TECHNICAL REPORT

BUFFERING STABILITY OF DYEBATH IN DISPERSE/DIRECT DYEING

Scientists of PCSIR Labs Complex Karachi.
M.Javaid Mughal, M.Naeem, Kamran Ahmed, Mohammad Aleem Ahmed, Mansoor Iqbal.

E-mail: javaidtextile@hotmail.com m_n_pearl@yahoo.com mansoorprocessing@hotmail.com

TEXTILE LABORATORY
APPLIED CHEMISTRY RESEARCH CENTRE.
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TABLE OF CONTENTS
S.No. 1 2 Topic Introduction Wet Processing Pretreatment Dyeing Jet Dyeing Machines Fully Flooded Jet Dyeing Machines The dyeing process Buffer solution Visits of XYZ Processing Industry (Pvt) Ltd. First visit Second visit Third visit Result of collected Samples from XYZ Processing Industry (Pvt) Ltd. Observation In Jet no 11 Lot No. 385. In Jet no 6 Lot No 399. Preparation of Buffer Solution and their effect on Shades Buffer solution No. 1 Buffer solution No. 2 Buffer solution No. 3 Buffer solution No. 4 Buffer solution No. 5 Buffer solution No. 6 Buffer solution No. 7 Buffer solution No. 8 Process Chart Proposed Process Chart Desizing / Washing Process Chart Special Process (SP) Caustic Chart Dyeing Process Chart Process Diagram Desizing Desize Wash SP-Process (CAUSTIC) Disperse / Direct Dyeing Suggestions about Process Control Page No. 1

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SUMMARY

A number of visits have been arranged by XYZ Processing Industry (Pvt) Ltd.and the problems (particularly in the regard of pH stability of dyeing bath) were discussed with the management of industry. After studying all the process and working conditions we have done initial study to solve the problems which management of XYZ Processing industry were facing. In this preliminary study we prepare different buffer solutions and dyed two sets of shade i.e. Olive and Beige, and compared the results on same shade by using XYZ Buffer solution. The corresponding colorimetric data for each dyeing with different buffer solution are displayed in the attached sheets. By using buffer solution 1, 3 and 7 the values of K/S are higher than Buffer Solution No. 8, which is of XYZ industry. A higher value of K/S means the higher depth of colour. Similarly lower value of L* for the same buffer solutions also proves the results. The hue of these solutions are also according to Munsell equation, having the lower value of a*. On the other hand due to the higher value of a* the hue has considerably change for XYZs buffer solution. This high value of a* may impart the fastness results also. By considering this data and on visual assessment of shade, Buffer Solution No. 1,3 and 7 are found to be most suitable in terms of required shade and also the chemicals used which ultimately reduced the production cost.

Introduction:
Colour has been playing a dominant role in the life of man from time immemorial. Even in the prehistoric times, the ancestors of man must have noticed (perhaps with or without understanding) the abundance of multitude of colours worn by nature. Thus he must have wondered at the spread of transient bright golden colour on the diffused clouds and on the landscape during dawn and sunset, the VIBGYOR colours of a rainbow, the vast expanse of the blue sky on a cloudless day or acres and acres of land crowned with chlorophyll dominated green coloured vegetation or even an infinite variety of plants and trees, bearing flowers and fruits of varied colours of an almost innumerable combination of yellow, red and blue hues in different depths and shades or even the multi-coloured stripes and dots on the bodies of the birds of the sky, animals of the land and the fish of the sea. With the growth of intelligence in man, he must also have noticed that most of the colours he saw in nature (colours at sunset, flowers on plants etc.) were not permanent; the fading of the colours of leaves changed to yellow or brown due to ageing, etc. There might have been an urge in him to try to retain the pleasing colours for longer periods and working in this direction, he might have found that certain plant juices and extracts from organisms produced colours which would last long. Textile is the backbone of Pakistans economy and shares more than 60% of the exports of Pakistan. Cotton being the main crop in Pakistan attracts more attention, as it is still the principal raw material for the textile industry in the world. Polyester is second important fiber used in textile made up, as a pure as well as blends with cotton, Polyester cotton can be dyed with disperse and direct dye.

Wet Processing
Pretreatment:
Pretreatment occurs immediately before dyeing/printing in the textile production chain, and prepares the fabric for these processes. The fibers may either be in the form of yarn or a woven fabric. Pretreatment normally occurs in the same facility as dyeing, often in the same machine (integrated processing). A series of mechanical and wet treatments prepare the fabric in a verity of ways. The nature and number of pretreatment stages depend upon both the fiber and the required end result.

Dyeing:
Jet Dyeing Machines:
The principle of using a jet of dye liquor to transport fabric in a dyeing machine was first patented in 1961 by Burlington Industries of USA. In this system, the fabric is rotated at a very high speed of about 400 meters per minute through a circular tube with the help of circulating dye liquor that is collected from the bottom of the machine and passed through a powerful pump and a heat exchanger to inject at the top of the machine. This equipment inspite of being much more expensive than a winch became a success because it could dye textured polyester fabric, a craze at that time, at 125 C. At this temperature, more rapid, well penetrated and better leveled dyeings obtained which makes an economic sense. The Burlington patent was purchased by the US machinery manufacturers, M/s. Gaston County and marketed the first jet machine in 1961. However, the machine became popular only after 1968 when the market for polyester textured and double jersey fabrics developed. The principle of jet dyeing was a revolutionary idea among the hitherto existing dyeing machines. As it often happens that once an idea is successfully established, many evolutionary developments take place in rapid succession to improve the original invention. In the next decade, almost every dyeing machinery maker marketed its own jet dyeing machine. It is not possible to give even the salient features of all types of these machines and only principles of the more popular jets will be discussed below.

Fully Flooded Jet Dyeing Machines:

In the Gaston County Jet, fabric is lifted and circulated with the help of a powerful jet of liquor and this tends to create longitudinal creases in the fabric. In order to reduce the tension, design of the machine was modified to give the fabric an upward lift by filling the dyeing tube with the dye solution. Machines have been patented having the dyeing tubes both in vertical and horizontal positions and a number of tubes mounted side by side with a common pump and heater. Capacity of each tube ranges between 100 to 150 kg and cloth movement speed varies from 100 to 200 m/min.

The dyeing process:

When a disperse dye is added to the dye bath for dyeing a hydrophobic fiber such as polyester, usually the dye is in excess of its solubility limit so that the dye is present in the dyebath in two forms (1) Completely soluble and (2) Insoluble but finely dispersed, the relative amounts being determined by the solubility of the dye in water at that temperature. When the fiber to be dyed is entered into the dyebath, the dissolved dye slips molecule by molecule into the narrow pores present in the fiber structure and gets attached there by certain forces. As a result, the concentration of the dissolved dye in the dyebath decreases and with this decrease more and more dispersed dye particles break up and go into solution, to be eventually absorbed by the fiber. Thus the dispersed particles of the dye act as a reservoir, which replenishes the dyebath, when it is depleted by dyeing. Since the dye has limited solubility in water, i.e., since it has an essentially hydrophobic nature, there is an inherent tendency in the dissolved dye to leave the aqueous phase. The dyeing of hydrophobic fibers with disperse dyes may be considered as a process of dye transfer from a liquid solvent (water) to a solid organic solvent (Fiber) and the dyeing is considered to take place in the following simultaneous steps: 1. Diffusion (Dispersion) of the dye in the solid phase into water by breaking up into individual molecules. 2. Adsorption of the dissolved dye from the solution onto the fiber surface. 3. Diffusion of the adsorbed dye from the fiber surface into the interior of the fiber substance towards the center. Since the first step of dyestuff diffusion in the dye bath depends on the dispersibility and solubility of dyestuff, further aided by the presence of dispersing agents in the dyebath and rise in temperature. It is not influenced by the fiber characteristics. The second step of dyestuff adsorption by the fiber surface is influenced by the solubility of the dye in the dyebath and that in the fibre. Low solubility should necessarily reduce the rate of adsorption. However, the converse need not be true, since the overall rate of dyeing is governed also by the third step of diffusion of the dye into 6

the interior of the fiber. Under the normal dyeing conditions of time and temperature, the adsorption rate is always higher than the diffusion rate (third step) and hence it is the third step that governs the overall rate of dyeing. When dyeing equilibrium is reached, the following subsidiary equilibria are also established. 1. Dye dispersed in the bath 2. Dye dissolved in the bath 3. Dye adsorbed on the fibre Dye dissolved in the bath. Dye adsorbed on the fibre. Dye diffused in the fibre.

The quality of dyeing is influenced by many factors, including the temperature and pH control. The main objective for controlling the pH throughout the dyeing cycle is to permit the dye to produce level and reproducible results. Colour reproducibility and the levelness of dye materials can be ensured by pH control systems such as the use of a buffer system or a pH sliding system. The use of buffer system requires a greater awareness not only of the factors that determine pH, but also those that stabilize it against interferences. The pH of the water supply may vary or drift during heating, and as a result a buffer system is required that resists the effect of such extraneous influences. A buffer system is usually based on two chemicals, namely a weak acid and its corresponding salts, such as acetic acid-sodium acetate. A pH sliding system is particularly useful for non-migrating disperse dye on polyester. The controlled lowering of the pH can be achieved by using products that release more acidic compounds as they undergo decomposition as the dyeing temperature increases.

Buffer solution:
A buffer solution is one that changes pH only slightly when small amounts of strong acid or a strong base are added. Buffer solutions have many important applications in the industry. A weak acid and its salt (conjugate base) the acetic acid sodium acetate solution acts as a buffer solution. One of the buffer components, the acid, is able to neutralize small amounts of OH-, and the other, the base, is able to neutralize small-added amounts of H3O+. pH = pKa + log [Conjugate base] [Weak Acid] This equation for the pH of an acetic acid-acetate ion buffer is a special case of more general equation, known as the Henderson-Hasselbalch equation.

Visits of XYZ Processing Industries (Pvt) Ltd.:

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First visit on 24th July 2007:

On first visit we met with the Director of XYZ Processing Industries (Pvt) Ltd. He pointed out the problems of their textile industry in various departments of wet processing and about the procedures of dyeing of blended fabric, consumption of chemicals and auxiliaries.

Second visit on 30th July 2007:

In our second visit of XYZ industry we observed the working procedures of wet processing. We had checked their production parameters e.g. (machine parameter, chemical parameters, Fabric parameters) and also observed all the processing in single lot of fabric step by step.

Photograph of XYZ Processing Industries (Pvt) Ltd. Jet Machine for Desizing and SP-Process.

1. In the first step the grey fabric was desized. In Desizing process, the sizing material was removed by the help of Desizing agent, ordinary well water was used in Desizing process. Desizing agent: X gm Wetting agent: Y gm Salt: Z gm Process time: 1hour Machine temp: 80oC

After 1 hr the Desizing process was completed, then desized fabric was washed water in the same jet.

with well

2. In 2nd step the special process in which caustic soda was used for the treatment of special process. Caustic soda: 10Kg/batch Anti foam: 500gm/batch Time:1hr 30min. Temp:130oC 3. In third step the neutralization process takes place in the same jet, which was used in sp process. Sulphuric acid; 1Kg/batch Wetting agent: 1Kg/batch Temp: 80oC Time: 30min. After neutralization process the chemical was drained and jet was again filled with fresh water, again run for 10min and unload the jet.

Photograph of Jet dyeing machine for Disperse dyeing

Photograph of Jigger dyeing machine Direct dyeing and for topping of Polyester/Cotton fabric 9

4. In fourth step of wet processing, dyeing was carried out in jet dyeing machine at high temperature. This is one bath dyeing for PC Blend. This process is high temperature dyeing in jet dyeing machine. Disperse dyes: X gm. Direct dyes: Y gm. Wetting agent: 1Kg Leveler: 1Kg (200gm/Kg) Acid: 2Kg ~ 4Kg. Temp: 130oC Heating time: 15min. Cooling time: 30min. Then washed with fresh well water. 5. Fifth step was hydroextraction. In this step water content of fabric was removed by high speed spin hydro extractor machine. In this visit we also collected the various samples of wet processing, which are. 1. Sample of grey fabric. 2. Sample of Sp process fabric. 3. Sample of neutralized fabric. 4. Sample of well water. 5. Sample of sp process waste water. 6. Sample of sp neutralized waste water. 7. Sample of dyeing waste water. 8. Sample of wetting agent. 9. Sample of (Sea salt- G-salt). 10. Sample of Buffer solution. 11. Sample of Acetic acid. 12. Sample of Sodium acetate. 13. Sample of dyes (Disperse and Direct dyes). 14. Sample of leveler. 15. Sample of HCl.

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Recipe of Buffer solution (According to Management) Acetic Acid: 28% Sodium Acetate: 10% HCl : 6.2%

Remaining water: X % Recipe of Buffer solution (According to Worker) Acetic Acid: 24.4% Sodium Acetate: 10.2% HCl Acid: 14.2% Remaining water: X %

Third visit on 13th August 2007:

In third visit we checked the pH of different processes. PH of Sp waste water = 9.5 pH of SP neutralized waste water = 5.0 pH of dyeing solution before dyeing = 7.4 pH of dyeing waste water = 8.4 pH of well water = 7.5

Result of collected Samples from XYZ Processing Industries (Pvt) Ltd.

S.No.
1. 2. 3. 4. 5. 6. 7. 8. 9. 10. 11.

Name of Sample
Well water Wetting agent 1% Company buffer Solution Sp Caustic waste water Sp neutralized waste Water Neutralized waste Water Dyeing waste water Sp neutralized fabric pH by extraction method % purity of Acetic acid % purity of HCl Acid Blend ratio of sp process (Caustic process) fabric Blend ratio of Neutralized fabric

pH
7.9 2.9 0.5 9.3 5.3 7.1 7.9 8.1 -

TDS
922 ppm -

Hardness
338 ppm -

Conc.
96 % 28.37 % -

Blend Ratio
Cotton=20% Polyester=80 %

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Cotton =19.75% Polyester= 80.25%

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Observations:
In Jet no 11 Lot No. 385. Workers did not maintain the temperature of Jet Workers did not check the pH of dyeing solution. No addition of salt in dyeing liquor. No control of liquor ratio. Jet was over loaded. Workers did not maintain the process time.

In Jet no 6 Lot No 399. Workers did not check the pH of dyeing solution pH is out of range. No control of liquor ratio. Workers cannot maintain the level of water in jet. Over dozing of leveling agent. Requirement was 1Kg but workers used 4Kg.

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Proposed Process Chart

Desizing / Washing Special Process (SP) Caustic

Process Chart Diagram See Page # 15

Process Chart Diagram See Page # 16

Washing / Neutralizing Process

Hydro Extracting Process

Check pH of the Fabric

Dyeing Process On High Temperature

Process Chart Diagram See Page # 17

Hydro Extracting Process

Check pH of the Fabric

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Desizing / Washing Process Chart Start

Fill Water L: R = 1:8 Set Nozzle Speed = 200 m/min Load Fabric Add Enzymatic Desizer 1-5 g/L Wetting Agent 0.5-1 g/L Set pH = 5.0 Salt 1-5 g/L Raise the Temperature Up to 80C for 1 hour
Not OK

Give Hot Wash on 100C and check with Iodine Solution

OK

Drain Bath and Refill

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Special Process (SP) Caustic Chart

Start

Fill Water L: R = 1:8 Set Nozzle Speed = 200 m/min Load Fabric Run for 5 minutes Add Caustic as per Recipe 1 Kg /150 Kg Fabric. Wetting Agent = 0.5-1 g/L Anti Foam = 0.5 g/L Start Programme Raise the Temperature up to 130C for 1 hour to 1 hour

Start Cooling at Programme End

Hot Wash and Add Acetic Acid for Neutralization Check the pH= 7.0 of Fabric
OK

Not OK

Cold Wash and Unload the Fabric Hydro Extraction END

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Dyeing Process Chart

Start

Fill Water L: R = 1:8 Set Nozzle Speed = 200 m/min Load Fabric Run for 5 minutes Add Dispersing Agent or leveling agent = 0.5 g/L Wetting Agent=0.5-1 g/L Adjust pH = 4.5 5.0 With Buffer Solution#1
OK

Start Cooling at Programme End

Not OK

Take Sample at 80C and add Salt=20 g/L

OK

Drain Refill Bath 1000 Liter Rinse Cold For 10 Minutes Drain & Unload Hydro Extraction END

Add Disperse and Direct Dyes

Not OK

Start Programme at 120C or 130C

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DESIZING
PROCESS DIAGRAM 100

90
80C 60 Min

80 TEMP (C)

70 60

Cooling

50

40
Water+Desizer+Detergent+Fabric+Salt

RT 0

10

20

30

40 50 60 TIME (IN MINUTES)

70

80

90

100

DESIZING WASHING DIAGRAM

100
90C HOT WASH 15 Minutes

90 TEMP (C)

80

60

40 RT 0
Fabric+Water

10

15

20

25

TIME (IN MINUTES) 23

SP-PROCESS (CAUSTIC)
PROCESS DIAGRAM
140
Hold Time 90 min

130
Cooling Gradient 4C

120 TEMP (C)

100 80
Gradient +2C/min Rinse and Neutralize

60 40
Add Caustic

Water+Fabric

RT 0 20 40 60 80 100 120 140 160 180

TIME (IN MINUTES)

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DESPERSE/DIRECT DYEING
PROCESS DIAGRAM
140
Hold Time 15 min depends on shade depth

130

120 TEMP (C)

Cooling Gradient 4C

100 80
Gradient +2C/min Add Sea Salt Hold 15 min

60 40

Add Disperse/Direct Dyes

RT 0

Water+Fabric+Leveler

10

20

30

40

50

60

70

80

90

TIME (IN MINUTES)

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Suggestions about Process Control:

We have observed the whole jet dyeing processing area during number of visits and found that there are some weaknesses in jet dyeing, SP process, dyeing equipment and processing techniques. Industry shall provide the Standard pH stripes pH = 0-14 (Merck) to the each jet operator. Industry shall abide by the process control chart and recipes. Industry shall equip the jets with heat exchanger or solenoid valves for controlling the steam and internal temperature of jet machine. Industry shall equip the jets with the automatic graph control system. Industry shall equip the jets with water gauge for correct filling of water and maintaining the L: R as according to the standard conditions. Operator shall check the pH after neutralizing with Standard universal indicator solution pH = 0-14 (Merck) in SP process and finally unload the fabric. Operator shall do the hydro extraction of fabric after SP-neutralization. Hydrochloric and Sulphuric acid are hazardous for labors. Sulphuric acid also affects on the cotton portions of PC blended fabric, it retards the cotton approximately about 0.25%. By the use of excess Sulphuric acid, sulphate ions are formed, which also affects on the shade of fabric. Industry shall use provided buffer recipe no.1 in dyeing processing. Operator shall maintain the pH of bath 4.5-5.0 and after that run; the color will be well mixed with water and then run the color at approximately 40C. Operator shall check the pH of bath after running the Programme approximately after hour and finally before unloading the fabric. Operator shall check the desizing efficiency of desized fabric with Iodine solution. Industry shall purchase the Tegawa Scale for measuring the correct degree of Desizing. Industry shall provide all pre weigh chemicals and dyestuffs to the jet operators. Jet operators cannot change any parameters or recipe without consulting or intimating the Management.

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