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Waste from eucalyptus wood steaming as a natural dye source for textile fibers
Accepted Manuscript Waste from eucalyptus wood steaming as a natural dye source for textile fibers T. Rossi, P.M.S. Silva, L.F. De Moura, M.C. Araújo, J.O. Brito, H.S. Freeman PII:
S0959-6526(16)32173-4
DOI:
10.1016/j.jclepro.2016.12.109
Reference:
JCLP 8684
To appear in:
Journal of Cleaner Production
Received Date: 9 June 2016 Revised Date:
18 December 2016
Accepted Date: 20 December 2016
Please cite this article as: Rossi T, Silva PMS, De Moura LF, Araújo MC, Brito JO, Freeman HS, Waste from eucalyptus wood steaming as a natural dye source for textile fibers, Journal of Cleaner Production (2017), doi: 10.1016/j.jclepro.2016.12.109. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Waste from eucalyptus wood steaming as a natural dye source for textile fibers1
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ROSSI, T. a*, SILVA, P.M.S. a, DE MOURA, L.F.b, ARAÚJO, M.C.a, BRITO, J.O. b, FREEMAN, H.S.c
a. School of Arts, Sciences and Humanities, University of São
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Paulo, São Paulo, Brazil
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b. Superior School of Agriculture "Luiz de Queiroz", University of São Paulo, Piracicaba, Brazil
c. College of Textiles, North Carolina State University,
Abstract
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Raleigh, North Carolina, USA
Natural dyes are gaining interest due their expected low risk to human health and
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the environment and biodegradability. In addition, there are ever-growing potential new sources of natural dyes in the form of production waste products that merit
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consideration for coloration of materials such as textiles. Thus, an innovative approach to waste minimization through source reduction has emerged. In the present study, the potential for using colored liquid waste produced in the steam treatment of eucalyptus wood as a natural coloring matter for textile fabrics was investigated. Specifically, eucalyptus wood extract was used to dye cotton, nylon
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The present study is a continuation of the research “Waste from Eucalyptus Wood Steaming as a Natural Dye Source for Dyeing Cotton” (Rossi et al, 2015)
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and wool in an exhaust dyeing process without the addition of the traditional mordanting agents. The resulting dyed fabrics were evaluated for color fastness and it was found that wash fastness of eucalyptus wood processing waste dyed
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fabrics was very good, while light fastness was typical of natural dyes in the absence of mordants.
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Key-words: eucalyptus extract, textile dyeing, wash fastness, light fastness, natural
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dyeing
1. Introduction
Currently, the textile industry uses large quantities of synthetic dyes to produce articles for different market areas, compared with natural dyes for which
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demand is relatively minor and for niche areas (Khandegar and Saroha, 2013; Sinha et al., 2012). This outcome is linked to the fact that synthetic dyes are more economical, have superior color fastness, wider color variety, and greater
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reproducibility (Bulut and Akar, 2012; Leitner et al., 2012). Nevertheless, some of these dyes have the potential to generate toxic effluents that adversely affect the
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aquatic ecosystem and may have mutagenic, carcinogenic, toxicological properties and, despite the low incidence, some are associated with contact dermatitis (Bulut and Akar, 2012; Malinauskiene et al., 2012; Shahid et al., 2013; Sinha et al., 2012). Historically, environmental initiatives in the textile industry have centered on pollution prevention and invariably were responses to regulatory pressures aimed at reducing the environmental impact of wastewater released from textile wet
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processing (preparation, dyeing and finishing) activities. Of special interest was the presence of residual color, high levels of electrolytes, toxic substances (e.g. metals and unreacted raw materials), and cancer-suspect agents in dyehouse wastewater,
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which led various regulatory policies designed to curtail certain dye manufacturing and dye application processes produced wastewaters that posed unacceptable environmental and health risks. In the case of textile dyeing operations, the
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concerns resulted from incomplete dyebath exhaustion and the presence of dyeing auxiliaries and metal ions (e.g. Cr, Cu, and Ni) that were toxic to aquatic life. With
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regard to dye manufacturing, unreacted raw materials used in dye syntheses, worker exposures to genotoxic aromatic amines, and the use of toxic metals in the synthesis of certain dyes and their intermediates raised concerns. As a consequence, companies involved in the manufacture and use of synthetic organic
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colorants have faced increasingly stringent domestic and international environmental regulations over the past two decades (Anon, 1996). While these policies have led to the removal of certain products from commerce, they have also
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provided a stimulus for new research pertaining to the environmental chemistry of synthetic colorants. Whereas the initial studies involved the design and
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development of wastewater treatment methods (Reife and Freeman, 1999), these methods provided time for the dye manufacturing and textile dyeing industries to pursue waste minimization source reduction approaches to their environmental "opportunities".
Our initial research in this arena arose from the recognition that certain synthetic dyes and their precursors and degradation products posed a potential
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risk to human health and the environment. In this regard, we conducted studies designed to: characterize the genotoxic products arising from the metabolism of azo dyes
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•
– by far the largest family of colorants used commercially (Freeman et al., 2013); •
use results of the aforementioned type studies to design benign alternatives
•
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beta-naphthylamine (Freeman, 2013);
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to genotoxic azo dye precursors (aromatic amines) such as benzidine and
characterize drinking water contaminants originating from textile wet processing operations and determine their contributions to fresh water toxicity;
•
develop experimental methods for characterizing the mechanisms of azo
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dye geno/ecotoxicity (Claxton et al., 2010). Having developed structure-genotoxicity-relationships for azo dyes and their
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intermediates and approaches to the design of environmentally friendly replacements for use in textile wet processing based on that knowledge and
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bearing in mind the widespread use of wastewater treatment methods to decolorize dye-based effluents, we turned our attention to determining the contribution of water treatment methods (e.g. chlorination) to the toxicity of drinking water downstream of industrial wastewater releases. As a starting point for these studies, we characterized the structures and ecotoxicity of products from the chlorination of water containing azo colorants for dyeing synthetic fibers (Vacchi et al., 2013).
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As an alternative to new dye design and synthesis, to replace synthetic dyes either derived from toxic precursors or prone to forming toxic metabolites, the return of natural dyes has increasingly been contemplated because of their
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biodegradability, low incidence of allergic reactions, and low toxicity
(Komboonchoo and Bechtold, 2009; Mirjalili et al., 2011; Shahid et al., 2013). This approach is aligned with the growing movement in our society towards
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sustainability, green and environmentally friendly products, in addition to
government intervention in favor of reducing environmental issues (Bechtold et al.,
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2007; Haws et al., 2014; UNEP, 2012; Xie, 2015). Therefore, several industry sectors, including textile industries, have been adopting strategies for Cleaner Production (CP) in order to eliminate the use of toxic raw materials, increasing the efficiency of water use, and energy reduction in wastewater treatment (Bai et al.,
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2015; Luken et al., 2016; Ortolano et al., 2014). As a result, the increased interest in natural materials and renewable resources has come to the forefront, which motivates the investigation of natural dyes. Further, it recognizes the use of
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natural dyes in foodstuffs (e.g. beta-carotene, Cochineal extract, riboflavin, annatto extract, paprika, saffron, turmeric), structures of which are illustrated in Figure 1
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(Marmion, 1991). Those used at varying levels for textile coloration are illustrated in Figure 2.
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O
CH3 OH
O
HO
CH3
CO2H OH OH
HO
O
CH3
H 3C
CH3
CH3
CH3
CH3
CH3
CH3
CH3
OH
beta-Carotene
Cochineal Dye
CH3O
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OH HO
OH OH OH
HO
CH CHCOCH2COCH CH
CH CH CH CH2OH
OH H3C
N
H3C
N
OCH3
Turmeric Dye
N
O
N
H
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O
Riboflavin
Molecular structures of some natural dyes used in food products
H X
N
C
C
N
O
OH
O
X
HO
H
OH
O
OH
CH3
C
CO2H
C
OH
O
2
HO
OH
O C
OH
OH
O
3
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1 (X = H, Br)
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Figure 1.
Figure 2. Representative molecular structures of natural dyes for textiles.
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The return of the use of natural dyes in modern dye houses must take into account the ability to conduct dyeing process in existing equipment, reproducibility
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of fabric shades from batch to batch, acceptable color fastness properties (i.e., the permanence of dyes under end-use conditions), and dye available in sufficient quantity for sustainable supply (Bechtold et al., 2007; Leitner et al., 2012). Historically, natural dyes have been obtained from various sources, such as leaves, flowers, fruits, seeds, bark, roots, wood, etc. (Siva, 2007). New ways of obtaining natural plant dyes have been gaining prominence, among which is the recovery
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and use of certain colored industrial wastes (Baliarsingh et al., 2013; Bechtold et al., 2006; Haddar et al., 2014). These wastes are potentially viable for the textile industry, as they are constantly generated and allow a continuous supply, in
recycling to the production process (Haddar et al., 2014).
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addition to adding value to a residual raw material by means of its recovery and
Some sources of waste that can be used as a natural dye include extracts
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from eucalyptus processing (Shahid et al., 2013). Researchers have reported the use of leaves (Mongkholrattanasit et al., 2010; Mongkholrattanasit et al., 2011;
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Rossi et al., 2012; Rungruangkitkrai et al., 2013) and bark (Ali et al., 2007; Naz et al., 2011) from some eucalyptus species as a dye for textiles. Eucalyptus is cultivated in many countries. Currently, there are over 20 million hectares of plantations worldwide, mainly located in Brazil, India and China (Booth, 2013),
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which are addressed to a variety of uses and undergo a series of processes. A typical processing mode of eucalyptus wood includes subjecting the lumber to steam at 95°C in a closed chamber. This process giv es the wood a uniform red
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tone, including the part of the sapwood, which is initially gray to white. In this process, the water in the treatment tank becomes dark brown, providing a colored
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waste that was considered for dyeing textiles in this study. Eucalyptus has a considerable amount of tannins: this compound is also
found in some other tree species, as Acacia mearnsii, Castanea sativa, Punica granatum and Tamarindus indica (Feng et al., 2013; Sachan and Kapoor, 2007; Shahid et al., 2013). Tannins are traditionally used in the leather industry because of their high reactivity with protein in animal skin and play an important role in
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dyeing with cellulosic fibers, along with metal salts, that form insoluble lakes with natural dyes, resulting in better fastness properties (Feng et al., 2013; Prabhu and Teli, 2014). In general, they can be divided into hydrolyzable tannins and
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condensed tannins (Feng et al., 2013). The condensed tannins contain complex chemical structures of polyphenolic compounds and their structure can vary
according to the plant species (Feng et al., 2013). In textile dyeing, the tannin
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present in extracts and waste of these plants acts as a “biomordant” (Sachan and Kapoor, 2007), which can increase the fastness properties and the substantivity of
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natural dyes (Shahid et al., 2013). This observation suggests that dyeing with eucalyptus extracts can be accomplished without the use of conventional mordants, such as metal salts, making the process more simple and cleaner, without generation of residual wastewater containing toxic metal ions (Sachan and Kapoor,
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2007; Shahid et al., 2013).
As a continuation of the previous research by Rossi et al (2015), the aim of this study was to evaluate the waste from steam treatment of eucalyptus wood as a
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source of natural dye for textiles, without using metal salt mordants. A method for applying the dye to textiles was developed and the end-use properties of the dyed
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textiles were determined to validate the viability of this idea.
2. Material and methods 2.1 Evaluations of eucalyptus waste Eucalyptus liquid residue from lumber steaming was supplied by Depinus
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Industry and Trade Timber Pinus, located in the city of Curiuva, Paraná, Brazil. The timber subjected to steaming was Eucalyptus grandis Hill Ex. Maiden. A 40-L sample was collected for evaluation and sent to the Integrated Laboratories of
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Chemistry, Pulp and Energy (LQCE), of Superior School of Agriculture "Luiz de
Queiroz" at the University of São Paulo (ESALQ/USP) in Piracicaba, São Paulo, Brazil.
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The analyses performed on the sample were pH, total solids (TS),
condensed tannins (CT) and UV-visible spectroscopy. The TS was determined by
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drying the sample in an oven at 103 ± 2°C to remove water and quantitative assessment of the dry residue. The determination of CT was performed using the method of Stiasny (Paes et al., 2010). Three repetitions were performed for each analysis.
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UV- visible (UV-VIS) spectra were recorded using an Agilent Technologies Cary 300 UV-VIS spectrophotometer equipped with Cary Win UV software. Elagic acid, rutin and quercetin were used as standards to characterize the eucalyptus
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extract. The concentration of the solutions used were 60mg/L for eucalyptus
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extract, 4.16 mg/L for elagic acid, 8.75 mg/L for quercetin and 20 mg/L for rutin.
2.2 Dyeing fabrics with eucalyptus extract Textile dyeing employing the liquid residue was carried out in the Textile
Laboratory at the School of Arts, Sciences and Humanities at the University of São Paulo (EACH/USP), in São Paulo, Brazil, using an HT Mathis machine for
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exhaustion dyeing. The knitted fabrics used were cotton 98% with 2% of elastane, 100% nylon 6-6, and 100% wool, all prepared for dyeing.
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Dye baths were prepared according to (Bechtold et al., 2003) and the dyeing was performed without addition of metal salts. For all treatments, the dye
concentration used was 1%, 10% and 20%, based on the fabric weight. Dye bath
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contained NaCl (20 g/L) and the liquor ratio was 10:1.
The amount of the colorant to be used in the dye bath was determined using
Mc = (Cc x Mf) / 100 x (100/TS)
(1)
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wherein:
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the equation (1):
Mc = mass of the colorant from eucalyptus to be applied to the fabric (g); Cc = target concentration of colorant on the fabric (%);
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Mf = mass of the fabric (g);
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TS = total solids of the colorant (%).
After dyeing, the fabrics received a wash with 1 g/L of neutral detergent in
distilled water for 10 min at 30ºC. After this, the fabrics were washed in running water and dried at 40ºC for 30 min. Two repetitions were performed for each fabric in each dye concentration.
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2.3 Color assessments X-Rite Colorimetric analysis was used to measure the L*a*b* and ∆E values.
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The operating conditions of the equipment were scanning from 360 to 700 nm, CIE illuminant D65, and observer angle of 10º. L*a*b* values were analyzed by
Analysis of Variance (ANOVA) with 95% confidence interval, followed by multiple comparisons among means (Tukey's tests). L* is a measure of the
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lightness/darkness of the fabric, which ranges from 100 (white) to 0 (black); a* is a measure of the redness/greenness of the fabric, with positive (+) values indicating
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red and negative (-) values green; and b* is a measure of the yellowness/blueness of the fabric, with positive (+) values yellow indicating and negative (-) values blue.
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The greater the magnitude of the a* and b* values, the deeper the colors.
2.4 Fastness properties
The color fastness to washing of dyed samples was determined according to
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ISO 105-C06:2010 (ISO, 2010), in Golden Química industry in Guarulhos, São Paulo, Brazil. The difference obtained between the control fabric and the multi-fiber,
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before and after washing, was visually compared with the gray scale to obtain the color change and the staining, according to the ISO 105-A02:1993 (ISO, 2005a) and ISO 105-A03:1993 (ISO, 2005b). The rating scale is 0 (poor) to 5 (excellent). For light fastness, AATCC Test Method 16.3:2012 (AATCC, 2014a) was
used and this assessment was conducted in the College of Textiles, Raleigh, North Carolina State University, USA. The exposure was conducted with irradiation of 55
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W/m², relative humidity of 50%, temperature of the black body of 63ºC and temperature in the chamber of 30ºC at 5, 10 and 20 h. The difference obtained between the control fabric and the exposed fabrics, were visually compared with
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the gray scale to obtain the color change, according to the AATCC Evaluation
Procedure 1:2012 (AATCC, 2014b). The rating scale is 0 (poor) to 5 (excellent). The fastness to rubbing was also conducted at the College of Textiles at
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North Carolina State University, using a crockmeter following the ISO 105-
X12:2001 (ISO, 2001). The crocking square evaluations were performed following
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the ISO 105-A03:1993 (ISO, 2005b). The rating scale is 0 (poor) to 5 (excellent) and a rating of at least 3.0 is considered acceptable.
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2.5 ICP-MS Analysis
ICPMS analysis was performed by the Environmental and Agricultural Testing Service Laboratory at North Carolina State University, Raleigh, NC, using
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the following procedure.
Dried eucalyptus extract (1.015g) was digested in concentrated HNO3 (5
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mL) and 30% H2O2 (2 mL). The volume was raised to 25 mL with deionized water and diluted twenty-fold for analysis on a Perkin Elmer ElanDRCII ICP-MS instrument. A quantitative run was conducted against a multi-element standard curve prepared from a certified multi-element stock solution. A method blank was employed and analyzed in the same way. Any level of analyte found in the blank was subtracted from that in the dye sample. The calculated values were expressed in µg/g (ppm) based on the digestate volume and sample mass.
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3. Results and discussion 3.1 Physicochemical assessments
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The results of the physicochemical evaluations, presented in Table 1 revealed an aqueous extract with acidic pH, light brown coloration and with ~1% of condensed tannins. Compared with the residue from eucalyptus leaves reported by
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Rossi et al. (2012), which had 0.6% of tannins, and a total solids content of 3.4%, the residue of this study contained a content of tannins about 1.5 times greater and
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50% less total solids. Ali et al. (2007), indicated that the eucalyptus extract has natural tannins and polyphenols ranging from 10% to 12%. The low tannin content obtained in this presented research, compared to percentage indicated by the authors, may be due to the fact that it is a dilute extract.
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Table 1. Physicochemical analyses of the residue from steaming eucalyptus wood. Average 5.1 2.2 0.9 24.3 0.4 0.2
Standard Deviation 0.048 0.050 0.063 0.03 0.06 0.06
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Analysis pH Total solids content (%) Condensed tannins content (%) CIE L* value CIE a* value CIE b* value
The UV-VIS spectrum showed that eucalyptus extract has a very broad,
albeit weak, band covering the 400-600nm region, which is consistent with its brown coloration and low color strength (Figure 3). This extract seems to be a mixture of various substances, in which elagic acid, quercetin and rutin are present.
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Figure 3. UV-visible spectra of eucalyptus extract, elagic and tanic acid (1),
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quercetin and rutin (2).
3.2 Dyeing outcomes
The results of L*a*b* color measurements on dyed cotton, nylon and wool
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are shown in Figures 4 to 6. The error bars (a, b, and c) in these figures represent the statistical differences between the colors obtained for the dyed fabrics at a
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given dye concentration, and indicate very good reproducibility in the shades obtained at the 95% confidence level.
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80
a
Cotton
b c
a
c
b
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L*
Wool
a a
b
60
Nylon
40
20
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0
10 20 Dye concentration (%)
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1
Figure 4. CIE L* values for dyed cotton, nylon and wool fabrics as a function of eucalyptus wood extract concentration. Cotton Wool
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a
a*
10 8
Nylon
a
a
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b b
b b
b b
6
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4 2
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0
1
10 Dye concentration (%)
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Figure 5. CIE a* values for dyed cotton, nylon and wool fabrics as a function of eucalyptus wood extract concentration.
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25
Cotton
Nylon
Wool a
a
20 b
a b*
c
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c
15
b c
b
10
0 1
10
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5
20
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Dye concentration (%)
Figure 6. CIE b* values for dyed cotton, nylon and wool fabrics as a function of eucalyptus wood extract concentration.
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The dyed fabrics had yellowish, brown and beige shades in general. The L*a*b* results show that the eucalyptus extract had more affinity for wool than nylon and cotton, probably due to the inherent ionic character of wool. One mole
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of tannins can bind 12 mole of protein (Monteiro et al., 2005), which explains the higher affinity for wool, a protein fiber. L*a*b* results also show that there is no
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need to use a eucalyptus extract concentration above the 10% level, as the fabric shade depths from 20% solutions show little difference.
3.3 Fastness properties Fastness properties to washing and light are shown in Tables 2 and 3, respectively. With regard to wash fastness, two types of data are reported in 3.
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Results from color loss (change) following washing indicate that very good retention of dye occurs on cotton at the 1% dyebath concentration level, with a drop in dye retention (rating = 3) when cotton was dyed in dyebaths containing 10%
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and 20% eucalyptus dye. These rating levels are similar to those obtained from
the widely used commercial direct dyes in the absence of a post-treatment step.
Table 2 also shows that very little to no color transfer (color staining) occurred from
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dyed cotton, nylon and wool fabrics to the adjacent multifiber fabric, in view of the 4.5 or above ratings, indicating that the eucalyptus dye would be suitable for
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various fabric blends. This is important, since most commercial fabrics contain 2 or more fiber types (e.g. polyester/cotton, nylon/wool).
Cotton
4 3 3 5 4.5 4.5 3 4.5 4.5
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Nylon
Color change
Wool
Color staining of adjacent fibers
Acetate
Cotton
Nylon
5 5 5 5 5 5 5 5 5
5 4.5 4.5 5 4.5 5 5 4.5 4.5
5 4.5 5 5 5 5 5 5 5
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Fabric
Dye concentration (%) 1 10 20 1 10 20 1 10 20
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Table 2. Color fastness to washing based in ISO 105-C06:2010.
Polyester Acrylic 5 5 5 5 5 5 5 5 5
5 5 5 5 5 5 5 5 5
Wool 4.5 5 4.5 5 4.5 4.5 5 5 5
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Table 3. Color fastness to light based AATCC Test Method 16.3-2012.
Nylon
20 1.5 1.5 2 1.5 1.5 2.5 1.5 2 2.5
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Wool
5 2.5 3 3 2.5 4 4.5 3 4 4
Color change Exposition (Hours) 10 2 2 3 2 2.5 4 2.5 3 3.5
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Cotton
Dye concentration (%) 1 10 20 1 10 20 1 10 20
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Fabric
The color change results from fabric washing reflected excellent ratings on nylon, between 4.5 and 5. Wool afforded ratings between 3 and 4-5. Color changes
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in cotton are considered acceptable, with ratings between 3 and 4. On cotton and nylon, the lowest dye concentration gave the best wash fastness. For wool, the opposite occurred. In terms of staining, the ratings were >4.5 for all the fibers,
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showing excellent fastness to staining. The results indicated that fastness levels for the dyeings obtained from eucalyptus were suitable for cotton, wool and nylon
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knitwear.
Light fastness results showed, in general, low light fastness on all fabrics
and at dye concentrations at the target 20-h exposure level. This characteristic of eucalyptus extract as a colorant would limit uses to lingerie and men's underwear. This is also consistent with the shades obtained in the present fabrics (yellowishbrown, brown and beige). Such shades are frequently present in color charts of all collections of all apparel brands, being a basic color of this segment. For these
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final uses, light fastness is not important, while wash fastness is important. The fastness to rubbing evaluations, showed at Table 4, revealed good to
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excellent rubbing fastness under dry conditions for all three fiber types and at all shade depths. It is also evident that rubbing fastness is reduced on dyed cotton
and wool when the fabrics are wet. This suggests that migration of dye molecules to the fiber surface occurs more readily within the hydrophilic fibers (Burkinshaw
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and Kumar, 2008). It should be noted, however, that wet rubbing fastness on cotton was quite good for dyeings obtained from 1% and 10% dyebath
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concentrations, while wool only gave a satisfactory rating from a 1% dyebath. Wet and dry rubbing fastness for dyed nylon was very good.
Table 4. Color fastness to rubbing based ISO 105-X12:2001. Dye concentration (%) 1 10 20 1 10 20 1 10 20
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Fabric
Cotton
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Wool
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Nylon
Color staining
Dry
Wet
5 5 5 4.5 4 3 4.5 4 3
4.5 3.5 2.5 3 2 1.5 4.5 4 4
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3.4 Considerations about the use of eucalyptus dye The use of eucalyptus liquid residue from processing of the wood aligns with
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the cleaner production strategies of the United Nations Industrial Development Organization (UNIDO, 2016) and United Nations Environment Programme (UNEP, 2016). Specifically, these strategies pertain to the reduction of waste generation, by transforming a residue that would otherwise be discarded by the timber industry
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to a useful product for the textile industry, namely a coloring matter. Thus, the
proposed use adds value to eucalyptus wood and the industrial processes involved,
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since these processes will result not only in the processing of timber for sale, but in a coloring matter that can be marketed as well. The timber companies that use this process can benefit economically because they can generate income from waste that would be tossed, and minimize the waste generated.
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In addition, the use of a liquid plant residue, which can be used directly in the dyeing phase eliminates the need of plant extraction to obtain the colorant, allowing better efficiency in the use of resources like water and energy in the
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production of this natural vegetable dye, generating cost savings, which, according
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to Luken et al. (2016) is a component of cleaner production. As a waste product generated only with the vaporization of water, it contains no chemicals added during the extraction process that must be removed prior to the dyeing, which is in agreement with key aspects pointed out by Leitner et al. (2012). This must be considered as part of the ecological profile when using plant-based natural dyes. Another component of cleaner production strategies is the elimination or reduction of hazardous raw materials entering the production process (UNEP,
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2016). In our case, the replacement of certain synthetic dyes for the use of waste from eucalyptus wood steaming for certain textile products would be advantageous, since, according to Bulut and Akar (2012), some synthetic dyes in the direct,
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reactive, and acid dye families contain heavy metals, such as Cu and Cr, built into their structure. The resultant dyes can give textiles having 300-750ppm metal
content in the dyed fabrics (Rovira et al, 2015, 2016). In wood, metals are typically
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concentrated in Group I and II based metal salts of carbonates, silicates, oxalates, and phosphates, which are mostly combined with K, Ba, and Mg. Most of these
structure (Sjöström, 1993).
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metal salts are moderately soluble or occur in inaccessible regions in the wood
ICP-MS analysis indicated that Zn (18 ppm), Al (26 ppm), and Ba (41 ppm) are the principal metals in eucalyptus extracts, with Pb (0.4 ppm), As (0.6 ppm), Cu
reported in Table 5.
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(0.8 ppm) Co (1.3 ppm), and Cr (2.2 ppm) detected at significantly lower levels, as
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Table 5. Metals and levels found in dried eucalyptus plant extract.
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Analyte Al As Ba Cd Co Cr Cu Mn Ni Pb Zn
Conc. (ppm) 26.1 0.62 40.7 0.02 1.31 2.15 0.85 0.16 5.52 0.44 18.0
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Also, the effluent generated in dyeing with this liquid containing natural dye does not contain chemical additives, and as a plant extract, it is biodegradable and therefore would be easily treated, unlike the vast majority of synthetic dyes, that,
decomposition by means of physico-chemical methods.
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according to Mijin et al. (2007), are not biodegradable and are resistant to
One of the most important aspects for the reintroduction of natural dyes in
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the modern dye house is the use of available technical equipment, rather than
requiring major additional capital investments (Leitner et al., 2012). The use of the
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present natural dye meets this requirement, because the dye can be applied using a standard textile dyeing machine. In fact, we employed a known process (Bittencourt et al., 2014).
However, there are barriers to the effective use of this natural dye. One of
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them is the textile industry need for a continuous supply of raw material, given the speed of production and consumption of associated materials, which the use of this residue may not meet. Despite being constantly generated, the residue production
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is limited when compared to the production of synthetic textile dyes current used.
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However, it must be considered that the use of natural dyes is not intended to replace synthetic dyes in textile industry. After all, according to Shahid et al. (2013), the natural dyes are still used only on a small scale. It should also be noted that the current dye extract is not meant to replace other natural dyes that allow dyeings with the same shades. In addition, some challenges may appear once scale up to production with this dye takes place.
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The natural dye studied here presents itself as a potential alternative for certain niche markets that place a premium on environmentally friendly products, by adding value to these products and has environmental appeal. In addition,
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recent literature on environmental and economic issues of textile dyeing with
natural dyes and the reduction of environmental impact throughout the life cycle
point to an emphasis on sustainable development in the future. In this context, this
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natural dye studied here offers this advantage.
It is worth noting that no restructuring of the textile industry is needed to use
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this natural dye. In this case, it would be lead to a connection between the timber industry and textile industry, with the goal of optimizing the technology. Companies that work with the generation of this residue must develop efficient and sustainable mechanisms to manipulate and transport the extract so that collection and storage
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do not undermine its properties. In the other hand, the companies that work with the textile dyeing should develop a mechanism to receive this by-product, store it
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and use it in dyeing textiles.
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4. Conclusions
It has been found that the liquid waste product from steaming eucalyptus
wood is a potential source of natural dye for dyeing cotton, nylon and wool fabrics. In this regard, the results from coloristic assessments indicate that pastel to medium shades having good fastness properties can be readily obtained. The precise nature of the colorants in eucalyptus wood extract was not determined, but preliminary results from spectroscopic analysis and results from previously
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published work suggest the presence of compounds such as elagic acid, quercetin, and rutin.
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In order to be used in a sustainable way by the textile industry, natural dyes must meet the need for environmentally friendly products that satisfy local regulatory requirements pertaining to production activities having minimal
environmental impact. The proposed process involves transforming a residue that
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would otherwise be discarded by the timber industry into a useful coloring matter for the textile industry. This process also eliminates the typical extraction phase of
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a vegetable (plant-based) dye and thus requires less water and energy during the textile component of the process. It does not use any hazardous materials such as heavy-metal-containing dyeing auxiliaries, but instead generates a biodegradable effluent. Altogether, the natural dye process meets the basic principles of cleaner
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production. In this way, it should be considered as a more sustainable alternative to other dyes, both environmentally, as for its production process, as well as its use
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by the textile industry.
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Acknowledgements
The authors acknowledge the CAPES Foundation for the financial support of
this research by the Program Ciências Sem Fronteiras (project nº 2124/13-0). The authors also acknowledge the companies Rosset and Dona Cor for providing fabrics to the study and the Golden Química industry for the support to the wash fastness analysis.
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Highlights
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1- We investigate colored waste liquid produced in the steam treatment of eucalyptus wood as a natural coloring matter for textile fabrics. 2- Liquid waste by-product from steaming eucalyptus wood showed to be an alternative source of natural dye for dyeing cotton, nylon and wool fabrics in an exhaust dyeing process.
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3- Dyed fabrics wash and rubbing fastness was very good, with light fastness results typical of natural dyes.
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S0959-6526(16)32173-4
DOI:
10.1016/j.jclepro.2016.12.109
Reference:
JCLP 8684
To appear in:
Journal of Cleaner Production
Received Date: 9 June 2016 Revised Date:
18 December 2016
Accepted Date: 20 December 2016
Please cite this article as: Rossi T, Silva PMS, De Moura LF, Araújo MC, Brito JO, Freeman HS, Waste from eucalyptus wood steaming as a natural dye source for textile fibers, Journal of Cleaner Production (2017), doi: 10.1016/j.jclepro.2016.12.109. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
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Waste from eucalyptus wood steaming as a natural dye source for textile fibers1
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ROSSI, T. a*, SILVA, P.M.S. a, DE MOURA, L.F.b, ARAÚJO, M.C.a, BRITO, J.O. b, FREEMAN, H.S.c
a. School of Arts, Sciences and Humanities, University of São
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Paulo, São Paulo, Brazil
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b. Superior School of Agriculture "Luiz de Queiroz", University of São Paulo, Piracicaba, Brazil
c. College of Textiles, North Carolina State University,
Abstract
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Raleigh, North Carolina, USA
Natural dyes are gaining interest due their expected low risk to human health and
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the environment and biodegradability. In addition, there are ever-growing potential new sources of natural dyes in the form of production waste products that merit
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consideration for coloration of materials such as textiles. Thus, an innovative approach to waste minimization through source reduction has emerged. In the present study, the potential for using colored liquid waste produced in the steam treatment of eucalyptus wood as a natural coloring matter for textile fabrics was investigated. Specifically, eucalyptus wood extract was used to dye cotton, nylon
1
The present study is a continuation of the research “Waste from Eucalyptus Wood Steaming as a Natural Dye Source for Dyeing Cotton” (Rossi et al, 2015)
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and wool in an exhaust dyeing process without the addition of the traditional mordanting agents. The resulting dyed fabrics were evaluated for color fastness and it was found that wash fastness of eucalyptus wood processing waste dyed
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fabrics was very good, while light fastness was typical of natural dyes in the absence of mordants.
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Key-words: eucalyptus extract, textile dyeing, wash fastness, light fastness, natural
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dyeing
1. Introduction
Currently, the textile industry uses large quantities of synthetic dyes to produce articles for different market areas, compared with natural dyes for which
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demand is relatively minor and for niche areas (Khandegar and Saroha, 2013; Sinha et al., 2012). This outcome is linked to the fact that synthetic dyes are more economical, have superior color fastness, wider color variety, and greater
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reproducibility (Bulut and Akar, 2012; Leitner et al., 2012). Nevertheless, some of these dyes have the potential to generate toxic effluents that adversely affect the
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aquatic ecosystem and may have mutagenic, carcinogenic, toxicological properties and, despite the low incidence, some are associated with contact dermatitis (Bulut and Akar, 2012; Malinauskiene et al., 2012; Shahid et al., 2013; Sinha et al., 2012). Historically, environmental initiatives in the textile industry have centered on pollution prevention and invariably were responses to regulatory pressures aimed at reducing the environmental impact of wastewater released from textile wet
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processing (preparation, dyeing and finishing) activities. Of special interest was the presence of residual color, high levels of electrolytes, toxic substances (e.g. metals and unreacted raw materials), and cancer-suspect agents in dyehouse wastewater,
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which led various regulatory policies designed to curtail certain dye manufacturing and dye application processes produced wastewaters that posed unacceptable environmental and health risks. In the case of textile dyeing operations, the
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concerns resulted from incomplete dyebath exhaustion and the presence of dyeing auxiliaries and metal ions (e.g. Cr, Cu, and Ni) that were toxic to aquatic life. With
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regard to dye manufacturing, unreacted raw materials used in dye syntheses, worker exposures to genotoxic aromatic amines, and the use of toxic metals in the synthesis of certain dyes and their intermediates raised concerns. As a consequence, companies involved in the manufacture and use of synthetic organic
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colorants have faced increasingly stringent domestic and international environmental regulations over the past two decades (Anon, 1996). While these policies have led to the removal of certain products from commerce, they have also
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provided a stimulus for new research pertaining to the environmental chemistry of synthetic colorants. Whereas the initial studies involved the design and
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development of wastewater treatment methods (Reife and Freeman, 1999), these methods provided time for the dye manufacturing and textile dyeing industries to pursue waste minimization source reduction approaches to their environmental "opportunities".
Our initial research in this arena arose from the recognition that certain synthetic dyes and their precursors and degradation products posed a potential
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risk to human health and the environment. In this regard, we conducted studies designed to: characterize the genotoxic products arising from the metabolism of azo dyes
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•
– by far the largest family of colorants used commercially (Freeman et al., 2013); •
use results of the aforementioned type studies to design benign alternatives
•
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beta-naphthylamine (Freeman, 2013);
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to genotoxic azo dye precursors (aromatic amines) such as benzidine and
characterize drinking water contaminants originating from textile wet processing operations and determine their contributions to fresh water toxicity;
•
develop experimental methods for characterizing the mechanisms of azo
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dye geno/ecotoxicity (Claxton et al., 2010). Having developed structure-genotoxicity-relationships for azo dyes and their
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intermediates and approaches to the design of environmentally friendly replacements for use in textile wet processing based on that knowledge and
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bearing in mind the widespread use of wastewater treatment methods to decolorize dye-based effluents, we turned our attention to determining the contribution of water treatment methods (e.g. chlorination) to the toxicity of drinking water downstream of industrial wastewater releases. As a starting point for these studies, we characterized the structures and ecotoxicity of products from the chlorination of water containing azo colorants for dyeing synthetic fibers (Vacchi et al., 2013).
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As an alternative to new dye design and synthesis, to replace synthetic dyes either derived from toxic precursors or prone to forming toxic metabolites, the return of natural dyes has increasingly been contemplated because of their
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biodegradability, low incidence of allergic reactions, and low toxicity
(Komboonchoo and Bechtold, 2009; Mirjalili et al., 2011; Shahid et al., 2013). This approach is aligned with the growing movement in our society towards
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sustainability, green and environmentally friendly products, in addition to
government intervention in favor of reducing environmental issues (Bechtold et al.,
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2007; Haws et al., 2014; UNEP, 2012; Xie, 2015). Therefore, several industry sectors, including textile industries, have been adopting strategies for Cleaner Production (CP) in order to eliminate the use of toxic raw materials, increasing the efficiency of water use, and energy reduction in wastewater treatment (Bai et al.,
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2015; Luken et al., 2016; Ortolano et al., 2014). As a result, the increased interest in natural materials and renewable resources has come to the forefront, which motivates the investigation of natural dyes. Further, it recognizes the use of
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natural dyes in foodstuffs (e.g. beta-carotene, Cochineal extract, riboflavin, annatto extract, paprika, saffron, turmeric), structures of which are illustrated in Figure 1
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(Marmion, 1991). Those used at varying levels for textile coloration are illustrated in Figure 2.
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O
CH3 OH
O
HO
CH3
CO2H OH OH
HO
O
CH3
H 3C
CH3
CH3
CH3
CH3
CH3
CH3
CH3
OH
beta-Carotene
Cochineal Dye
CH3O
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OH HO
OH OH OH
HO
CH CHCOCH2COCH CH
CH CH CH CH2OH
OH H3C
N
H3C
N
OCH3
Turmeric Dye
N
O
N
H
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O
Riboflavin
Molecular structures of some natural dyes used in food products
H X
N
C
C
N
O
OH
O
X
HO
H
OH
O
OH
CH3
C
CO2H
C
OH
O
2
HO
OH
O C
OH
OH
O
3
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1 (X = H, Br)
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Figure 1.
Figure 2. Representative molecular structures of natural dyes for textiles.
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The return of the use of natural dyes in modern dye houses must take into account the ability to conduct dyeing process in existing equipment, reproducibility
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of fabric shades from batch to batch, acceptable color fastness properties (i.e., the permanence of dyes under end-use conditions), and dye available in sufficient quantity for sustainable supply (Bechtold et al., 2007; Leitner et al., 2012). Historically, natural dyes have been obtained from various sources, such as leaves, flowers, fruits, seeds, bark, roots, wood, etc. (Siva, 2007). New ways of obtaining natural plant dyes have been gaining prominence, among which is the recovery
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and use of certain colored industrial wastes (Baliarsingh et al., 2013; Bechtold et al., 2006; Haddar et al., 2014). These wastes are potentially viable for the textile industry, as they are constantly generated and allow a continuous supply, in
recycling to the production process (Haddar et al., 2014).
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addition to adding value to a residual raw material by means of its recovery and
Some sources of waste that can be used as a natural dye include extracts
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from eucalyptus processing (Shahid et al., 2013). Researchers have reported the use of leaves (Mongkholrattanasit et al., 2010; Mongkholrattanasit et al., 2011;
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Rossi et al., 2012; Rungruangkitkrai et al., 2013) and bark (Ali et al., 2007; Naz et al., 2011) from some eucalyptus species as a dye for textiles. Eucalyptus is cultivated in many countries. Currently, there are over 20 million hectares of plantations worldwide, mainly located in Brazil, India and China (Booth, 2013),
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which are addressed to a variety of uses and undergo a series of processes. A typical processing mode of eucalyptus wood includes subjecting the lumber to steam at 95°C in a closed chamber. This process giv es the wood a uniform red
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tone, including the part of the sapwood, which is initially gray to white. In this process, the water in the treatment tank becomes dark brown, providing a colored
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waste that was considered for dyeing textiles in this study. Eucalyptus has a considerable amount of tannins: this compound is also
found in some other tree species, as Acacia mearnsii, Castanea sativa, Punica granatum and Tamarindus indica (Feng et al., 2013; Sachan and Kapoor, 2007; Shahid et al., 2013). Tannins are traditionally used in the leather industry because of their high reactivity with protein in animal skin and play an important role in
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dyeing with cellulosic fibers, along with metal salts, that form insoluble lakes with natural dyes, resulting in better fastness properties (Feng et al., 2013; Prabhu and Teli, 2014). In general, they can be divided into hydrolyzable tannins and
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condensed tannins (Feng et al., 2013). The condensed tannins contain complex chemical structures of polyphenolic compounds and their structure can vary
according to the plant species (Feng et al., 2013). In textile dyeing, the tannin
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present in extracts and waste of these plants acts as a “biomordant” (Sachan and Kapoor, 2007), which can increase the fastness properties and the substantivity of
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natural dyes (Shahid et al., 2013). This observation suggests that dyeing with eucalyptus extracts can be accomplished without the use of conventional mordants, such as metal salts, making the process more simple and cleaner, without generation of residual wastewater containing toxic metal ions (Sachan and Kapoor,
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2007; Shahid et al., 2013).
As a continuation of the previous research by Rossi et al (2015), the aim of this study was to evaluate the waste from steam treatment of eucalyptus wood as a
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source of natural dye for textiles, without using metal salt mordants. A method for applying the dye to textiles was developed and the end-use properties of the dyed
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textiles were determined to validate the viability of this idea.
2. Material and methods 2.1 Evaluations of eucalyptus waste Eucalyptus liquid residue from lumber steaming was supplied by Depinus
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Industry and Trade Timber Pinus, located in the city of Curiuva, Paraná, Brazil. The timber subjected to steaming was Eucalyptus grandis Hill Ex. Maiden. A 40-L sample was collected for evaluation and sent to the Integrated Laboratories of
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Chemistry, Pulp and Energy (LQCE), of Superior School of Agriculture "Luiz de
Queiroz" at the University of São Paulo (ESALQ/USP) in Piracicaba, São Paulo, Brazil.
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The analyses performed on the sample were pH, total solids (TS),
condensed tannins (CT) and UV-visible spectroscopy. The TS was determined by
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drying the sample in an oven at 103 ± 2°C to remove water and quantitative assessment of the dry residue. The determination of CT was performed using the method of Stiasny (Paes et al., 2010). Three repetitions were performed for each analysis.
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UV- visible (UV-VIS) spectra were recorded using an Agilent Technologies Cary 300 UV-VIS spectrophotometer equipped with Cary Win UV software. Elagic acid, rutin and quercetin were used as standards to characterize the eucalyptus
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extract. The concentration of the solutions used were 60mg/L for eucalyptus
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extract, 4.16 mg/L for elagic acid, 8.75 mg/L for quercetin and 20 mg/L for rutin.
2.2 Dyeing fabrics with eucalyptus extract Textile dyeing employing the liquid residue was carried out in the Textile
Laboratory at the School of Arts, Sciences and Humanities at the University of São Paulo (EACH/USP), in São Paulo, Brazil, using an HT Mathis machine for
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exhaustion dyeing. The knitted fabrics used were cotton 98% with 2% of elastane, 100% nylon 6-6, and 100% wool, all prepared for dyeing.
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Dye baths were prepared according to (Bechtold et al., 2003) and the dyeing was performed without addition of metal salts. For all treatments, the dye
concentration used was 1%, 10% and 20%, based on the fabric weight. Dye bath
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contained NaCl (20 g/L) and the liquor ratio was 10:1.
The amount of the colorant to be used in the dye bath was determined using
Mc = (Cc x Mf) / 100 x (100/TS)
(1)
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wherein:
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the equation (1):
Mc = mass of the colorant from eucalyptus to be applied to the fabric (g); Cc = target concentration of colorant on the fabric (%);
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Mf = mass of the fabric (g);
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TS = total solids of the colorant (%).
After dyeing, the fabrics received a wash with 1 g/L of neutral detergent in
distilled water for 10 min at 30ºC. After this, the fabrics were washed in running water and dried at 40ºC for 30 min. Two repetitions were performed for each fabric in each dye concentration.
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2.3 Color assessments X-Rite Colorimetric analysis was used to measure the L*a*b* and ∆E values.
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The operating conditions of the equipment were scanning from 360 to 700 nm, CIE illuminant D65, and observer angle of 10º. L*a*b* values were analyzed by
Analysis of Variance (ANOVA) with 95% confidence interval, followed by multiple comparisons among means (Tukey's tests). L* is a measure of the
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lightness/darkness of the fabric, which ranges from 100 (white) to 0 (black); a* is a measure of the redness/greenness of the fabric, with positive (+) values indicating
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red and negative (-) values green; and b* is a measure of the yellowness/blueness of the fabric, with positive (+) values yellow indicating and negative (-) values blue.
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The greater the magnitude of the a* and b* values, the deeper the colors.
2.4 Fastness properties
The color fastness to washing of dyed samples was determined according to
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ISO 105-C06:2010 (ISO, 2010), in Golden Química industry in Guarulhos, São Paulo, Brazil. The difference obtained between the control fabric and the multi-fiber,
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before and after washing, was visually compared with the gray scale to obtain the color change and the staining, according to the ISO 105-A02:1993 (ISO, 2005a) and ISO 105-A03:1993 (ISO, 2005b). The rating scale is 0 (poor) to 5 (excellent). For light fastness, AATCC Test Method 16.3:2012 (AATCC, 2014a) was
used and this assessment was conducted in the College of Textiles, Raleigh, North Carolina State University, USA. The exposure was conducted with irradiation of 55
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W/m², relative humidity of 50%, temperature of the black body of 63ºC and temperature in the chamber of 30ºC at 5, 10 and 20 h. The difference obtained between the control fabric and the exposed fabrics, were visually compared with
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the gray scale to obtain the color change, according to the AATCC Evaluation
Procedure 1:2012 (AATCC, 2014b). The rating scale is 0 (poor) to 5 (excellent). The fastness to rubbing was also conducted at the College of Textiles at
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North Carolina State University, using a crockmeter following the ISO 105-
X12:2001 (ISO, 2001). The crocking square evaluations were performed following
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the ISO 105-A03:1993 (ISO, 2005b). The rating scale is 0 (poor) to 5 (excellent) and a rating of at least 3.0 is considered acceptable.
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2.5 ICP-MS Analysis
ICPMS analysis was performed by the Environmental and Agricultural Testing Service Laboratory at North Carolina State University, Raleigh, NC, using
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the following procedure.
Dried eucalyptus extract (1.015g) was digested in concentrated HNO3 (5
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mL) and 30% H2O2 (2 mL). The volume was raised to 25 mL with deionized water and diluted twenty-fold for analysis on a Perkin Elmer ElanDRCII ICP-MS instrument. A quantitative run was conducted against a multi-element standard curve prepared from a certified multi-element stock solution. A method blank was employed and analyzed in the same way. Any level of analyte found in the blank was subtracted from that in the dye sample. The calculated values were expressed in µg/g (ppm) based on the digestate volume and sample mass.
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3. Results and discussion 3.1 Physicochemical assessments
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The results of the physicochemical evaluations, presented in Table 1 revealed an aqueous extract with acidic pH, light brown coloration and with ~1% of condensed tannins. Compared with the residue from eucalyptus leaves reported by
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Rossi et al. (2012), which had 0.6% of tannins, and a total solids content of 3.4%, the residue of this study contained a content of tannins about 1.5 times greater and
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50% less total solids. Ali et al. (2007), indicated that the eucalyptus extract has natural tannins and polyphenols ranging from 10% to 12%. The low tannin content obtained in this presented research, compared to percentage indicated by the authors, may be due to the fact that it is a dilute extract.
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Table 1. Physicochemical analyses of the residue from steaming eucalyptus wood. Average 5.1 2.2 0.9 24.3 0.4 0.2
Standard Deviation 0.048 0.050 0.063 0.03 0.06 0.06
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Analysis pH Total solids content (%) Condensed tannins content (%) CIE L* value CIE a* value CIE b* value
The UV-VIS spectrum showed that eucalyptus extract has a very broad,
albeit weak, band covering the 400-600nm region, which is consistent with its brown coloration and low color strength (Figure 3). This extract seems to be a mixture of various substances, in which elagic acid, quercetin and rutin are present.
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2
Figure 3. UV-visible spectra of eucalyptus extract, elagic and tanic acid (1),
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quercetin and rutin (2).
3.2 Dyeing outcomes
The results of L*a*b* color measurements on dyed cotton, nylon and wool
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are shown in Figures 4 to 6. The error bars (a, b, and c) in these figures represent the statistical differences between the colors obtained for the dyed fabrics at a
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given dye concentration, and indicate very good reproducibility in the shades obtained at the 95% confidence level.
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80
a
Cotton
b c
a
c
b
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L*
Wool
a a
b
60
Nylon
40
20
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0
10 20 Dye concentration (%)
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1
Figure 4. CIE L* values for dyed cotton, nylon and wool fabrics as a function of eucalyptus wood extract concentration. Cotton Wool
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a
a*
10 8
Nylon
a
a
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b b
b b
b b
6
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4 2
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0
1
10 Dye concentration (%)
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Figure 5. CIE a* values for dyed cotton, nylon and wool fabrics as a function of eucalyptus wood extract concentration.
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Cotton
Nylon
Wool a
a
20 b
a b*
c
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c
15
b c
b
10
0 1
10
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5
20
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Dye concentration (%)
Figure 6. CIE b* values for dyed cotton, nylon and wool fabrics as a function of eucalyptus wood extract concentration.
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The dyed fabrics had yellowish, brown and beige shades in general. The L*a*b* results show that the eucalyptus extract had more affinity for wool than nylon and cotton, probably due to the inherent ionic character of wool. One mole
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of tannins can bind 12 mole of protein (Monteiro et al., 2005), which explains the higher affinity for wool, a protein fiber. L*a*b* results also show that there is no
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need to use a eucalyptus extract concentration above the 10% level, as the fabric shade depths from 20% solutions show little difference.
3.3 Fastness properties Fastness properties to washing and light are shown in Tables 2 and 3, respectively. With regard to wash fastness, two types of data are reported in 3.
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Results from color loss (change) following washing indicate that very good retention of dye occurs on cotton at the 1% dyebath concentration level, with a drop in dye retention (rating = 3) when cotton was dyed in dyebaths containing 10%
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and 20% eucalyptus dye. These rating levels are similar to those obtained from
the widely used commercial direct dyes in the absence of a post-treatment step.
Table 2 also shows that very little to no color transfer (color staining) occurred from
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dyed cotton, nylon and wool fabrics to the adjacent multifiber fabric, in view of the 4.5 or above ratings, indicating that the eucalyptus dye would be suitable for
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various fabric blends. This is important, since most commercial fabrics contain 2 or more fiber types (e.g. polyester/cotton, nylon/wool).
Cotton
4 3 3 5 4.5 4.5 3 4.5 4.5
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Nylon
Color change
Wool
Color staining of adjacent fibers
Acetate
Cotton
Nylon
5 5 5 5 5 5 5 5 5
5 4.5 4.5 5 4.5 5 5 4.5 4.5
5 4.5 5 5 5 5 5 5 5
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Fabric
Dye concentration (%) 1 10 20 1 10 20 1 10 20
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Table 2. Color fastness to washing based in ISO 105-C06:2010.
Polyester Acrylic 5 5 5 5 5 5 5 5 5
5 5 5 5 5 5 5 5 5
Wool 4.5 5 4.5 5 4.5 4.5 5 5 5
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Table 3. Color fastness to light based AATCC Test Method 16.3-2012.
Nylon
20 1.5 1.5 2 1.5 1.5 2.5 1.5 2 2.5
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Wool
5 2.5 3 3 2.5 4 4.5 3 4 4
Color change Exposition (Hours) 10 2 2 3 2 2.5 4 2.5 3 3.5
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Cotton
Dye concentration (%) 1 10 20 1 10 20 1 10 20
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Fabric
The color change results from fabric washing reflected excellent ratings on nylon, between 4.5 and 5. Wool afforded ratings between 3 and 4-5. Color changes
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in cotton are considered acceptable, with ratings between 3 and 4. On cotton and nylon, the lowest dye concentration gave the best wash fastness. For wool, the opposite occurred. In terms of staining, the ratings were >4.5 for all the fibers,
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showing excellent fastness to staining. The results indicated that fastness levels for the dyeings obtained from eucalyptus were suitable for cotton, wool and nylon
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knitwear.
Light fastness results showed, in general, low light fastness on all fabrics
and at dye concentrations at the target 20-h exposure level. This characteristic of eucalyptus extract as a colorant would limit uses to lingerie and men's underwear. This is also consistent with the shades obtained in the present fabrics (yellowishbrown, brown and beige). Such shades are frequently present in color charts of all collections of all apparel brands, being a basic color of this segment. For these
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final uses, light fastness is not important, while wash fastness is important. The fastness to rubbing evaluations, showed at Table 4, revealed good to
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excellent rubbing fastness under dry conditions for all three fiber types and at all shade depths. It is also evident that rubbing fastness is reduced on dyed cotton
and wool when the fabrics are wet. This suggests that migration of dye molecules to the fiber surface occurs more readily within the hydrophilic fibers (Burkinshaw
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and Kumar, 2008). It should be noted, however, that wet rubbing fastness on cotton was quite good for dyeings obtained from 1% and 10% dyebath
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concentrations, while wool only gave a satisfactory rating from a 1% dyebath. Wet and dry rubbing fastness for dyed nylon was very good.
Table 4. Color fastness to rubbing based ISO 105-X12:2001. Dye concentration (%) 1 10 20 1 10 20 1 10 20
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Fabric
Cotton
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Wool
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Nylon
Color staining
Dry
Wet
5 5 5 4.5 4 3 4.5 4 3
4.5 3.5 2.5 3 2 1.5 4.5 4 4
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3.4 Considerations about the use of eucalyptus dye The use of eucalyptus liquid residue from processing of the wood aligns with
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the cleaner production strategies of the United Nations Industrial Development Organization (UNIDO, 2016) and United Nations Environment Programme (UNEP, 2016). Specifically, these strategies pertain to the reduction of waste generation, by transforming a residue that would otherwise be discarded by the timber industry
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to a useful product for the textile industry, namely a coloring matter. Thus, the
proposed use adds value to eucalyptus wood and the industrial processes involved,
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since these processes will result not only in the processing of timber for sale, but in a coloring matter that can be marketed as well. The timber companies that use this process can benefit economically because they can generate income from waste that would be tossed, and minimize the waste generated.
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In addition, the use of a liquid plant residue, which can be used directly in the dyeing phase eliminates the need of plant extraction to obtain the colorant, allowing better efficiency in the use of resources like water and energy in the
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production of this natural vegetable dye, generating cost savings, which, according
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to Luken et al. (2016) is a component of cleaner production. As a waste product generated only with the vaporization of water, it contains no chemicals added during the extraction process that must be removed prior to the dyeing, which is in agreement with key aspects pointed out by Leitner et al. (2012). This must be considered as part of the ecological profile when using plant-based natural dyes. Another component of cleaner production strategies is the elimination or reduction of hazardous raw materials entering the production process (UNEP,
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2016). In our case, the replacement of certain synthetic dyes for the use of waste from eucalyptus wood steaming for certain textile products would be advantageous, since, according to Bulut and Akar (2012), some synthetic dyes in the direct,
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reactive, and acid dye families contain heavy metals, such as Cu and Cr, built into their structure. The resultant dyes can give textiles having 300-750ppm metal
content in the dyed fabrics (Rovira et al, 2015, 2016). In wood, metals are typically
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concentrated in Group I and II based metal salts of carbonates, silicates, oxalates, and phosphates, which are mostly combined with K, Ba, and Mg. Most of these
structure (Sjöström, 1993).
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metal salts are moderately soluble or occur in inaccessible regions in the wood
ICP-MS analysis indicated that Zn (18 ppm), Al (26 ppm), and Ba (41 ppm) are the principal metals in eucalyptus extracts, with Pb (0.4 ppm), As (0.6 ppm), Cu
reported in Table 5.
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(0.8 ppm) Co (1.3 ppm), and Cr (2.2 ppm) detected at significantly lower levels, as
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Table 5. Metals and levels found in dried eucalyptus plant extract.
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Analyte Al As Ba Cd Co Cr Cu Mn Ni Pb Zn
Conc. (ppm) 26.1 0.62 40.7 0.02 1.31 2.15 0.85 0.16 5.52 0.44 18.0
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Also, the effluent generated in dyeing with this liquid containing natural dye does not contain chemical additives, and as a plant extract, it is biodegradable and therefore would be easily treated, unlike the vast majority of synthetic dyes, that,
decomposition by means of physico-chemical methods.
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according to Mijin et al. (2007), are not biodegradable and are resistant to
One of the most important aspects for the reintroduction of natural dyes in
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the modern dye house is the use of available technical equipment, rather than
requiring major additional capital investments (Leitner et al., 2012). The use of the
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present natural dye meets this requirement, because the dye can be applied using a standard textile dyeing machine. In fact, we employed a known process (Bittencourt et al., 2014).
However, there are barriers to the effective use of this natural dye. One of
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them is the textile industry need for a continuous supply of raw material, given the speed of production and consumption of associated materials, which the use of this residue may not meet. Despite being constantly generated, the residue production
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is limited when compared to the production of synthetic textile dyes current used.
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However, it must be considered that the use of natural dyes is not intended to replace synthetic dyes in textile industry. After all, according to Shahid et al. (2013), the natural dyes are still used only on a small scale. It should also be noted that the current dye extract is not meant to replace other natural dyes that allow dyeings with the same shades. In addition, some challenges may appear once scale up to production with this dye takes place.
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The natural dye studied here presents itself as a potential alternative for certain niche markets that place a premium on environmentally friendly products, by adding value to these products and has environmental appeal. In addition,
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recent literature on environmental and economic issues of textile dyeing with
natural dyes and the reduction of environmental impact throughout the life cycle
point to an emphasis on sustainable development in the future. In this context, this
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natural dye studied here offers this advantage.
It is worth noting that no restructuring of the textile industry is needed to use
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this natural dye. In this case, it would be lead to a connection between the timber industry and textile industry, with the goal of optimizing the technology. Companies that work with the generation of this residue must develop efficient and sustainable mechanisms to manipulate and transport the extract so that collection and storage
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do not undermine its properties. In the other hand, the companies that work with the textile dyeing should develop a mechanism to receive this by-product, store it
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and use it in dyeing textiles.
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4. Conclusions
It has been found that the liquid waste product from steaming eucalyptus
wood is a potential source of natural dye for dyeing cotton, nylon and wool fabrics. In this regard, the results from coloristic assessments indicate that pastel to medium shades having good fastness properties can be readily obtained. The precise nature of the colorants in eucalyptus wood extract was not determined, but preliminary results from spectroscopic analysis and results from previously
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published work suggest the presence of compounds such as elagic acid, quercetin, and rutin.
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In order to be used in a sustainable way by the textile industry, natural dyes must meet the need for environmentally friendly products that satisfy local regulatory requirements pertaining to production activities having minimal
environmental impact. The proposed process involves transforming a residue that
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would otherwise be discarded by the timber industry into a useful coloring matter for the textile industry. This process also eliminates the typical extraction phase of
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a vegetable (plant-based) dye and thus requires less water and energy during the textile component of the process. It does not use any hazardous materials such as heavy-metal-containing dyeing auxiliaries, but instead generates a biodegradable effluent. Altogether, the natural dye process meets the basic principles of cleaner
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production. In this way, it should be considered as a more sustainable alternative to other dyes, both environmentally, as for its production process, as well as its use
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by the textile industry.
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Acknowledgements
The authors acknowledge the CAPES Foundation for the financial support of
this research by the Program Ciências Sem Fronteiras (project nº 2124/13-0). The authors also acknowledge the companies Rosset and Dona Cor for providing fabrics to the study and the Golden Química industry for the support to the wash fastness analysis.
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Highlights
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1- We investigate colored waste liquid produced in the steam treatment of eucalyptus wood as a natural coloring matter for textile fabrics. 2- Liquid waste by-product from steaming eucalyptus wood showed to be an alternative source of natural dye for dyeing cotton, nylon and wool fabrics in an exhaust dyeing process.
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3- Dyed fabrics wash and rubbing fastness was very good, with light fastness results typical of natural dyes.
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