UNIVERSITI TEKNOLOGI MARA

COLORANT FROM MELASTOMA MALABATHRICUML. PLANT

MOHD AZLIN BIN MOHD NOR

Thesis submitted in fulfilment of the requirements for the degree of

Master of Science

Faculty of Applied Sciences

June 2012

AUTHOR'S DECLARATION

I declare that the work in this thesis was carried out in accordance with the regulations

of Universiti Teknologi MARA. It is original and is the result of my own work, unless

otherwise indicated or acknowledged as referenced work. This thesis has not been

submitted to any other academic institution or non-academic institution for any degree

or qualification.

I, hereby, acknowledge that I have been supplied with the Academic Rules and

Regulations for Post Graduate, Universiti Teknologi MARA, regulating the conduct of

my study and research.

Name of Student : Mohd Azlin bin Mohd Nor

Student I.D. No. : 2007130997

Programme : Master of Science (Textile Technology)

Faculty Applied Sciences

Thesis Title : Colorant from Melastoma Malabathricum L. Plant

Signature of Student

Date : June 2012

ABSTRACT

Malaysian bushes and forest are really rich with various types of plants that can be used as raw material for conversions into useful products. The current trends, where consumers are more likely to buy green product, have shifted the usage of synthetic dyes to natural dyes. The main problem of dyeing using synthetic dyes is the release of toxic industrial waste and the usage of natural dyes could minimise this problem. Natural dyes in powder form are really rare and most of them are grinded directly from parts of plant. The main aim of the investigation is to use parts of Melastoma Malabathricum L. plant for production of natural dyes in liquid and powder form as colourant for dyeing silk fabrics. The process started with extraction of raw material, grinded into powder form and application of colourant for both liquid and powder form on silk fabrics. Several mordant were used to fix the colour on fabrics and at same time a variety of shades can be obtained. The dried paste obtained after extraction was not directly grinded since it cause uneven dyeing. However, an alternative approach was used involving the usage of beta-cyclodextrin mixed with dried paste to form powder that gave even shade on silks. The depths of shades were compared by measuring the dyed fabrics using Gretag McBeth Colour-Eye 7000A spectrophotometer. Dyeing with wood ash gave the highest reflectance while iron turns out the deepest colour among all mordant. Results for colourfastness to washing were encouraging and comparable with other natural dyes which were in the range of 2/3 to 4/5 for all samples. However, it can be observed that the colourfastness properties of dyed fabrics using powder form gave better rating than liquid form for staining. The result showed that the fastness property for dyed samples was good ranging from 3/4 to 5. The size of colourant in powder form ranged from micron to nano size.

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ACKNOWLEDGEMENTS

The author would like to extend his gratitude to the following people upon completion of the guidelines on Thesis:

Professor Wan Yunus Wan Ahmad, Ph.D., CText FTI, for his invaluable guidance, patience and encouragement during the course of this research project

Project co-supervisor, Nor'ashikin Saim, Ph.D., for her help and understanding.

The all staff of the Textile Technology Programme, especially Mr. Zainal Sukail, Assistant Lecturer of Textile Technology programme for his advice and assistance.

Last, but by no means least, my parents, my wife, Nur Azihan Yusof for her understanding and encouragement throughout the work and my daughter Nurul Aulia Raiisa for her warmest love and inspiration.

Without them, I would not have seen the light of the day.

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TABLE OF CONTENTS

PAGE TITLE PAGE AUTHOR'S DECLARATION ABSTRACT ACKNOWLEDGEMENT ,v TABLE OF CONTENTS v LIST OF TABLES viii LIST OF FIGURES ix

CHAPTER ONE : INTRODUCTION 1 1.1 BACKGROUND OF THE STUDY 1 1.2 PROBLEM STATEMENT 2

1.3 SIGNIFICANCE OF THE STUDY 3 1.4 RESEARCH OBJECTIVES 4

1.5 SCOPES AND LIMITATIONS OF STUDY 4

CHAPTER TWO : LITERATURE REVIEW 6 2.1 COLOUR 6 2.2 A BRIEF HISTORY OF NATURAL DYES 6 2.3 SOURCES OF NATURAL DYES 8

2.3.1 Natural Dyes From Plants 8

2.3.2 Natural Dyes From Animals 9 2.3.3 Natural Dyes From Minerals n

2.4 CHEMISTRY OF NATURAL DYES 12

2.5 MORDANT 13

2.5.1 Alum 14 2.5.2 Iron 14

2.5.3 Tin 15 2.5.4 Tawas 15

2.5.5 Wood Ash 15

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2.6 MELASTOMA MALABATHRICUML. (SENDUDOK) 16 2.7 BETA-CYCLODEXTRIN 16 2.8 PREVIOUS STUDY ON NATURAL DYES FROM MELASTOMA

MALABATHRICUM L. 18

2.9 PREVIOUS STUDY ON EXTRACTION METHODS 18 2.10 PLANT PIGMENT 21

2.10.1 Chlorophylls 21

2.10.2 Carotenoids 22

2.10.3 Flavonoids 23

2.10.4 Betalains 26

CHAPTER THREE : MATERIALS AND METHODS 27 3.1 FLOWCHART OF THE RESEARCH 27

3.2 FABRICS 28

3.3 MORDANT 28

3.4 MELASTOMA MALABATHRICUML. PLANT 28

3.5 CHEMICALS 29 3.6 RESEARCH METHODS 31

3.6.1 Water Extraction Technique 31 3.6.2 Solvent Extraction Technique 31 3.6.3 Grinding Process 32 3.6.4 Dyeing Process 34 3.6.5 Colourfastness to Washing 34 3.6.6 Colour Measurement 36

3.6.7 UV Spectrophotometer 36 3.6.8 Scanning Electron Microscope (SEM) 36

CHAPTER FOUR : RESULTS AND DISCUSSION 38 4.1 PERCENT YIELD OF PASTE FROM PARTS OF MELASTOMA

MALABATHRICUML. PLANT 38

4.2 DYED SAMPLES 39

4.3 COLOUR MEASUREMENT (REFLECTANCE CURVE) 44

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4.3.1 Melastoma Malabathricum L. Fruit (MF) 44 4.3.2 Melastoma Malabathricum L. LeafXML) 47 4.3.3 Melastoma Malabathricum L. Petal (MP) 49 4.3.4 Melastoma Malabathricum L. Root (MR) 52

4.4 COLOUR MEASUREMENT (CIE L*A*B*) 55 4.4.1 Melastoma Malabathricum L. Fruit (MF) 55 4.4.2 Melastoma Malabathricum L. LeafXML) 60 4.4.3 Melastoma Malabathricum L. Petal (MP) 64 4.4.4 Melastoma Malabathricum L. Root (MR) 69

4.5 FASTNESS PROPERTIES 74 4.5.1 Colourfastness To Washing 74

4.6 UV/VISIBLE SPECTROPHOTOMETER 77 4.7 MORPHOLOGY OF DYES 82

4.8 SUMMARY OF RESULTS 85

CHAPTER FIVE : CONCLUSION AND RECOMMENDATIONS 87 5.1 CONCLUSION 87 5.2 RECOMMENDATIONS 88

REFERENCES 100 APPENDICES 101

'PENDIXA 102 APPENJ&fxB APBENDIX C

'PENDEK D H

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TABLES

LIST OF TABLES

PAGE

Table 3.1. Soap Solution Formulation 35 Table 4.1. Dyed Silk using Melastoma Malabathricum L. Fruit

(MF) with different mordant 40 Table 4.2. Dyed silk using Melastoma Malabathricum L. Leaf (ML)

with different mordant 41

Table 4.3. Dyed silk using Melastoma Malabathricum L. Petal (MP) with different mordant 42

Table 4.4. Dyed silk using Melastoma Malabathricum L. Root

(MR) with different mordant 43 Table 4.5. CIE L*a*b* values for MF (Boiling) 55 Table 4.6. CIE L*a*b* values for MF - ME and ME/ A 57 Table 4.7. CIE L*a*b* values for MF - ME / P andME/A/P 58 Table 4.8. CIE L*a*b* values for ML (Boiling) 60 Table 4.9. CIE L*a*b* values for ML - ME & MEA 61 Table 4.10. CIE L*a*b* values for M L - M E / P and M E / A / P 63 Table 4.11. CIE L*a*b* values for MP - Boiling 65 Table 4.12. CIE L*a*b* values for MP - ME and ME/ A 66 Table 4.13. CIE L*a*b* values for M P - M E / P and M E / A / P 68

Table 4.14. CIE L*a*b* values for MR - Boiling 69 Table 4.15. CIE L*a*b* values for MR - M E and MEA 71

Table 4.16. CIE L*a*b* values for MR - ME / P and ME/A / P 72 Table 4.17. Results of Colourfastness to Washing for dyed silk (MF) 74 Table 4.18. Results of Colourfastness to Washing for dyed silk (ML) 75 Table 4.19. Results of Colourfastness to Washing for dyed silk (MP) 75 Table 4.20. Results of Colourfastness to Washing for dyed silk (MR) 76

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LIST OF FIGURES

FIGURES PAGE

Figure 2.1. Molluscs 10

Figure 2.2. Kermes 11

Figure 2.3. Cochineal 11

Figure 2.4. Melastoma malabathricum L. plant 16 Figure 2.5. Chemical Structure of the Three Main Types of Cyclodextrins 17

Figure 2.6. Chemical structure (a) and shape (b) of P-cyclodextrin 17 Figure 2.7. Chlorophyll 22

Figure 2.8. Hemoglobin 22

Figure 2.9. Structure of Flavonoids 23 Figure 2.10. Structure of Flavone 24

Figure 2.11. Structure of Flavanone 24

Figure 2.12. Structure of Isoflavone 24

Figure 2.13. Structure of Anthocyanin 25 Figure 2.14. General structures of betalamic acid (a), betacyanins (b) and

betaxanthins (c).Betanin: Ri = R2 = H. R3 = amine or amino acid group 26

Figure 3.1. Flowchart of Research Methodology 27

Figure 3.2. Plain Weave Silk Fabric Structure 28

Figure 3.3. Melastoma malabathricum L. Petal (MP) 29 Figure 3.4. Melastoma malabathricum L. Fruit (MF) 29 Figure 3.5. Melastoma malabathricum L. LeafXML) 30 Figure 3.6. Melastoma malabathricum L. Root (MR) 30 Figure 3.7. Sample for Extraction 31

Figure 3.8. The Excess Solution after Filtration 32

Figure 3.9. Rotary Evaporator 32 Figure 3.10. Planetary Ball Mill Grinder 33

Figure 3.11. SDL Autowash Machine 34

Figure 3.12. Composite Sample for Colourfastness to Washing 35

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Figure 3.13. Scanning Electron Microscopre (SEM) 37 Figure 4.1. Percentage of paste extracted using methanol and acidified

methanol 38

Figure 4.2. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Fruit (MF) / Boiling 45 Figure 4.3. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Fruit (MF) / ME (Liquid) 45 Figure 4.4. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Fruit (MF) / MEA (Liquid) 46 Figure 4.5. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Fruit (MF) / ME (Powder) 46 Figure 4.6. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Fruit (MF) / MEA (Powder) 47 Figure 4.7. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Leaf (ML) / Boiling 47 Figure 4.8. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Leaf (ML) / ME (Liquid) 48 Figure 4.9. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Leaf (ML) / MEA (Liquid) 48 Figure 4.10. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Leaf (ML) / ME (Powder) 49 Figure 4.11. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Leaf (ML) / MEA (Powder) 49 Figure 4.12. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Petal (MP) / Boiling 50 Figure 4.13. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Petal (MP) / ME (Liquid) 50 Figure 4.14. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Petal (MP) / MEA (Liquid) 51 Figure 4.15. Reflectance curves for silk samples dyed with Melastoma

Malabathricum L. Petal (MP) / ME (Powder) 51

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Figure 4.16. Reflectance curves for silk samples dyed with Melastoma Malabathhcum L. Petal (MP) / MEA (Powder) 52

Figure 4.17. Reflectance curves for silk samples dyed with Melastoma

Malabathhcum L. Root (MR) / Boiling 52 Figure 4.18. Reflectance curves for silk samples dyed with Melastoma

Malabathhcum L. Root (MR) / ME (Liquid) 53 Figure 4.19. Reflectance curves for silk samples dyed with Melastoma

Malabathhcum L. Root (MR) / MEA (Liquid) 53 Figure 4.20. Reflectance curves for silk samples dyed with Melastoma

Malabathhcum L. Root (MR) / ME (Powder) 54 Figure 4.21. Reflectance curves for silk samples dyed with Melastoma

Malabathhcum L. Root (MR) / MEA (Powder) 54 Figure 4.22. Positioning of samples on 2D colour plot for MF (Boiling) 56 Figure 4.23. Positioning of samples on 2D colour plot for MF (ME & MEA) 58 Figure 4.24. Positioning of samples on 2D colour plot for MF

(ME / P & ME / A / P) 59 Figure 4.25. Positioning of samples on 2D colour plot for ML (Boiling) 61 Figure 4.26. Positioning of samples on 2D colour plot for ML (ME & MEA) 62 Figure 4.27. Positioning of samples on 2D colour plot for ML 64

(ME / P & ME / A / P) Figure 4.28. Positioning of samples on 2D colour plot for MP (Boiling) 65 Figure 4.29. Positioning of samples on 2D colour plot for MP (ME & MEA) 67 Figure 4.30. Positioning of samples on 2D colour plot for MP

(ME / P & ME / A / P) 69 Figure 4.31. Positioning of samples on 2D colour plot for MR (Boiling) 70 Figure 4.32. Positioning of samples on 2D colour plot for MR (ME & MEA) 72 Figure 4.33. Positioning of samples on 2D colour plot for MR

(ME / P & ME / A / P) 73 Figure 4.34. UV Visible Spectrum of Melastoma Malabathhcum L. Fruit

(MF) at various concentrations 78 Figure 4.35. UV/Vis Spectrum of Melastoma Malabathhcum L. Fruit (MF)

at 0.0002 g/ml 79

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Figure 4.36. UV Visible Spectrum of Melastoma Malabathricum L. Leaf (ML) 80

Figure 4.37. UV/Vis Spectrum of Melastoma Malabathricum L. Petal (MP) at 0.002 g/ml 80

Figure 4.38. UV Visible Spectrum of Melastoma Malabathricum L. Petal

(MP) at 0.0002 g/ml 78 Figure 4.39. UV/Vis Spectrum of Melastoma Malabathricum L. Root (MR) 82 Figure 4.40. Dye Particles after grinded using Planetary Mono Mill under

SEM 83

Figure 4.41. Particles in nano size form 83

Figure 4.42. Particles in micron size 84

Figure 4.43. Particles in the fabric structure 85

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CHAPTER ONE INTRODUCTION

1.1 BACKGROUND OF THE STUDY

Natural dyestuffs have been utilised for ages. Early generation found out berry stains on their fingers and went from there to imparting colours in their daily lives (Smith, 2002). Natural dye was also discovered unexpectedly, but their role has turned a great deal of human life and it is hard to conceive of modern times without dyes (Krishnamurthy, Siva & Kumar, 2002).

Natural dyes can be classified into three classes, which could be obtained from plants, animals and minerals (Siva, 2007). Natural dyes do not interact directly on the fabrics but require mordant to fix the dyes onto the fabrics and prevent the colour from fading. Mordant consists of chemical compounds that attach the dyes onto the fabrics. It is an assisting element to the reaction between the fibre and dye which is commonly used during natural dyeing process (Siva, 2007). Dyeing natural dyes with different mordant create unique attributes that yield different colours on the dyed fabrics even from the same source.

Natural dyes work best with natural fibres such as silk, wool, cotton, jute, sisal, linen, ramie and almost all of them need some kind of mordant (Vankar, 2000) to be utilised during dyeing. Unfortunately, natural dyes are rarely used in the dyeing process except by craft dyers and specialist companies. It has become a common misconception that natural dyes solely bring out beige, brown colours and washed-out shades. In reality, a comparable colour between natural with synthetic dyes can be produced and sometimes natural dyes are more eye-catching colours (Gilbert & Cooke, 2001).

Malaysia is among the mega biodiversity countries in the world and one of its local plant, Melastoma malabathricum L. has been discovered to have a great potential as dye-yielding plant (Lemmens & Spetjiptoed, 1991). The plant comes with attractive purplish petals and can be found everywhere. In Malaysia, it grows wild in the bushes and along nearly every Malaysian highway. The purplish flower makes it valuable to be

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used as decorative plant and at the same time has the potential as a source for natural dye extraction (Janna, Khairul, Maziah & Mohd, 2006). Natural dyes from plant can be obtained from several parts such as leaves, fruits, seeds, flowers, barks and roots (Lemmens & Spetjiptoed, 1991). The main drawback of these natural dyes lies in terms of the volume of their extraction yield that only able to get a few grams of extract for a certain weight of raw material (Velmurugan, Kamala-Kannan, Balachandar, Lakshmanaperumalsamy, Chae & Oh, 2010). With innovation and advancement of technology, various types of extraction methods could be invented in raising the amount of natural dye extract in time to come.

Natural dyes are also safer and environmental friendly (Kumar & Sinha, 2004) which stimulates people's interest regarding the utilisation of natural dyes. Natural dyes show better biodegradability and are generally environmentally friendly. In spite of their mediocre fastness properties, natural dyes are suitable for community with high environmental awareness throughout the world (Deo & Desai, 1999). Moreover, the concern in discovering new renewable low-cost sources of natural dyes to be utilised by industry is growing and many waste material from fruits or vegetables has been used as material to produce natural dyes. Although it is unlikely all dyestuffs will be produced solely from plants, it is an interesting and exciting prospect that one day some of everyday colours could be derived from plant (Gilbert & Cooke, 2001).

Natural dyestuff can also offer an attractive alternative as in certain areas, the synthetic dyes and other additives are imported thus causing their price becoming relatively expensive (Bhattacharya & Shah, 2000).

1.2 PROBLEM STATEMENT

The usage of non-toxic, non-allergic and eco-friendly natural dyes on textiles has become a matter of significant due to the awareness among world population to avoid some hazardous synthetic dyes (Samantha, & Agarwal, 2009). The usage of natural dyes for fabric dyeing almost vanished with the appearance of synthetic dyes. The wide range of colours available with acceptable fastness properties at average costs was the main

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reason for the substitution of natural dyes by their synthetic dyes (Schweppe, 1992). However, production and usage of synthetic dyes develop severe toxic industrial waste problems (Gurley & Boulder, 1995).

The problem of toxic effluent discharge by synthetic dyes can be reduced by using natural dyes thus creating more eco-friendly environment ("Overcapacity and Stringent Regulations Drag Textile Dyes Market," 2007). This advantage plays important role in saving nature and provide options for nature lovers. The unique colours obtained from natural dyes also have their own followers. Most of natural dyes are extracted from plants and one of them is Melastoma malabathricum L. plant. This plant can be obtained abundantly especially in Malaysian bushes and their potential as a source for natural dyes has been identified. Moreover, some of natural dyes also could produce brightest colour such as Turmeric that could give bright yellow and some of them also has medicinal value that act to revitalizes the skin while indigo could give cooling sensation (Siva, 2007). Natural dyes also have no disposal problem and obtained from renewable sources (Patel, 2011). Natural dyes also could offer quite a wide range of colours since it could be dyed using various mordant (Ekrami, Mafi & Motlagh, 2011).

1.3 SIGNIFICANCE OF THE STUDY

Since the emerging of widely available and cheaper synthetic dyes in 1856 that gives average to excellent colourfastness properties, the usage of natural dyes of having poor to moderate light and wash fastness has declined (Samanta & Agarwal, 2009). Synthetic dyes are commercially accessible due to the ease of use and produce various colour shades. However, currently environmental problems are the main concern making natural dyes to become a better choice because they exhibit less toxicity and allergic reactions for consumers (Khanchaiyapoom & Prachayawarakorn, 2008).

Natural dyes from plants have high aesthetical value although it has a limited range of colours. It is expected that natural dyes from plants can be used in other non-textile application such as painting and art. Hence, it can be commercialised since our country is rich with the sources with low raw material cost. Natural dyestuffs also create

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unique colours that might be different from dye lot to other dye lot (Smith, 2002). The usage of natural dyes is considered as a way of exploiting renewable resources, causing least pollution expose to the environment and giving a low risk to human health (Gulrajani, Srivastava& Goel, 2001).

Natural dyes can provide not only a varied source of material, but also the possibility of income through sustainable harvest and sale of these dye-yielding plants. A lot of dyestuffs are available from plants which are still underutilised or can be easily grown in the bushes or gardens (Vankar, 2000). The underutilised plant are also considered as waste plant since it is abundantly available but still not fully exploited to produce other products.

The application of natural dyes from waste plants could implement the 'waste-to-wealth' principle as suggested by previous Prime Minister ("The Star," 1 March 2005) by converting natural 'waste' such as rocks/soils and underutilised plants to useful products.

1.4 RESEARCH OBJECTIVES

The objectives of this research are: 1. To identify coloured compound in Melastoma malabathricum L. plant extracts

by using UV-visible spectrophotometer instrument. 2. To extract colorants from parts of Melastoma malabathricum L. plant through

water and solvent extraction in liquid and powder forms (microns and submicrons).

3. To assess the shades and colourfastness properties of the dyed samples.

1.5 SCOPES AND LIMITATIONS OF STUDY

The focus of this study is to extract colorants from parts of Melastoma malabathricum L. plant using water and solvent extraction methods. Several scopes and limitations have been identified in order to fulfil the objectives of this research.

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1. The parts of Melastoma malabathricum L. plant has been collected around Shah Alam, Selangor and the voucher specimens of Melastoma malabathricum L. (FRI-48920), has been deposited at the Herbarium of Forest Research Institute Malaysia (FRIM) Kepong, Malaysia. The plant was chosen because it can produce attractive colours according to previous study conducted by other researchers. In addition, it is also available abundantly and their usage was still not fully utilized.

2. Parts of Melastoma malabathricum L. plant also has been tested to identify coloured compound using UV-visible spectrophotometer.

3. 100% white satin-weave silk will be used in this research. 4. Planetary ball mill located at Textile Technology Laboratory, Faculty of

Applied Sciences, Universiti Teknologi MARA (UiTM) will be used in order to grind the dyes to produce microns and submicron sizes powder form. Scanning Electron Microscopy (SEM) will be used at Material Technology Laboratory, Faculty of Applied Sciences, Universiti Teknologi MARA (UiTM), Shah Alam. Shimadzu UV-Visible Spectrophotometer at Blok G, Faculty of Applied Sciences, Universtiti Teknologi MARA.

5. All dyeing processes and colourfastness testing will be carried out at Textile Technology Laboratory, Faculty of Applied Sciences, UiTM Shah Alam.

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CHAPTER TWO LITERATURE REVIEW

2.1 COLOUR

Colour is obtained by applying chemical compound called chromophore that produces colour on the dyed fabrics. The chromophore must be captured as strongly as possible into fibre structure during dyeing process and the colour must be resistant to washing. Colour is introduced on fabrics through dyeing process using dyes and pigment. The obvious difference between these colorants is in terms of their solubility where dyes are soluble while pigments are insoluble. Dyes also were defined as soluble coloured compound that mainly used to colour textile materials from solution in water, while pigments normally integrated by a diffusion process into products such as paints and printing inks (Bechtold & Mussak, 2009).

Prehistoric people have employed colour into their daily life for instance in adorning their bodies, colouring animal skins, furs for their clothes and decorating paintings on the cave wall. At that time, all the colours that were utilised for beautifying purposes were derived from natural resources taken from their surroundings (Christie, 2001). The consumption of natural dyes extracted from natural sources is controlled due to the scarcity of the materials as well as the intricate extraction and dyeing procedure. Since the first appearance of synthetic dyes introduced by Perkin in 1856, more convenient and cheap synthetic dyes have emerged and made the usage of natural dyes declined due to their poor price competitiveness compared to synthetics (Zollinger, 1991).

2.2 A BRIEF HISTORY OF NATURAL DYES

Beautiful natural colours of plants and minerals have been admired by humans since several centuries. It has been acknowledged and applied for thousands of years for body painting and making foods for ancient humans (Kirk-Othmer, 1998). The action

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was exercised in Europe during the Bronze Age. The first written evidence of the usage of natural dyes was discovered in China dated 2600 BC. However, dyeing process was believed to start as early as 2500 BC in the Indus Valley and this information has been supported by findings of traces of madder dye and coloured garments of cloth in the ruins of the Indus Valley Civilization at Mohenjo-Daro and Harappa 3500 BC period (Driessen, n.d.).

Dyes from natural sources have become the main source of textile colouring material till the mid to late 19th century (Peggie, Hulme, McNab & Quye, 2008). During the the mid of 19th century almost all dyes were extracted from the leaves stems, roots, berries, petals of various dye-yielding plants and from animals such as insects, shellfish as well as from minerals (ocher). Chemical tests of red fabrics found in the tomb of King Tutankhamen in Egypt showing the presence of alizarin which is a pigment that can be extracted from the roots of the madder plant. The coloured fabric was considered of having brilliant and exotic colours. (Driessen, n.d.).

According to Kris (n.d.), by the 4th century AD natural dyes from Brazilwood, weld, indigo, madder, woad and dark reddish-purple were identified while in the 15th century, dyes from Kermes and cochineal were turning to be increased in popularity for dyeing. However, Schetky (1986) stated that in the Mediterranean prior to the arrival of Christianity, almost all dyeing industry came up around Tyrian purple. Tyrian purple is derived from the mucous gland adjacent to the respiratory cavity within some species of Purpura and Murex.

In 1869, William Henry Perkin introduced the first synthetic dyes thus making natural dyes to lose their popularity. In the end of the 19th century, some tweed producers from Scotland were the only ones who were still using natural dyes and later the use of natural dyes on a commercial scale hardly exists. At that time, natural dye was mainly used in remote areas where people have either limited access to synthetic dyes or a vested concern in continuing their ancient dyeing traditions only (Schetky, 1986).

The usage of natural dyes is gaining popularity again with the resurgence of new developed technology in hand crafting, most notably in the fields of weaving, spinning, papermaking, leather craft and basketry (Driessen, n.d.). The renewed technology and historic concern in natural dyeing assist to identify dyestuffs discovered by archaeologist

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in order to preserve the dyed textiles housed in museums and private collections (Schetky, 1986). As Grierson (1989) said in her book Dyeing and Dyestuffs, "Whilst the dyeing industry of today keeps pace with modern science, the future use of natural dyes will also follow a new path, but one firmly rooted in tradition".

2.3 SOURCES OF NATURAL DYES

Natural dyes have been used since prehistoric times for dyeing and printing fabrics. There are primarily three main sources from which natural dyes can be obtained such as from plants, animals and minerals.

2.3.1 Natural Dyes From Plants

Julie (2007) stated that prior to the introduction of synthetic dyes, plants were a major source of colorants for dyes, inks and paints. Dyes from plants were grown as farm crops such as indigo (a deep blue dye), woad, madder (red dye), henna (a reddish-brown dye used on hair, skin, and fingernails), saffiower petals (a red dye used to make cosmetic rouge) and autumn crocus (a yellow pigment used to colour textiles and food products).

Plants which are abundantly available in almost every country in the world have played their role as important sources of natural dyes for natural dyeing process (Bechtold, Turcanu, Ganglberger & Geissler, 2003). Several parts of plants such as barks, stems, fruits, leaves, roots, berries and seeds might bear colouring matter which can be worked as natural dyes. Some plants may have many colours depending upon which part of the plants to be used (Vankar, 2000).

In India, it has been recorded that approximately 450 plants are able to produce natural dyes. Some of them also possess medicinal value in addition to their dye-producing characteristics. Natural dyes from turmeric that produced bright yellow colours are a powerful antiseptic which can revitalise the skin while indigo gives a cooling sensation. Several other sources of plant dyes rich in naphthoquinones such as Lawsonia

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inermis L.(henna), juglone from walnut and lapachol from alkanet are reported to have antifungal and antibacterial activity (Siva, 2007).

Indian researchers also studied the antibacterial activity of other plants such as Acacia catechu Willd, Acanthophonax trifoliatum L., Adhatoda vasica Nees. Aloe barbadensis L., Bixa orellena L. , Butea monosperma Lam., Capsicum annuum L., Carthamus tinctorious L., Elaeodendron glaucum Pers. and Azadirachta indica A. that also show antimicrobial activity and consist of pigment which can be used as source of natural dyes (Chengaiah, 2010).

Moreover, currently most of researchers are trying to find an alternative source other than parts of the plant such as by-products of farming and forestry as well as wastes from food and beverage industry to be used as raw material for production of natural dyes. The by-product and waste such as bark or saw-dust from timber industry, onion peels, pressed berries and black tea residue (Pauline, Gargadenne, Garcia, Dupont, Lecoeur, Candelier, et al., 2006; Dawson, 2008; Kumarsi, Abomahboub, Rashedi, & Parvinzadeh, 2009; Parvinzadeh & Kumarsi, 2008; Bechtold, Mahmud-Ali, & Mussak, 2007; Sabeti, 1994) were used as dye source. The usage of these materials as raw material for natural dyes can contribute to preservation of the environment and also reduce the cost of natural dyeing process.

At present, Ekrami & Tayebi (2011) has successfully used forest tree wood disposals as natural dye that extracted from Alder (Alnus. Glutnisa) and dyed on nylon fibre. The wood of Alder forest tree is known to contain extractable natural dyes such as hydroxycinnamic acid derivatives and tannins (Pauline et. al., 2006).

2.3.2 Natural Dyes from Animals

The earliest animal dyes come from various species of snails that can be found along the coasts of the Mediterranean. One of them is Tyrian purple which was discovered by the Phoenicians around 1500 BC and became the most important dye of the civilizations that fell and rose in the area (Clair, 1986). The molluscs as shown in Figure 2.1 were gathered as dye factories arisen along the West African coasts,

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Mediterranean and Phoenician traders brought the dye to Italy, France and Spain. Historically, Julius Caesar, Cleopatra and Alexander the Great among those who wore dyed clothes with Tyrian purple (Siva, 2007).

FIGURE 2.1. Molluscs (Potrykus, n.d.)

Other animal dyes were obtained from insects (Smith, 2002; Siva, 2007) Kermes (Figure 2.2) was a scarlet dye obtained from Coccus ilicis, a tree scale insects that lived on oak. Moss (2008) reported that it has been used since ancient times and other writers referred to it as captured booty in 1400 B.C. Kermes varied in colour from bluish-red to brilliant scarlet depending on the mordant used. Mexican dyers discovered a dye very similar to kermes called Cochineal about 1000 B.C. Cochineal (Figure 2.3) is derived from another scale insect, Dactylopius coccus that lived on cactus. The insects were picked up by hand before they were dried in the sun. The dried insects resembled rust-coloured grain seeds and gave scarlet dye when soaked in water.

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FIGURE 2.2. Kermes (Mary, n.d.)

FIGURE 2.3. Cochineal (Sheila, 2010)

2.3.3 Natural Dyes from Minerals

Colours also can be produced from mineral dyes such as manganese, Prussian blue (Fe7(CN)i8), antimony orange, chrome yellow, bronze, teal green and iron buff. However, lately more sources of mineral dyes were introduced including dyes from ferruginous clay and sedimentary rocks (Driessen, n.d.). Mineral natural dyes commonly gave colours like yellow (limonite) or red (hematite). The development of natural dyes from minerals has not been well documented since the ancient times.

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Red ocher also known as "a la almagra" or red ceramics has first attracted attention in the Iberian Peninsula based on observations held in the 1930's in several areas of Andalusia. Most of remains in at archaeological spot were two types of red ceramics (Ferna'ndez, 2004; Pen, 1987; Navarrete, 1976; Navarrete, 2004) were discovered that can be distinguished from direct observation where a first type has a red (intense red to orange) external colour adhering very well to the ceramic surface and a second type is considered as painted ceramic which is less firm and very friable which is believed were coloured using red ocher (Capel, Huertas, Pozzuoli, & Linares, 2006).

Additionally, Ab. Kadir, Wan Ahmad, Ruznan, & Yusoh, (2010) in their research extracted colorant from soils/rocks. The material was grinded into small micron size and then dyed on silk and polyester fabrics. The colourfastness results obtained were encouraging and comparable to other natural colorant. Nano-size rocks' colorants have been proven suitable on polyester with good fastness properties and can be marketed as niche products for niche market as well as for crafts and probably for painting colorants. The colorants are cheap, easily source even though they are difficult to be prepared (Wan Ahmad, Ruznan, Ab. Kadir, Ahmad, Abdul Hamid, 2008).

2.4 CHEMISTRY OF NATURAL DYES

Natural dyes can be defined as dyes that can be derived from animals and plants with no or very little chemical processing. They are mainly mordant dyes but include some vat dyes, a few solvent dyes, some pigments, some direct, acid dyes and one natural basic dye.

Natural dyes can be divided into two categories which are substantive and adjective (Mary, n.d.). Substantive or also known as direct dyes become chemically deposited without the assistance of any other additives to the fibre such as indigo and certain dyes from lichens. The substantive dyes also do not need mordant in order to colour the fibre and include the tannic acid from gall nuts, walnut leaves, turmeric as well as indigo, cochineal and alizarin reds from annatto, safflower and the purple of some

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