive chemical. Caustic soda of not higher concentration of 38Be should be preferably used to avoid saturation. 4.3 Automated solution preparation and dyebath dispensing In large dyehouses it is economically sensible to use automated solution preparation and dyebath dispensing. These techniques also increase the accuracy and consistency of lab dyeings. In particular it is advisable for all dyehouse laboratories to use automated or semiautomated solution making for reasons of enhanced accuracy. There are several different types of dye liquor dispensing and many of these deliver the dye solutions by means of a separate pipe for each dye solution or by means of a syringe injection. The accuracy of these methods is limited to the weight of a water droplet (+ 20 mg). For best accuracy we should use electronic pipettes or the Robolab (Talos) equipment. Here the accuracy is determined by the weighing scale and is usually + 3 mg. The Robolab equipment also has the advantage of incorporating solution preparation and dispensing in the same equipment which avoids some human intervention and permits automatic correction during dispensing for small errors in solution preparation. In general we should encourage the use of automation in the lab and in particular recommend the use of such systems are integrated with an instrumental colour matching system.

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5. PREPARATION OF FABRIC SAMPLES The fabric samples to be processed in the lab should be cut out from the bulk fabric after the preparation stage. It is preferred that the fabric dyed in the lab should be from the batch that is going to be processed in the production. If the same fabric quality is processed in production from time to time, then a few meters of the bulk-prepared fabric can be initially cut in order to be used in the lab over a longer period of time. It is very important to use the same fabric quality as that used in production to prevent avoidable shade discrepancies. Since the fabric is already prepared, it should have at least acceptable wetting properties, thus it is not necessary to wet it out before placing it in the dyepot. In any case it is better to put a dry sample in the dyepot, otherwise the liquor ratio will not be easily determined. If a wet sample is used, then less water should be added into the dyepot and in this case the fabric sample should be squeezed by a pad mangle to a known expression (or water content) to allow an accurate compensation of liquor ratio. Also it is necessary to make a small correction for the difference in weight of fabric between grey and prepared fabric (ie to correct for the weight loss of oils and waxes which are removed in preparation).

6. LABORATORY DYEING The dyeing of the fabric sample should be carried out in appropriate laboratory-scale dyeing machines with calibrated thermometers in order to successfully simulate the timetemperature profile followed in the large-scale machines. Certain guidelines should be generally followed, as far as the laboratory dyeing processes are concerned, in relation to bulk processing: Same dyeing LR (exactly). Same water quality. Same quality (of production prepared) fabric exact same batch Same time-temperature dyeing profile. Same chemicals. The concentration of the chemicals should also be the same as in the production. That means according to the initial liquor ratio. In the case of salt (electrolyte) transfer before dyestuff addition, dosing systems may be used and if they are the programme should be followed. If, as is more usual, the salt is added manually to the pot at the same time as the dye, then the procedure following the dye addition must be followed accurately. With salt dosing after the dyestuff addition should be made ideally with the same time and dosing curve but this is not possible in the most widely used rotadyer type of machine and salt dosing must be simulated by syringe type transfer systems. Alkali dosing. Similar time and dosing curve or simulation by portion-wise addition.

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Fixation stage Special care should be given in the time of the fixation stage. This time should be either the same as that of the production or it should be prolonged for about 10-15 min in order to ensure simulation of production fixation levels. The necessary time to achieve the same fixation with the production can be determined by measuring the possible dyestuff hydrolysis percentage in the laboratory. This percentage should be as close as possible to that of the production. We can also extract useful conclusions by comparing reflectance measurements of production and laboratory dyeings preferably using colour difference equations. In making pass-fail decisions it is widely agreed that the best freely available equation is CMC 2.1 (although the Marks and Spencer equations are equally consistent throughout Colour Space). Among earlier equations JPC79 is to be preferred.

Laboratory Dyeing Machines Recently a review of Dyeing Laboratory Developments has been written by James Park for the Review of Progress in Coloration to be published by the Society of Dyers and Colourists. This is an extract on laboratory dyeing machines from that review: LABORATORY MACHINES FOR EXHAUST DYEING Previous reviews have discussed the development and categorisation of lab dyeing machines for exhaust dyeing, together with the selection of equipment types according to their advantageous characteristics [2, 3, 8]. This information is still highly relevant and need not be repeated here. For the busy matching laboratory, requiring high productivity and versatility in terms of substrate form, liquor ratio, temperature range and substrate mass (usually 5 to 100 g), the multi-position rotating- tube machine (often referred to as the rotadyer) in its multi-bath form is the most widely used equipment. The original heating medium was a high boiling-point liquid, such as polyethylene glycol, although water could be used for low-temperature dyeing methods. Fluid-bed heating systems have largely replaced the use of liquids with an improvement in cleanliness and ease of operation. The end-over-end tube rotation and the specific geometry of the dyeing tubes contribute to levelness and reproducibility on all substrate types and forms under a wide range of dyeing conditions. The variety of tube sizes available provides scope for a multiplicity of substrate weights and liquor ratio combinations [3, 8]. The introduction in the late 1980s of a second generation of multi-position rotatingtube machines in which heating is provided by infra-red (IR) radiators [3] resulted in a totally dry and clean machine, which has proved mechanically robust in use. In the original design, the dyeing tubes were mounted at a specific angle on a rotating disc usually situated at the back of the heating chamber containing the IR elements. Early models of the Pyrotec (Roaches International) [10] and the Nuance (Ahiba) [11] ranges have been described. The Nuance Top Speed II [12] has powerful blowers for cooling which results in shorter total cycle times. This equipment is typified by the most recent versions of the Labomat BFA (Mathis) [13, 14], the Pyrotec 2000 (Roaches) [8, 15], the Nuance Top Speed II and Eco (Ahiba) versions, the latter being targeted towards the smaller laboratory with limited
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requirements. The three Nuance machines currently on the Ahiba range have variable rotation speeds within the limits 5 to 50 rpm. The microwave heating in the Labomat MWA (Mathis) is claimed to give heating rates up to 9C per minute with low energy consumption and ease of handling of both tubes and substrates [13]. The Easydye (Ahiba now withdrawn) was an IR machine in which the tubes were given a rocking motion. Comparative dyeings over a wide range of substrates and variety of forms using a large number of dye classes and application techniques showed that there was a high level of correlation between the conventional rotadyer machine and the rotating-disc IR equipment, as shown in Table 1 [16]. The Pyrotec MB (Roaches) [8] combines the advantages of IR heating and the end-over-end tube rotation of the rotadyer machine. Multibath versions incorporating both features combine IR convenience and the productivity, versatility, level-dyeing and reproducibility of conventional rotating-tube machines with the benefit of reliability and low maintenance in use. As with the rotadyer type, additions can be made during dyeing to both types of IR machine, using systems such as the Adchem (Roaches) technique [3, 8]. Table 1 Comparison of rotating-tube dyeing machines [16] Average colour difference - E(CMC) Fluid-bed rotadyer Rotating-disc IR 0.2 0.21 0.3 0.3 0.3

Measurement factor Levelness within dyeings Agreement between tubes Agreement between machines

Lab dyeing machines with liquor circulation are seldom used for routine matching functions on the grounds of cost and productivity, this being the province of the machines discussed above. Circulating-liquor machines may be either multi- or single-position units and offer the following features: (a) the physical condition of the substrate after dyeing is closer to that of bulk production (b) larger samples of substrate are available for further testing and evaluation (c) fundamental dyeing studies under a wide range of conditions, including adjustable machine parameters (d) process simulation of complete production procedures. All substrates in their various forms can be package-dyed. In the case of yarn, it is advantageous that the dyeing vessel can accommodate a package from bulk production so that results are directly transferable. Perhaps typical of multi-position machines are the Chroma 4 (Roaches) [8, 17, 18] and the Turby (Mathis) [19] equipment. The Chroma 4 is a fully-automatic four-beaker machine with independent temperature control and dosing of dyes and chemicals to each dyeing position. Liquor circulation is by means of independent gear pumps and the machine is fully programmable through a PC to include all the usual dyeing parameters. Full data management is provided including graphical and numerical data presentation. All forms of substrate (up to 20 g) can be package-dyed. One advantage of this equipment is that fullyautomatic operation is possible without direct supervision. Roaches has recently developed a Multi-dye six-position machine designed for larger samples (up to 200 g) of yarn in package form or beam-wound fabric. The Mathis Turby T twelve-station machine has a magnetic stirrer circulation system and is suitable for dyeing wound samples (10 to 40 g). Development of the Colorstar (Mathis) laboratory dyeing units containing a singleposition, glass dyeing vessel has been described [20]. Atmospheric and high-temperature dyeing of all substrate types is possible. Current versions of this equipment centre on the Colorstar CJ type [15, 19, 21]. Liquor circulation is by means of a magnetically driven gear
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pump. Various dyeing vessel sizes are available and the operating liquor ratio is 8:1 or longer. Numerous parameters can be controlled and measured, including flow rate and differential pressures, pump reversal, pH and dosing of chemicals. Whilst the ColorstarFoamy CF [19, 20] can be used for dyeing, its principle function is to study the generation and dissipation of foam during the process, the foam being generated by passing the liquor through a special nozzle inside the dye vessel. Ahiba has recently rationalised its range of lab dyeing machines. In addition to the three versions of the Nuance IR machines discussed earlier, the Multiprecise TC equipment has been introduced [21], together with a winder, Model SE/1, to produce the necessary packages. Two independent dyeing positions can be fitted with either one- or two-litre vessels, accommodating samples (up to 300 g) at liquor ratios down to 5:1. Full automatic control is available including functions such as liquor volume, flow rate, dosing and rinsing. The Colortec (Roaches) [8] is a fully-automated machine for dyeing fibre, yarn or fabric (up to 200 g), essentially in package form. Liquor circulation is by means of a gear pump to give a positive forward or reverse flow, the flow rate being measured by flow meter together with differential pressure indication. An addition tank provides access for solids and sampling of liquors via an interlock, whereas liquids are dosed automatically. On-line pH measurement up to 130C is available. Direct linkage of a spectrophotometer to a dyeing vessel was reported following ITMA 1991 [22] and the Colortec has the option of a UV spectrophotometer to give on-line information regarding absorption, exhaustion and dye compatibility. The relative costs of the various types of lab dyeing machines have been compared [8]. These are normally fitted with controls that are available at various levels of sophistication; this has increased significantly over the period under review. Machines of the rotating-tube type are equipped, as a minimum, with dye-cycle controllers and capacity for storing numerous programs. Circulating-liquor machines normally have sophisticated controllers to monitor and record the large numbers of functions that can be varied and to hold programs for a wide range of dyeing cycles. Controllers of this kind are also installed on pilot-plant equipment which is discussed later. The Roaches Supervisory Data-logging System (RSDS) [15] operates on a personal computer (PC) in Windows 98 (Microsoft) with an RS422 serial communication system to network equipment. The RSDS can be fitted as an option to all types of dyeing equipment and records details of all dyeing parameters. There is capability for storing programs centrally, which can be downloaded with the touch screen controller to any machine and can be uploaded to a central computer. Most lab dyeing machinery makers will supply PC-driven control and data recording systems [15].

7. AFTERTREATMENT Aftertreatment includes every process that follows after the dyeing stage and while the fabric is still in the machine, i.e. washing-off, fixing, softening. Cotton dyed with reactive dyes has to be washed-off sufficiently after dyeing, in order to remove the unfixed, hydrolysed, dye. A general recommendation is to follow the processes of the production as closely as possible (chemicals, time-temperature profile).

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7.1. Wash-off process The wash-off process is of paramount importance, since inadequate wash-off can lead to poor fastness to washing. It usually involves a rinsing stage and at least one soaping stage where the dyed material is washed using typically an anionic or non-ionic surfactant near the boil. Rinsing temperatures can vary between cold and hot (up to 70C), depending on the application temperature of the dye. For instance, in the case of monochlorotriazine dyes hot rinsing is usually employed, as the dyes are more substantive at room temperature compared to that of the application. The initial rinsing process results in the reduction of electrolyte concentration as well as the substantivity of the unfixed dye. It is very important that the carry-over of contaminated liquor between rinsing and soaping is kept as low as possible. This is safely achieved with the AquachronTM technology. Monofunctional haloheterocyclic reactive dyeings may suffer acid bleeding, whilst vinylsulphonyl dye-fibre bonds are unstable under alkaline conditions. Thus, such phenomena are directly dependent on the pH within the fibre (also known as internal pH). Internal pH can be related to the external dyebath pH, the electrolyte concentration and the amount of dye fixed to the fibre. For a certain amount of fixed dye, external pH is reduced by dilution of the alkali while internal pH is further reduced by dilution of the electrolyte. Consequently, internal pH can be very low in the later stages of wash-off due to higher dilution of electrolyte. If the internal pH is too low before drying, significant dye-fibre bond hydrolysis may occur as a result of exposure to heat, leading to lower wash fastness properties. The adverse effect of trace metal ions, such as calcium and magnesium, on the dyeing and wash-off processes should also be noted. In wash-off, hydrolysed reactive dye can be removed easier with soft rather than hard water, as the fixed dye molecules retain such divalent cations, which in turn inhibit the outward diffusion of hydrolysed dye anions. The washing-off in the laboratory is difficult to simulate that of the production, due to the lack of lab apparatus that can simulate the typical optimised rinsing systems found in production equipment. In general, the following steps are suggested after dyeing: The material should be rinsed thoroughly under a running cold tap to remove most of the salt and alkali. the material should be placed in a beaker with a slightly acidic pH (6) in order to be neutralised the soaping stage should be carried out with the same amount of chemicals and time-temperature profile as in the production if deemed necessary, rinsing stages at a certain temperature/time might be introduced before and/or after the soaping stage via a trial and error process.

8. FASTNESS TESTING An important criterion of the quality of a coloured textile material is its fastness to various agencies and treatments that it can be subjected to during its life, depending on the end-use.

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The exposure of a coloured material to, for instance, washing, light or dry cleaning, can result in an alteration of the actual colour of the material. Furthermore, should any dye, for example during domestic laundering, be removed from dyed fabric, the dye may be transferred to, and thus cause staining of, the adjacent material. This is especially true in the case of cotton dyed with reactive dyes as it has been found that a 0.003% omf (on mass of fibre) can be enough to cause a stain rated 4 on the gray scales. In essence, colour fastness is the ability of a coloured textile article to withstand the various agencies to which it can be exposed. Colour fastness is of considerable importance and an accurate determination and description of the fastness properties of dyed textiles is therefore required. A large number of standard methods for the determination of fastness of textiles exist as international standards by the International Standards Organisation. Fastness testing essentially consists of: subjecting a sample of the coloured material (together with adjacent undyed materials where staining must be determined) to conditions which accurately represent or simulate those encountered in practice assessing any changes in the colour of the sample and the staining of the adjacent undyed materials, as objectively as possible. 8.1. Fastness to washing Although a dyed textile can be subjected to a variety of wet treatments, such as water, perspiration, bleach, etc., washing is the most important wet treatment to which a coloured article may be exposed, with domestic laundering being the most commonly encountered. The early methods for testing wash fastness were primarily soap-based. However, modern domestic washing powders are detergent-based formulations. ISO 105 C06 is a series of wash fastness tests based on a standard detergent/perborate formulation, which is designed to mimic conditions likely to be encountered in real life. Typically, a swatch, 10 cm by 4 cm, of the dyed fabric to be tested, is placed between two adjacent undyed pieces of fabric of the same size. The adjacent fabrics are cotton and viscose, if cotton is tested. Fabrics to be used as adjacents with other materials are defined in the SDC and ISO test methods. Alternatively and more usually nowadays, a single piece of SDC multifibre strip, consisting of wool, acrylic, polyester, nylon, cotton and secondary acetate can be employed as the adjacent. This composite specimen is stapled together at either end to maintain close contact throughout the test. The fabrics are then evaluated using the gray scales. 8.2. Light fastness Clearly, for certain textile applications such as curtains and blinds the light fastness of the dyed material is of paramount importance, with wash fastness of much less significance. In the case of textiles for apparel, very good wash fastness properties are often demanded, particularly for frequently washed articles. However, light fastness is an important factor and cannot be overlooked. In general, reactive dyeings possess only moderate light fastness of around 3-5 on a 1-8 scale, but these levels are acceptable commercially. Direct and sulphur dyeings display, typically, slightly higher light fastness values ~4-6. Some aftertreatment products can reduce the light fastness by 1-2 points, which is undesirable, but careful selection of dyes and aftertreatment product can minimise the effect. Unlike domestic laundering, which will reveal any wash fastness defects in a short space of time, fading due to light can take much longer to become apparent. Although there are test methods based on natural sunlight, it is more normal to use an accelerated method, based on a synthetic source of radiation, which is less time consuming and is more consistent.

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9. INSTRUMENTAL COLOUR MEASUREMENT In the case of evaluating a subjective phenomenon such as the colour of a substrate, several factors can influence the judgement of the observer, for instance the lighting conditions, size of the sample and surrounding colours. Thus, extreme care in measuring colour in consistent and standard conditions should be undertaken, as well as utilising objective (instrumental) techniques where possible, although in the case of colour fastness to washing, human evaluation is still essential. The need for communicating colour in a consistent and objective manner is of great importance in both the academic and the industrial environment. This is a very difficult task however, since, as mentioned above, several factors can affect how the colour of a substrate is perceived by an observer. Under conditions of controlled illumination, sample size and background colour, the technique of instrumental colour measurement can be used with the aid of a reflectance spectrophotometer. Thus, a number of properties can be measured (known as colour co-ordinates), permitting the comparison of coloured substrates without the need for physical samples. Nevertheless, it still is very difficult to replace completely the human observer, since the high sensitivity of the eye enables the distinction of subtle differences that are not possible to truly appreciate with instrumental measurement alone. 9.1. Colour co-ordinates The Commission Internationale de lclairage (CIE) L* a* b* system was developed in order to provide the following: a three dimensional space in which all surface colours can be represented; the distance between points representing the colours of two samples is intended to be proportional to the visual colour difference between the samples; the axes are scaled so that just a perceptible colour difference is represented by unit distance; the L* a* b* values can be easily interpreted in terms of the lightness, hue and depth of a colour. This system is internationally agreed for surface colour specification; the arrangement of the CIE L* a* b* (1976) colour space is shown in Figure 9.1.

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White L*

L* Lime green

Yellow b* C* h a*
Orange

Green

Black

Red

Cyan Magenta

Blue
Figure 9.1 The arrangement of the CIE L* a* b* (1976) colour space Where: L* is the vertical axis that represents lightness; a perfect black has L*=0 and a perfect white sample has L*=100; a* is the axis in the plane normal to L* which represents the redness-greenness quality of the colour. Positive values denote redness and negative values indicate greenness; b* is the axis normal to both L* and a* which represents the yellowness-blueness quality of the colour. Positive values denote yellowness and negative values denote blueness. The co-ordinates of the points representing the colour of a sample can also be expressed in cylindrical co-ordinates, lightness L*, chroma C* and hue h. C* is chroma C* = [(a*)2 + (b*)2]0..5, a neutral gray has C*=0; h is hue angle h = tan-1[(b*)/(a*)]. 9.2. Colour strength Colour strength is a numerical value indicating the relative strength of the colour. A complex mathematical expression is required to relate dye concentration to light reflectance and the Kubelka-Munk equation is widely used, relating the reflectance to the absorption and scattering of light. The Kubelka-Munk equation (9.1) is as follows: K (1 R) 2 = (9.1) S 2R where: K and S are the absorption coefficient and scattering coefficient of a colorant at a given wavelength and R is reflectance. The K/S value is directly proportional to the amount of dye present on the dyed fibre and is calculated using the above equation from the reflectance at the wavelength of maximum absorption, max. However, a group of specialists from the major European dyestuff manufacturers developed and recommend the use of the relative colour strength function, fk, which is the sum of the weighted K/S values in the visible region of the spectrum (400 to 700 nm); fk is calculated using equation 2.2:
700

fk =

(K/S) [x
= 400

10

( ) + y10 ( ) + z10 ( )]

(9.2)

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where: x10 ( ), y10 ( ) and z10 ( ) are the colour matching functions for the 10 standard observer at each wavelength measured (ISO 7724/1-1984). 9.3. The reflectance spectrophotometer A reflectance spectrophotometer measures the ratio of reflected to incident light (reflectance) from a specimen at many points across the visible spectrum. In practice, reflectance measurements are typically taken over the 400-700nm range at 10nm intervals. A number of different illuminants can be chosen when measuring the reflectance of a sample, with D65 (that represents daylight) being one of the most popular ones. A pulsed xenon light with the appropriate filters is the most typical light source. Another important aspect is instrument geometry, since the angles and method by which a sample is illuminated can have a dramatic effect on the observed colour. Diffuse/0 or 0/diffuse geometries can be used. In the first, the sample is illuminated diffusely by an integrating sphere. The angle between the normal to the sample and the axis of the viewing beam should not exceed 10. In the second geometry on the other hand, the sample is illuminated by a beam whose axis is at an angle not exceeding 10 from the normal to the sample. 10. LABORATORY APPARATUS It is very important to have a properly equipped laboratory. Although the quantities (of glassware for example) and nature of equipment may vary significantly according to certain special needs, the following list is a representative example:
Reflectance Spectrophotometer HT Laboratory Dyeing Machine Wash fastness machine (although wash fastness testing may be carried out in the same lab dyeing machine) Balance with at least 3 decimals accuracy pH meter Light cabinet with D65, TL83, TL84, UV illuminants Oven Blow dryer Soft water apparatus Hot plates with magnetic stirring capabilities Gray scales (shade change and staining) Multifibre testing strips (depending on the wash fastness test) Glassware of at least grade B, i.e. volumetric cylinders (50,100,250 ml), volumetric flasks (250,500,1000 ml), glass beakers (100,250,500 ml), glass containers with stoppers, pipettes (0.5,1,2,5,10,20 ml), glass rods, testing tubes Lab spoons Large metal beakers Fabric scissors Water hardness test kit

Peroxide residue strips

11. LAB-TO-BULK RECIPE TRANSFER The successful and repeatable transfer of a recipe from the laboratory to the bulk production is the single most important issue and our ultimate goal. All the aforementioned suggestions aim to simulate and successfully relate the bulk processes with those carried out in the laboratory.

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The fact that thus far there is no detailed information given anywhere in the literature, is evidence enough for the difficulty of the task, which stems mainly from the involvement of a vast number of factors that govern and affect the textile dyeing and finishing processes. Nevertheless, since the benefits are too many to ignore, a methodical and continuous effort should be made to achieve the best possible lab-to-bulk recipe transfer. 11.1.Instrumental approach This can be a very effective way of extracting correlation factors between lab and bulk recipes. The reflectance spectrophotometer plays a central role in this method, and as such, it should be well maintained and calibrated and ideally kept in a separate room with a controlled atmosphere where the samples could be conditioned overnight before measurement (though this is, understandably, extremely difficult to implement in practice). A correctly and comprehensively built database on the spectrophotometer is very important and helpful to this respect. The procedure is the following (Table 11.1): for a given lab recipe (actual weight of a trichromat), a dyed sample is produced the lab sample is then measured at the spectrophotometer and the measured weight of each dye is recorded (lab Read) a sample from the fabric dyed at the bulk production with the given recipe is measured at the spectrophotometer and the corresponding dye weights are recorded (ACTP) the correlation factor between laboratory recipe and production is produced by the ratio ACTP/Lab Read

Table 11.1 Instrumental method for the extraction of factors Spectrophotometric Measurement Given Colour Yellow Red Blue Actual weight (g) 0.22 0.01 0.95 Lab Read Colour Yellow Red Blue Measured weight (g) 0.20 0.007 0.96 Factor (ACTP/Lab Read) x 0.95 x 1.14 x 0.96 Spectrophotometric Measurement ACTP (Actual Production) Colour Measured Weight (g) Yellow 0.19 Red 0.008 Blue 0.92

The factors extracted, are implemented in the next batch and further corrections are made as necessary until there is no further need for correction, thus arriving in a standard set of factors for a given recipe that can be successfully followed in subsequent dyeings. It should be stressed that these factors are unique to each dyehouse, since the number of variables involved are too many and extremely difficult to take into account, between different dyehouses.

Arthur Welham 05/04/08

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