UV-VIS absorbance peaks at different wavelength for few purified natural dyes.
\\n\\n
Dr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\\n\\nSeeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\\n\\nOver these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\\n\\nWe are excited about the present, and we look forward to sharing many more successes in the future.
\\n\\nThank you all for being part of the journey. 5,000 times thank you!
\\n\\nNow with 5,000 titles available Open Access, which one will you read next?
\\n\\nRead, share and download for free: https://www.intechopen.com/books
\\n\\n\\n\\n
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'
Preparation of Space Experiments edited by international leading expert Dr. Vladimir Pletser, Director of Space Training Operations at Blue Abyss is the 5,000th Open Access book published by IntechOpen and our milestone publication!
\n\n"This book presents some of the current trends in space microgravity research. The eleven chapters introduce various facets of space research in physical sciences, human physiology and technology developed using the microgravity environment not only to improve our fundamental understanding in these domains but also to adapt this new knowledge for application on earth." says the editor. Listen what else Dr. Pletser has to say...
\n\n\n\nDr. Pletser’s experience includes 30 years of working with the European Space Agency as a Senior Physicist/Engineer and coordinating their parabolic flight campaigns, and he is the Guinness World Record holder for the most number of aircraft flown (12) in parabolas, personally logging more than 7,300 parabolas.
\n\nSeeing the 5,000th book published makes us at the same time proud, happy, humble, and grateful. This is a great opportunity to stop and celebrate what we have done so far, but is also an opportunity to engage even more, grow, and succeed. It wouldn't be possible to get here without the synergy of team members’ hard work and authors and editors who devote time and their expertise into Open Access book publishing with us.
\n\nOver these years, we have gone from pioneering the scientific Open Access book publishing field to being the world’s largest Open Access book publisher. Nonetheless, our vision has remained the same: to meet the challenges of making relevant knowledge available to the worldwide community under the Open Access model.
\n\nWe are excited about the present, and we look forward to sharing many more successes in the future.
\n\nThank you all for being part of the journey. 5,000 times thank you!
\n\nNow with 5,000 titles available Open Access, which one will you read next?
\n\nRead, share and download for free: https://www.intechopen.com/books
\n\n\n\n
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\r\n\tResponding to global public health emergencies require well-tested and effective approaches. During the current pandemic, healthcare systems worldwide were ill-prepared to respond to the rapid and far reaching impact of COVID-19. This should prompt researchers to re-examine policies, practices, methods and approaches that governments, health care and civic organizations may use to address health emergencies. With over 100 years of research on the implementation of innovative practices, system and organizational scientists are poised to help states, health care systems and other systems to develop, establish and employ evidence-based practices (EBPs) to effectively respond to public health emergencies.
\r\n\r\n\tThe primary aim of this book is to present theoretical and empirical knowledge on evidence-based policies, organizational practices, group and individual practices and approaches that may allow States and healthcare systems to effectively confront current (e.g., the COVID-19 pandemic), ongoing (e.g. HIV, opioid overdose) and upcoming epidemics affecting population health. The overall goal of this book is to advance knowledge on the development and dissemination of EBPs that contribute to a responsive, coordinated, reliable and effective public health system.
",isbn:"978-1-83969-144-7",printIsbn:"978-1-83969-143-0",pdfIsbn:"978-1-83969-145-4",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"355f26e9a65d22c4de7311a424d1e3eb",bookSignature:"Dr. Erick Guerrero",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/9504.jpg",keywords:"Implementation, Dynamic Systems, Public Health, Emergencies, Coordination, Collaboration, Networks, Teams, Organizational Learning, Implementation, Public Health Crises, Pay for Performance",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"October 19th 2020",dateEndSecondStepPublish:"November 27th 2020",dateEndThirdStepPublish:"January 26th 2021",dateEndFourthStepPublish:"April 16th 2021",dateEndFifthStepPublish:"June 15th 2021",remainingDaysToSecondStep:"3 months",secondStepPassed:!0,currentStepOfPublishingProcess:4,editedByType:null,kuFlag:!1,biosketch:"Dr. Erick Guerrero is an internationally recognized researcher in healthcare access and redesign and Co-Principal Investigator in several public health research projects in the United States, Latin American, and Europe. He is also leading culturally responsive consortiums to respond to other public health crises including institutional racism and COVID-19.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"294761",title:"Dr.",name:"Erick",middleName:null,surname:"Guerrero",slug:"erick-guerrero",fullName:"Erick Guerrero",profilePictureURL:"https://mts.intechopen.com/storage/users/294761/images/system/294761.jpg",biography:"Erick Guerrero completed his doctoral degree at the University of Chicago in 2009. In 2016, Dr. Guerrero received tenure as Associate Professor at the University of Southern California. Since 2018, he has been serving as the Founder and Director at the I-LEAD Institute, a research and consulting firm in Silicon Beach. Dr Guerrero has a background in clinical psychology and organizational behavior. As a clinician, he has provided counseling to individuals and families for the past 23 years. As an organizational researcher, Dr Guerrero has published more than 60 peer-reviewed manuscripts and 2 books on implementation of evidence-based practices in health and human service organizations. Dr Guerrero currently co-leads three large studies on disparities and implementation research to respond to the opioid epidemic funded by the U.S. National Institute of Health. 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From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. 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Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"69818",title:"Radioimaging Diagnosis of Vaterian Ampulloma: Technique, Semiology, and Differential Diagnosis - Review",doi:"10.5772/intechopen.89948",slug:"radioimaging-diagnosis-of-vaterian-ampulloma-technique-semiology-and-differential-diagnosis-review",body:'The region of the ampulla of Vater is an anatomical and functional complex, a separate entity, mainly comprising the biliopancreaticoduodenal confluence area. The ampulla territory includes in its structure the terminal portion of the choledoch, including the Oddi sphincter and the main duct of Wirsung, forming the papilla at the duodenal level. In 85% of cases, the openings of the main bile duct and the pancreatic canal are common. The terminal choledoch, after crossing the duodenal wall, next to the duct of Wirsung, opens in the ampulla of Vater. The choledoch implants in the papilla is variable. In most cases, the choledoch has a tangential implantation through the duodenal wall, reaching the level of the ampulla, the choledoch ends differently, either with a highly developed sphincter in the case of a small ampulla or with a much less developed sphincter in the case of a well-highlighted ampulla [1].
The localization of the papilla at the duodenum level is in most cases on the medial contour of the descending duodenum, at the junction of the middle third with the lower third, but ectopic positions of the papilla are known, cranial at 1–2 cm below the bulb level, or caudal at the lower duodenal knee level [1].
A special place is occupied by the cancers of the ampulla of Vater, which are distinct entities, separate from those of the duodenum, although the anatomical location of the ampulla of Vater is at the level of the descending duodenum, due to their embryological origins and the different histological structures [1].
Neoplasms of the vaterian region, also known as vaterian ampulloma, may have as a starting point the cylindrical choledochal epithelium, the Wirsungian cubic epithelium, or the glandular epithelium of the papilla. Due to their origin in an epithelial type tissue structure, histopathologically these tumors are adenocarcinomas [1].
The involvement of the duodenum in the neighboring tumor pathology is explained primarily by the multitude of anatomical direct relationships that this organ has with the pancreas, liver, right kidney, colonic hepatic angle, etc.
Neoplasms of the vicinity that have been shown to be invasive in the duodenum are pancreatic tumors, regardless of the segment of this organ, hepatomas, gallbladder cancers, cholangiocarcinomas, malignancies of the right kidney, and colonic, retroperitoneal, as well as gastric duodenal lymphoma. Of these, the most common are the pancreatic neoplasms and the vaterian ampullomas [1].
From our experience, duodenal neoplasms can reach 13% of the total number of neoplasms of the pancreatic-duodenal region, most common being the invasive pancreatic cancer in the duodenum, with a percentage reaching up to 65%, followed by the vaterian ampullomas with a frequency of over 10% [1].
Talamini et al. [2] considers in a study conducted over a 28-year period that ampullary adenocarcinomas are the second most common malignancy in the periampullary region. In the present work, the vaterian ampullomas are in second place by frequency, after the pancreatic neoplasms, but in a ratio equal to the duodenal malignancies themselves.
The objectives of the radio-imagistic explorations in the vaterian ampulloma are:
Detection of the tumor lesion, providing information on the location, shape, dimensions, and contours of the space replacement process, as well as on the presence of any ulcerations or fistulas and the degree of lumen stenosis
The state of the duodenal mucosa, insisting on the morphofunctional and autoplastic changes
Modifications of the duodenal papilla
Changes in size of the duodenal wall
Extension of the ampullary lesion in the periduodenal space
The existence of modifications of the parenchymatous organs or segments of the digestive tract potentially involved in the mechanisms of tumor onset or the degree of tumor invasion in the neighboring organs
The existence of possible subdiaphragmatic adenopathies
By its anatomical location, any lesion at the level of the ampulla of Vater requires the radiological study of the duodenal framework, especially the descending duodenum.
Examination of the duodenum follows that of the stomach, which is why some aspects are difficult to highlight or elude the examiner due to technical defects or because he is distracted by the presence of other concomitant or associated lesions of the esophagus or stomach.
The technique of examining the duodenum using simple contrast is that used in routine examination, following that of the esophagus and the stomach [1]. During this examination the patient ingests 240–360 ml of barium sulfate suspension in water, concentration 30–40%. It is preferable for the contrast agent to have small particles with a high dispersion degree of 4000–6000 particles/cm2. For a better adhesion of the contrast agent to the mucosal folds, it is recommended to associate a homogenizing agent such as methyl cellulose in the barium sulfate suspension.
Preparation of the patient in the event of a suspected vaterian ampulloma should be done with great care, including an adequate diet, avoiding fermentable foods, long-molecule cellulose, and excess lipids, prohibiting any food intake 6–8 hours before examination, or secretion evacuation if the existence of a stenosis is a certainty. In order not to modify the functional duodenal mechano-secretory behavior, it is advisable to avoid the administration of drugs with implication in the duodenopancreatic physiology.
In this method of examination, the bulb and the rest of the duodenal frame are filled with contrast agent due to gravity and normal peristaltic movements of the stomach, the patient being in orthostatism, ventral decubitus, or right lateral decubitus.
The technique of simple contrast duodenal exploration is a routine examination. It can be performed at any radiology office. However, the method also has drawbacks, the main ones being the overlap of the antrum and the sometimes-insufficient distension of the duodenum.
This technique can be mainly achieved in two ways [1]:
Double-contrast hypotonic duodenography
Probe duodenography
Evaluation of the duodenum in double contrast may be part of the standard double contrast of the upper gastrointestinal tract. The examination starts with the carrying out of a seriography after ingesting a single barium swallow that allows a good lining of the digestive mucosa; this represents the mucographic time. At the same time, the exact position of the different portions of the gastric segment is noted.
The double-contrast hypotonic duodenography can be obtained using two methods: the double-contrast method performed during the eso-gastro-duodenal examination, using glucagon and a gaseous potion as a pharmacodynamics, or the hypotonic duodenography in which the patient is given an antispastic after administration of the contrast agent.
In the first method, the double-contrast phase can be obtained by inducing a short-term hypotonia by injecting 0.1 mg of glucagon IV at the beginning of the examination, after which the patient ingests the gaseous agent, respectively, a mixture of citric acid and sodium bicarbonate, with 10 ml of water and high-density barium sulfate, of about 200–250 wt/vol%. After 5–10 min, during which the esophagus and stomach are examined, the hypotonic effect of the glucagon is finished so that the air and barium pass easily through the pylorus and reach the duodenum. The positioning of the patient in ventral and left posterior oblique decubitus fills the duodenal bulb with high-density barium. The compression performed in ventral decubitus is not as useful as in simple contrast due to the increased barium density. We can obtain a series of double-contrast images of both the bulb and duodenal frame in the right anterior oblique position after the patient ingests 240 ml of low-density barium suspension.
The method has maximum reliability for examining the stomach, duodenal bulb, and possibly the descending duodenum. It has the disadvantage that it does not allow a good assessment of the state of the duodenal mucosa, and the overlaps of the antral portion cannot always be excluded. Also, the two fractions of barium suspension can be mixed, which may induce interpretation errors.
In the second method, the exploration is required to be carried out quickly; the patient should swallow 100–150 ml of barium sulfate suspension. The patient is placed in dorsal decubitus, then the antispastic is injected, after which the subject is immediately repositioned in the right lateral decubitus, a position in which he ingests the effervescent potion through a pipette or cannula. The contrast agent enters the duodenum which is already in hypotonic state. The duodenum in repletion and hypotonia is radiographed in this position and in several incidences in left posterior oblique position. The duodenal distension fades in dorsal decubitus and the root of the mesentery no longer ensuring its compression on D3. An accumulation of contrast agents is observed in the bulb. In this situation it is sufficient to raise the table by 30° in order to evacuate it and to be able to carry out the correct seriographies on the duodenum, especially the descending portion and the bulb, which, due to the hypotony, expands with the gas released by the effervescent potion.
There is also a method that can prevent overlapping of the gastric antral. This consists of introducing an Einhorn probe into the duodenum and through it 10 ml of xylin, with high viscosity administered at body temperature, which can achieve a hypotonia of the duodenum after a few minutes. Instead of xylin, scobutil can be used, administered intravenously. The hypotonic effect occurs in about 15–30 min. Barium sulfate suspension administration on the probe allows the duodenal framework to be completely opacified.
The method also has disadvantages. Antispasmodics alter the kinetics, tonicity, and duodenal secretion. During this time, due to the induced changes, the duodenal stasis is accentuated. For this reason, the low-density barium sulfate suspension is mixed with the stasis liquid, and if we do not use a homogenizing agent, bubbles may appear at the air-liquid interface that can fix themselves on the mucous folds, leading to an erroneous diagnosis. The method gives exclusively morphological information which means an incomplete radiological diagnosis. Due to hypotonia and hypokinesia, any stiffness and the study of autoplasty cannot be properly appreciated.
This method is used when the radiologist is interested in studying the duodenal framework or when, following previous examinations, the suspicion of a strictly localized lesion at this level is raised.
An enteral probe is used to perform this technique. The probe is introduced nasally or orally after the pharyngeal mucosa is embrocated or anesthetic solution is gargled. The distal end of the probe should reach the mid-level of D2; insertion of the probe into the stomach is done with the patient in a seated position, after which the patient lies in a right lateral decubitus and the probe is passed through the pylorus. To avoid coiling the probe, it is good to use either a probe weighted at the end or a metallic, soft, and flexible guide. The positioning of the probe will be done under radioscopic control. Then the duodenum is aspirated, after which the barium suspension is introduced under pressure, in a volume of about 30–50 ml. The suspension of barium sulfate must be fluid, homogeneous, and very adherent. It is indicated that the barium sulfate has a high dispersion degree and the suspension contains a methyl cellulose-type surfactant. Double contrast is obtained by blowing about 80–100 cm3 of air into the duodenum. The insufflation is gradual, under radioscopic control during examination.
The examination is performed in several positions and incidences, being mandatory to start from dorsal and right oblique anterior decubitus, continuing with the ventral and oblique posterior left decubitus, performing serial X-rays. Highlighting any anomalies requires X-rays of different incidences and intermediate positions, being able to better highlight the lesion.
The results are good, but they require a perfect knowledge of the anatomy of the region and the normal radiological aspect, since it differs from the known radiological anatomy.
The main advantage of the method is that it is possible to avoid overlaps with other segments of the digestive tract, especially with the gastric antrum. Also, by this method, small lesions of the mucosa can be detected, which can elude the examiner in simple contrast or in double contrast performed during the eso-gastro-duodenal examination. Antispastic substances that modify normal duodenal tonicity and kinetics and which modify duodenal secretion are not used. In this way the examination can also provide functional data of the investigated segment.
The examination is unpleasant for the patient due to the need to introduce the probe; therefore it is advisable that the examination be preceded by a brief discussion with the subject, in which the technique and the need for the examination will be explained to him. The crossing of the pylorus cannot always be realized; at position changes, a withdrawal of the probe into the stomach can occur, an incident that can also occur at a sharp intake of breath. This can be avoided if the examination is performed using a probe with a balloon at the end, which will set it to the desired level. The advantage of using such a probe is to prevent airflow back into the gastric antrum.
The time required for the examination is long. The technique is not of first intention, usually being performed only when there are clear clinical indications about the presence of a space replacement process.
The radiological techniques described can assess the overall duodenal morphology. Under distension and hypotony, the duodenal frame as a whole appears slightly enlarged. The examination allows to identify the duodenal anatomical segments and their possible anatomical variants (reverse V duodenum, mobile duodenum, small duodenal frame, surrounding the bulb, as in the case of gastric ptosis).
On the postero-external border of the descending duodenum, it is possible to highlight a possible imprint, due to the direct relations with the right kidney at this level.
Duodenal distension is exercised up to the level of its horizontal portion, immediately after the lower knee, when the examination is performed in ventral and oblique posterior left decubitus, being determined by the compression of the mesenter’s root over D3; in dorsal decubitus the compression is attenuated.
In dorsal decubitus the large papilla is visualized as a round-oval or oval transparency, contoured by the contrast substance. This area corresponds to the intramural pathway of the choledoch. The surrounding, well-visualized folds can converge into a single longitudinal fold or a bifid fold. The small papilla is rarely seen as a round lacunar image, with a diameter of about 5 mm, located cranially and medially to the large papilla.
In lateral decubitus, the longitudinal fold is highlighted on the endoluminal face, and the external duodenal contour becomes rectilinear due to the distension that erases the connivent valves. At the place of formation of the longitudinal fold, toward the tuber, a notch can be distinguished, which corresponds to the choledochian sphincter at this level. The small papilla is sometimes viewed as a notch located cranially to the large papilla.
Conventional radiological techniques represent at this time methods that are really historical, computed tomography replacing almost all of them.
Technological progress (much shorter scanning time, better spatial resolution) and the new adapted examination protocols allow accurate study of the digestive wall and extra-parietal lesion extension [1, 3, 4, 5, 6, 7, 8].
The main problem is obtaining an optimal distension of the duodenum in order to be able to correctly estimate the thickness of its wall, which is the most important computed tomography criterion of normality.
The duodenum is the most difficult region to examine due to the difficulty of obtaining adequate opacity, this being determined by the accelerated transport of water into the lumen, the water that dilutes the contrast agent.
Therefore, for the study of the duodenum, in fact of the entire upper digestive floor, the CT scan must be preceded by the ingestion of 600 ml of iodinated, water-soluble contrast substance, in a dilution of 2–3% approx. 5–10 min beforehand. IV antispastics can also be associated, which allow for a good study of the duodenal framework and the dissociation of the pancreas head. The exclusive use of air distension, as well as the use of simple water in combination with gastroduodenal hypotonia, increases the quality of parietography. The normal thickness of the duodenal wall is considered to be 3–4 mm.
The use of antispasmodics administered IV may diminish the artifacts generated by peristalsis, but due to the current ability to use a scanning time of less than 5 seconds, it is no longer of interest.
The intravenous administration of the iodinated contrast agent should be systematic for assessing the iodophilia of the lesion and for studying the relationships with the neighboring structures. It is also used to assess the extent of the tumor lesion, by determining the metastases, as well as to assess the existence of any abnormalities in the parenchymal organs, in relation to the duodenal disease or simultaneous with it.
In view of the frequent involvement of the duodenum in the neighboring tumors, especially those in the pancreas, in the vaterian ampulloma, etc., performing the computed tomographic examination both native and with contrast agent becomes almost obligatory. Thus, computed tomography becomes the essential method of establishing the starting point in duodenal tumor determinations, at the same time achieving the pre-therapeutic balance of the lesion extension. The administration of the intravenous contrast substance allows at the same time to opacify the vascular landmarks of this region, particularly the renal vein, inferior vena cava, as well as of the superior splenic and mesenteric vessels. The possibility of conducting the spiral computed tomographic examination gives almost overlapping information with the angiographic examination.
The acquisition is made through contiguous sections, 5 mm thick, but 3 mm sections can be used to allow analysis of small organs or to obtain details on the lesion.
The patient is initially placed in dorsal decubitus. The computed tomographic examination can be complemented, depending on the needs, with sections performed in ventral decubitus, lateral decubitus, sections that highlight the digestive connection of large tumor masses, and their dissociation from the adjacent viscera.
The use of some image processing techniques allows biplane or spatial reconstruction of the bile ducts and the duct of Wirsung and is usually used to detect lesions of distal bile ducts and in the vaterian ampulloma.
Ultrasonography as an imaging exploration of the duodenum is not a primary intention technique [1, 9]. It can be performed transabdominally—routine examination in which the primary information is related to the pathology of the parenchymal organs—and echoendoscopy, a method with maximum reliability on the pathology of the duodenal wall and the eventual differential diagnosis between primitive duodenal lesions/invasion by contiguity.
If the first technique of ultrasonographic exploration has a general addressability and accessibility, not requiring a special training of the patient, the second technique requires special equipment and a special skillset, being used especially by the doctors performing endoscopy, as a complement to a routine endoscopic examination.
Transparietal ultrasound can reveal changes of the duodenal peristaltic, duodenal stasis, or parietal duodenal infiltration. Complementing the examination with the Doppler technique may bring additional information to the duodenal tumor pathology. Probes of at least 5 MHz should be used for better lesion detection.
Ultrasound examination of the pancreas and distal bile ducts is the primary method for any suspected tumor pathology.
The specificity and sensitivity of the method depend on the quality of the equipment, but in particular, on the experience of the one using the method.
MRI scanning is not a primary imaging technique for patients with suspected tumor pathology of the duodenum-pancreatic region [1, 10, 11, 12, 13, 14, 15, 16, 17]. The possibility of clearly highlighting soft structures and multiplane images makes this method superior to computer tomographic exploration. Magnetic resonance highlights both the duodenal wall and the intraluminal duodenal content.
The body antenna is most commonly used. The spin echo sequences are constituted as reference sequences. T1-weighted sequences with short TR and TE allow excellent spatial resolution, providing the best morphological information of abdominal viscera.
T2-weighted sequences with long TR and TE have a good resolution in contrast and allow a more reliable tissue study. Given the relatively long acquisition time, at least 3 min, FLASH or SPGR gradient echo sequences are used more frequently, although they have a lower signal-to-noise ratio.
The use of fat saturation sequences reduces respiratory and structural artifacts but has a longer acquisition time.
For a complete study, it is absolutely necessary to use sequences specific to the study of vessels.
In case of suspicion of an ampullary tumor, MRCP is mandatory. In the last three decades, this technique has become absolutely necessary in the diagnosis of a biliary duct obstruction, obstruction which is caused at the right level by an ampullary tumor. MRCP is a diagnostic method, while ERCP remained a rather interventional method. T2 hyperintensive sequences are used, which make the content of both biliary and Wirsung ducts white in contrast to the rest of the structures. Sequences with thin sections (3–5 mm), which have the purpose of an MIP type reconstruction, and sequences with thick sections (30–50 mm), which have a short acquisition time (<5 s) and which are performed in multiple planes, are used. The acquisitions are made in the coronal and oblique coronal plane. If we refer strictly to MRCP, the administration of the contrast agent is not obligatory, but in the case of the ampullary tumors, this is a complementary sequence that is associated with the abdominal MRI scan. The MRCP highlights the contents and implicitly the size of the bile ducts and the duct of Wirsung, but does not give details on their wall, which was done by an abdominal MRI scan.
However, with MRCP you can administer negative oral contrast agent that reduces the hypersignal of gastric and intestinal fluids, thus increasing the contrast of the contents of the bile ducts and the duct of Wirsung.
In addition, the MRCP technique can provide information on the pancreatic function. This is achieved by the intravenous administration of secretin which has the role of increasing the pancreatic exocrine function, so it will increase the flow and quantity of pancreatic juice, and implicitly it will expand to the maximum the pancreatic ducts, thus being able to highlight both the main duct and the secondary ones.
The axial plane examination constitutes the reference sequences of the examination. In order to specify the exact anatomical reports or for the study of the vessels, frontal and coronal acquisitions are also made.
The mucosal study is performed using water per os or more reliably through the probe. The study of parietal changes requires sequences with paramagnetic contrast products.
The MR exploration, due to the possibilities of acquisition, processing, and reconstruction of the images, allows the study of the biliary ducts, having major importance in the tumor pathology of the duodenopancreatic region and the study dedicated to the vessels related to this region.
The histological structure comprises the tunics of the duodenal wall but also a separate muscular entity—the Oddi sphincter [1]. In terms of structure, the smooth musculature of the Oddi sphincter differs both anatomically and embryologically from the surrounding duodenal musculature. Its mechanical and electrical activity is independent and different from that of the duodenal muscle, but it is integrated into myogenic, regulating mechanisms through innervation and hormonal activity.
The mucus of the Vater papilla forms a complicated system of folds whose main function is the creation of “valves” with anti-reflux role, especially for biliary drainage. The ampulla of Vater is visible during the radiological examination in double contrast of the duodenum, being recognizable due to the presence of a superior fold and the longitudinal fold, located on the posteromedial face of the descending duodenum. Frequently at this level, there are two oblique folds. In conventional radiological exploration, in simple contrast, visualization of the papilla is much more difficult.
These are briefly some of the anatomical, functional, and embryological arguments that cause the tumor pathology of the ampulla of Vater to be treated separately from that of the duodenum, although the location of the Vater papilla is at the level of the descending duodenum, approximately in the middle of it.
These considerations have a very important practical substrate. According to Dudiak et al. [7], there is a direct interrelation between the anatomy and the embryology of the papilla and the radiological and endoscopic exploration possibilities, but especially in interventional radiology and endoscopy.
Regardless of the radioimaging method used, in the case of neoplasms of the ampulla of Vater, several signs that can guide the diagnosis can be highlighted (Figure 1).
Vaterian ampulloma: Conventional exploration.
Computed tomography and magnetic resonance imaging are particularly reliable in diagnosing cancers of the ampulla of Vater (Figures 2 and 3).
Vaterian ampulloma: CT exploration.
Vaterian ampulloma: MRI exploration.
Next we tried an analysis of these signs, direct or indirect, which alone or associated would help the radiologist to diagnose the lesion as accurately as possible.
The classical radiological appearance of the ampullar neoplasm consists of a lacunar image located in the region of the ampulla of Vater, which can be located intraluminally or marginally, on the internal contour of the second portion of the duodenum. This radiological change is also mentioned as a radiological sign of probability of a vaterian ampulloma by Caroli et al. [18].
The lacuna, as an elementary change in the radiological diagnosis of the ampulla, has lost its importance with the advent of other techniques of radioimaging investigation. In view of its existence, relatively frequently encountered today in standard radiological exploration protocols, we introduced the analysis of this radiological sign in this study as well.
The lacuna can be highlighted in a percentage of less than 40% of the total cases of malignancies of the pancreatic-duodenal region [1] (Figure 4).
The lacuna in a vaterian ampulloma.
The standardized criteria of malignancy of a lacuna considers that it must have an irregular and erased contour; it must interrupt the folds, due to peritumoral malignant infiltration, coexisting with the presence of possible superficial ulcerations; and, in principle, it is larger than 2–3 cm. Although it is known that ampullary carcinomas do not reach overly large sizes until the moment of diagnosis, due to the relatively rapid installation of jaundice, the specialized literature attests the presence of areas of neoplastic cells in the structure of a vaterian adenoma, even of very small dimensions.
Because of this, but also due to the fact that a conventional radiological examination, no matter how well performed, cannot accomplish the benign-malignant differentiation in the case of ampullary tumors, we consider that only the contours and dimensions of the ampullae should be analyzed.
From a dimensional point of view, we classified the lacunas in the ampulloma in gaps with diameters between 1–3, 3–5, and over 5 cm.
It is proven that this neoplastic entity is in the form of a small space replacement process, below 3 cm in a percentage of 70%, the remaining 30% being tumors with dimensions between 3 and 5 cm. You can also see the absence of space replacement processes with dimensions over 5 cm.
Semelka et al. [19], following a study carried out over a 2-year period, regarding the ampullary carcinoma, have concluded that the dimensions of this type of neoplasia do not exceed 5.5 cm.
These are arguments in favor of the authors’ assertions that vaterian carcinoma is largely the result of malignant transformation of an adenoma.
Also, the reduced size and the histopathological nature of the ampullary adenocarcinoma lead to the conclusion that this type of neoplasm is one with reduced aggressiveness.
The conventional radiological examination is excellently complemented by the computed tomographic exploration or by magnetic resonance that can detect space replacement processes with dimensions up to 1 cm. These are seen as small occurrences in the duodenal lumen, which cannot be detected by the standard radiological examination.
The report of detection of space replacement processes by the two associated methods, the examination of the duodenum in double-contrast and computed tomography or MRI, actually highlights a double number of processes of space replacement at the level of the ampulla of Vater, regardless of its size. Comparison of these two exploration techniques with each other, but also with endoscopic exploration, reveals a greater specificity of magnetic resonance exploration than computed tomographic exploration.
Semelka et al. [19], in a study on the reliability of radiological and imaging scanning techniques versus ERCP, concluded on the superior specificity of magnetic resonance scanning compared to computed tomography. At the same time, considering the potential risks of retrograde endoscopic cholangiopancreatography, it recommends MRI as the diagnostic method with the highest degree of specificity.
In conclusion, we have considered all the radio-imagistic methods of detecting the process of space replacement in the case of the vaterian ampullomas, which we presented at the beginning of this subchapter.
The Frostberg sign, also known as the inverted “3” sign (Figure 5), represents, from a radiological point of view, a semiological contour modification, which translates into an enlargement of the duodenal papilla, in the center of which the insertion of the biliary and pancreatic ducts remains fixed.
Frostberg sign.
From the etiological point of view, this radiological modification is nonspecific; it can be present both in the malignant tumors of the ampulla of Vater and in any enlargement of the head of the pancreas, whatever the cause.
The existence of Frostberg’s sign actually pleads for the secondary invasion of the ampullar “carrefour.”
Radiologically the two convexities connected between them represent in fact the edges of the papilla, and the opacified spines between them correspond to filling the papillary orifice with contrast agent.
The existence of the Oddi sphincter, but at the same time the tumor infiltration, does not allow the reflux of the contrast agent neither in the duct of Wirsung nor in the main biliary duct.
The conventional treatises of conventional radiology place Frostberg’s sign as the second in frequency in the radiological semiology of the vaterian ampulloma. At the same time, the specificity of this radiological manifestation is relatively small, recognizing that translating the enlargement of the papilla, in fact a papillary suffering, is incriminated, without being able to indicate its substrate.
Ferruci [20] considers the Frostberg sign to be a relatively rare sign, which has specificity with regard to the damage of the duodenal papilla, without being able to define the cause of this change.
The presence of the Frostberg sign in almost 60% of cases is detected in the vaterian ampullomas.
Although not pathognomonic, it is also found in pancreatic disorders; the Frostberg sign is frequently detected in ampullary carcinomas. With it we can differentiate, using the conventional radiological exploration only as a method of investigation, the vaterian ampulloma from the primitive duodenal malignancies. This assertion is based on the fact that any primitive malignant tumor, in which the developing area also includes the papilla, infiltrates the ampullae by erasing its outlines and damaging the specific architecture of the papillary folds.
Being a radiological contour modification, in the case of the double-contrast duodenum examinations, an exploration that achieves the maximum luminal distension is much better highlighted and thus reveals the finest modification of the duodenal contour.
In the case of ampullary adenocarcinomas, the segmental rigidity, from the level of the internal contour of the descending duodenum, above and/or underlying the tumor lesion, translates the neoplastic invasion by contiguity of the duodenal wall itself.
It is considered that the presence of rigidity on the internal contour of the descending duodenum is a radiological sign, which, associated with the lacuna, gives the radiological image a certain specificity regarding the vaterian ampulloma.
Taking into account the pathophysiological substrate of rigidity and considering that the vaterian ampullomas are neoplasms with reduced aggression, a small percentage of only 20% is explained, so the duodenal invasion is present in less than a quarter of cases [1].
The presence of rigidity is considered important because it is one of the first signs that can be highlighted by the standard radiological examination, especially by the double-contrast probe duodenography, the method that achieves the most reliable distension of the duodenal lumen. Highlighting a segment that presents rigidity, including the duodenal papilla, may be useful in associating the Frostberg sign. In this case, a radiological differential diagnosis can be made between the vaterian ampulloma and papillary disorders of other etiologies. The presence of rigidity in the absence of the Frostberg sign reduces the probability of the existence of a vaterian ampulloma, but it cannot completely exclude this diagnostic possibility. At the opposite pole is the hypotonic duodenography, which, due to the lack of duodenal functional information, highlights the rigidity with more difficulty.
From a dimensional point of view, the rigidity in the case it exists within the vaterian ampulloma has dimensions between 3 and 5 cm.
Ferruci [20] considers the imprint an important sign of conventional radiological exploration in detecting a space replacement process located in the vicinity of the duodenum, without necessarily having the meaning of a neoplasm.
Although it is an intrinsic neoplastic process, the vaterian ampulloma may induce imprinting due to the accompanying pancreatic reaction or, another explanation would be that the vaterian ampulloma invaded the pancreas. Regardless of the nature of the cause in the situation of the vaterian adenocarcinoma, the impression is the result of the dimensional increase at the level of the head of the pancreas.
In the case of the vaterian ampullomas, the imprint is found in up to 20% of cases.
The vaterian neoplasm is not a type of malignancy of the duodenum, but is localized within the duodenum, the vaterian ampulla being not a neighboring organ.
The imprint may occur due to the segmental enlargement of the head of the pancreas, due to the perilesional edema.
In any case, the imprint due to vaterian ampulloma is less spread on the contour of the descending duodenum than in the case of pancreatic cephalic malignancies. In the case of neoplasms with localization in the head of the pancreas, the association of changes in the extremity of the mucosal folds in the vicinity of the neoplasm is mentioned almost constantly, by the appearance of what bears the name of “T fold.” Vaterian ampullomas never associate this change in orientation of the mucosal folds (Figure 6).
Vaterian ampulloma: Imprint.
The presence of the imprint could possibly be a radiological sign of differentiation between the duodenal malignancies and the vaterian ampullomas but with a higher specificity between the duodenal tumors and any other tumor spread to the level of the descending duodenum.
Although the tumor process originates from the epithelium of the structures of the ampulla of Vater, its location makes the effect on the duodenal mucosal folds important.
In 70% of vaterian ampullomas, modifications of the mucosal folds are described, and unlike the primitive duodenal malignancies, there are also 30% of cases in which there is no evidence of duodenal mucosal damage.
Alignment of the extremities of the folds on the internal contour of the descending duodenum may indicate a neoplastic process, either ampullary or neighboring—head of the pancreas–but may also be encountered in the case of pancreatitis or perivisceritis, being a nonspecific sign. In the case of the vaterian ampullomas, the alignment of the folds takes place above the papilla (Figure 7).
Folds aligned above the lesion.
The presence of disorganized folds, although reduced in number, is important from a diagnostic point of view [1], being considered the disorganized folds in the descending duodenum as a sign of damage to the duodenal papilla. It can be concluded that this type of radiological modification cannot differentiate between ampullary malignancies and invasion of the ampulla of Vater by pancreatic cephalic neoplasms.
A more important extension at the level of the duodenal mucosa determines the presence of folds interrupted at the level of the second topographic segment of the duodenum.
The existence of ampulla of Vater adenocarcinoma does not, however, require the disappearance of all mucosal folds at the papilla level. A neoplastic infiltration of the papilla can lead to the deletion of the longitudinal fold and at the same time to a thickening of the superior fold, in which the diagnosis can only be made endoscopically, possibly with the association of multiple biopsies.
It should be noted that the dual contrast method of duodenography allows for a much more reliable study of mucosal folds, especially those at the duodenal papilla level, which requires maximum distension of the duodenal lumen, as well as double-contrast air-barium exploration.
Direct measurement of the thickness of the duodenal wall, either by computed tomography or magnetic resonance examination, is one of the most reliable indicators that show the damage of the duodenal wall, regardless of whether it is a neoplastic invasion or an inflammatory reaction (Figure 8).
Duodenal parietal change in the papilla.
If one compares the changes in the thickness of the duodenal wall from the duodenal tumors and the vaterian ampullomas, it is concluded that the ratio is exactly reversed, that is, in the case of the ampullomas, the probability that the duodenal wall has a normal thickness is 80%. Thus, the thickened wall raises the assumption of a primitive duodenal neoplasm more quickly than of a vaterian ampulloma but does not exclude it.
At the same time, the analysis of the dimensions of the parietal thickening according to the classification in the three subgroups, namely, the wall thickness with values between 4–6, 6–8, and over 8 mm, will show that in the case of the vaterian ampullomas, the wall can be thickened only up to 6 mm.
In conclusion, in the case of an ampullary neoplasia besides the fact that the probability of the presence of a thick duodenal wall is relatively small, in less than one fifth of cases, this thickening is minimal, the duodenal wall not exceeding 6 mm, as opposed to the duodenal malignancies in which at least in two-thirds of the cases we encountered a parietal thickening of more than 6 mm.
Also, the parietal thickening, in the case of neoplasms of the ampulla of Vater, has been shown to be unilateral, so it is an impairment of the duodenal wall through contiguity and at the same time limited.
The measurement of the parietal thickness is done either within the CT scan or by magnetic resonance scan, the results being identical [1, 21, 22].
As with parietal thickening, the study of tumoral extension, either by contiguity, or by lymphatic or blood route, of the vaterian ampullomas is carried out by the two radioimaging methods, namely, computed tomography and magnetic resonance imaging. The comparative results of the two methods proved to be identical.
The extension by contiguity, in the case of the ampullary neoplasms, consisted in reality only in the invasion of the pancreatic cephalic portion, the periduodenal space, as we described in the previous subchapters being normal.
Invasion of the head of the pancreas can be detected only in up to 20% of patients with vaterian ampulloma.
If we compare the existing data with those described in the case of the primitive duodenal malignancies, it can be observed that the numbers and the percentages of pancreatic invasions in the case of duodenal neoplasms are higher than the results in the case of the vaterian ampulloma. Thus, duodenal malignancies invade the pancreas in about 30% of cases, while in the case of ampullar carcinoma, this percentage is only 20%. This is an additional argument to support the idea that the vaterian ampulloma is a less aggressive form of neoplasm, even more “benign” than primitive duodenal malignancies.
The lymphatic extension results in radio-imagistic findings of adenopathy. In specialized literature, they are described as being possibly present in the case of vaterian ampullomas, as claimed by Semelka et al. [19], but they are extremely rare.
Extension through the bloodstream is evidenced by the presence of organ metastases, respectively located in the liver. Semelka et al. [19] describes the possibility of the existence of liver metastases in the case of the vaterian ampulloma.
The frequency of metastasis in ampullary neoplasms has been shown to be lower than in the case of primitive duodenal malignancies.
In conclusion, the vaterian ampullomas are neoplasms with reduced aggression, which is why Talamini et al. [2] state that compared to pancreatic carcinomas, ampullary carcinomas have a significantly higher resectability rate and a much better prognosis.
If, in the case of the duodenal neoplasms, the impairment of the bile ducts was only limited to the increase of the choledoch caliber in a few cases, the dilation in these cases was moderate, that is, it did not exceed 1.5 cm; in the situation of the vaterian ampullae, an enlargement of the bile duct tree size is detected in all cases.
In order to be able to classify the caliber changes of the biliary ducts, we divided the cases into three groups, namely, those with a diameter of less than 1.5 cm, but over 0.9 cm, those with diameters between 1.5 and 2 cm, and those with a caliber of over 2 cm.
The value of 0.9 cm is considered by all authors to be the maximum value of the choledoch duct that can be considered normal.
It can be seen that most of the vaterian ampullomas, that is to say, 70% have a choledoch with a size between 1.5 and 2 cm and over 20% with a size of over 2 cm. A percentage of less than 10% shows a moderate increase in the size of the choledoch duct, i.e., up to 1.5 cm [1] (Figure 9a,b).
(a, b) Changes of bile ducts in the vaterian ampulloma.
Semelka et al. [19] concluded that most of the neoplasms of the ampulla of Vater are defined by a significant increase in the size of the choledoch duct, considered by him to be over 1.5 cm, and that only in a limited number of cases does the choledochal dilation not exceed 1.5 cm.
Regarding the radioimaging method for determining the dimensions of the choledoch duct, the same author, in a comparative study, concludes that the magnetic resonance scan, which also includes cholangio-MRI, is superior to the computed tomography, especially due to its ability to detect once again very small processes of space replacement at the level of the ampulla of Vater, which are not evidenced by the computed tomographic examination. He also argues that the magnetic resonance method is similar to ERCP from these points of view, but unlike the latter it is a noninvasive method.
If we compare it with the neoplasms of the head of the pancreas, we will notice that the dilation of the choledoch duct is reduced in terms of caliber, that is, in the case of pancreatic cephalic malignancies, the frequency of the presence of the choledoch dilation is much lower, of only about 30%, and dimensionally the choledoch rarely exceeds 1.5 cm.
Magnetic resonance exploration at the same time allows the study of the contours of the terminal part of the choledoch (Figure 10).
Changes in the bile duct in the ampulloma: Cholangio-MRI.
The existence of an irregular contour, particular to a neoplastic infiltration, cannot be discussed, considering that the Oddi sphincter usually represents an anatomical barrier in the superior extension of the tumor. The association of the terminal part of the choledoch narrowing with its irregular contours guides the diagnosis either toward a distal cholangiocarcinoma or in the case of a choledochal invasion by a pancreatic neoplasm.
This is the reason why the analysis of changes in the biliary duct was limited to dimensional evaluation.
Due to the anatomical position, the ampullar neoplasm also determines the dilation of the duct of Wirsung but only in a third of the cases. Semelka et al. [19] considers the presence of a high-caliber Wirsung as a nonspecific sign, accompanying the choledochal dilation, in a ratio similar to that found in our study.
In the case of the vaterian ampullomas, changes of the gallbladder can also occur, namely, in volume, wall, as well as the presence of calcifications inside (Figure 11).
Lithiasis and bladder distension associated with a vaterian ampulloma.
The changes of the gallbladder are detected by computed tomography or magnetic resonance in 33% of occurrences in the case of the vaterian ampullomas, but without being able to distinguish if they were preexisting or caused by neoplasia [1].
Comparing to primitive duodenal neoplasms, there are no changes to the cholecyst.
It is considered that over 60% of the changes of the gallbladder in the tumor pathology of the duodenopancreatic region are detected in the cases of neoplasms of the ampulla of Vater. This leads to the conclusion that the presence of a gap in the periampullary region associated with changes in the choledochal caliber and with changes in the cholecyst leads the diagnosis to a vaterian ampulloma.
It is considered that there are no intracholecystic tumor masses and that the presence of vesicular lithiasis predominated in the case of the vaterian ampullomas.
In the case of ampullary carcinomas, there is no analysis of the changes of the vessels, due to their nonexistence, taking into account the anatomical reports of the ampulla of Vater.
The vaterian ampulloma is a neoplastic entity with precise diagnostic elements, which reduces the list of possible differential diagnoses.
By anatomical topography, the only possible differential diagnoses are pancreatic neoplasm and duodenal malignancy.
For both diagnoses the role of CT and MRI is defined.
Pancreatic head neoplasm:
With the help of CT, but especially MRI, it is established from the beginning the location of the tumor mass, the size, the changes in structure, and the contrast of the pancreatic cephalic tumor mass. MRCP contributes to the analysis of changes in the biliary tree and duct of Wirsung, specific to pancreatic cephalic neoplasm.
Diagnostic elements from conventional radiological examination are not practically discussed.
Malignant duodenal tumors:
Historically, there were conventional radiological signs, most of them indirect, to suspect a malignant duodenal tumor.
Basically, the real differential diagnosis is made using CT/MRI examination.
Duodenal parietal changes, luminal stenosis, localization, structural analysis, and contrast enhancement are defining elements in establishing the diagnosis of duodenal malignancy.
computed tomography
magnetic resonance cholangiopancreatography
magnetic resonance imaging
intravenous
endoscopic retrograde cholangiopancreatography
descending duodenum
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A sustainable textile product can be defined as one that is created, produced, transported, used and disposed of with due consideration to environmental impacts, social aspects and economic implications, thereby satisfying all three pillars of sustainability, and is expected to create the minimum possible or very least environmental and social impacts throughout its entire life cycle. In a specific product life cycle of any textiles, it uses different materials and consumes different forms of energy and many other processing inputs to produce or generate the desirable textile products as desirable outputs in different stages of their manufacture, packaging, despatch, use and final disposal. To make this life cycle sustainable for any textile goods, all these inputs and outputs are to be environment-friendly and eco-safe particularly to the living bodies on earth including humans for the entire life cycle, i.e. it should be noncarcinogenic and has to utilize renewable/recycled input streams with the least energy consumption.
When synthetic dyes were not known to humankind, dyeing of textiles was dependant on natural colors only. Later, when synthetic dyes were made available at ease and were started their commercial selling at low cost under different classes as ready-made dye powders to use with low cost and processing advantages, large-scale textile manufacturers and even small-scale dyers had been shifted to use more and more of synthetic dyes and pigments. But, with the enhancement of knowledge on environmental concern, people started to search for eco-friendly dyeing approaches as alternatives, as synthetic dyes are made from a non-renewable source of petrochemical base with chances of generating toxic chemicals as the by-product, which are not environment-friendly. Hence, the importance of eco-friendly dyeing of textile goods has started re-examination with the growing interest of consumers towards the use of eco-friendly natural dyed fiber-based textile products, which thus have been revived now needing more and more scientific information and analysis on those.
Moreover, the century-old natural dyeing processes had never died or discarded fully, and it is being practised still in different corners of the world and India is not an exception. Considering the niche market of eco-friendly dyed and finished natural fiber-based or organic textiles, recently, most of the textile dyers-cum-exporters are showing fresh interest for using natural dyes and natural finishing agents for textile dyeing, printing and finishing, if it can bring much more value addition (than using synthetic dyes), as a sustainable textile processing for eco-textile products. Natural dyes in addition of being eco-friendly produce very uncommon, soothing and soft shades in comparison with synthetic dyes [9]. For a successful commercial use of natural dyes for any particular natural fibre-based textiles, there has to be a standardization of process variables [9, 10] for extraction, mordanting and dyeing of that particular fiber-natural dye system with its testing and characterization [11], identification of important ingredients and other scientific analysis and process standardization for application of such bio-/natural dyes, bio-/natural mordants and bio-/natural finishing agents on natural fiber-based textiles. To obtain newer compound shades using a mixture of natural dyes needs a test of compatibility [12, 13]. The scientific determination of the dyeing rate, dyeing kinetics/thermodynamics and other physico-chemical parameters [14] of dyeing of a specific natural dye for specific textiles should be derived to establish appropriate standardized scientific dyeing techniques/procedures with the optimization of dyeing process variables and to decide the required after-treatment process necessary for obtaining an acceptable color fastness behavior with reproducible and uniform color yield. The status of natural dyeing up to 2001 [4], a comprehensive review on scientific studies on natural dyes up to 2009 [5, 6] including the characterization and scientific analysis for natural dyes, eco-friendly natural dyeing with bio-mordants [15], use of sonicator/ultrasonic assistance [16, 17] in natural dyeing and enzyme-based preparation and natural dyeing of textiles [18] and functional properties of selective natural dyes like UV protection [19, 20] and antibacterial properties [21, 22] are available in the literature.
However, the major problem of natural dyes encountered is their sufficient availability due to difficulty in collection, cost, poor color fastness and standardized methods of their application. Till date, there are limited studies available in the literature on scientific evaluation and testing, characterization, identification of important ingredients and process standardization related to optimization of dyeing process variables, mechanism of dye-mordant-fiber fixation, role of different mordants and mordanting assistants/additives and chemical pre-treatments/post-treatments/modifications for natural dyeing with evaluation of dyeing rate, dyeing kinetics and to develop compound shades (to overcome shade limitations) by use of binary or ternary mixture. Hence, there is a need for precise scientific and technological knowledge and development of systematic scientific methods of dyeing textiles with natural dyes and natural finishing agents.
Natural colorants have the following advantages as compared to synthetic colorants, but natural dyes have some disadvantages too.
The advantages [6, 7, 8, 9] of natural colorants and natural finishing agents:
Eco-friendliness: Natural dyes are less toxic, less polluting, less health hazardous, noncarcinogenic and non-toxic. Most of the natural dyes are considered to be eco-friendly as these are obtained from renewable resources as compared to synthetic dyes (derived from non-renewable petroleum resources and synthesized in an intermediate route involving many chemical hazards).
Soothing to the human eye: They have harmonizing colors, are gentle, soft and subtle and create a restful effect producing a soothing shade.
Biodegradability: Unlike non-renewable basic raw materials for synthetic dyes, the natural dyes of plant sources are usually agro-renewable/vegetable-based products and at the same time are biodegradable.
Availability of a wide range of colors: Natural dyestuff also can produce a wide range of colors by a mix-and-match system. A very small variation in the dyeing technique or the use of different mordants with the same dye or different concentrations of mordants on the same dye can create a variety of new shades.
Functional benefits of natural dyes/finishing agents towards wearers: Many natural dyes and natural finishing agents can be used as UV-protective and antibacterial materials. Natural textiles dyed with suitable natural colorants and finished with specific natural finishing agents can thus provide protection from UV rays, microbes or even mosquito bites. Natural dyes, e.g. myrobalan, turmeric, madder/manjistha (MJ), Arjuna, safflower, etc., possess a medical curative property as Ayurvedic medicine.
Despite so many advantages, natural dyes have some drawbacks [6, 7, 8, 9] too as listed below:
Requirement of a longer time: Natural dyes require a longer dyeing time for extraction and purification and also for actual dyeing via mordanting in comparison with time required to apply synthetic dyes on same textiles, for additional step of mordanting. Dye extraction steps require additional time and setup. The exhaustion of most of the natural dyes on textile materials is poor in spite of using the mordant which leaves a large quantity of colorant component in the dye bath after dyeing due to poor exhaustion, which increases the cost of dyeing though natural dyes are eco-safe as compared to dyeing with synthetic dyes.
Shade range limitations: It is difficult to obtain all desirable shades from natural dyes, i.e. ranges of shade available from natural dyes and pigments are limited. Out of the required three primary colors—red, green and blue—although there are several sources for reddish and greenish dyes, there is only one major source of the blue natural dye, i.e. from natural indigo. As different natural dyes and pigments are differing in their chemistry and application process, only few natural dyes are compatible to be applied together in a binary/ternary mixture and obviously are noncompatible for producing compound shades.
Non-reproducible shade: Due to the difference in proportion of constituents, the variation of these agro-products from one crop season to another in terms of location, species maturity period and consistent shade always cannot be obtained. However, after extraction, by UV spectral analysis, if the dye extract can be diluted to bring it to the same concentration level of colored solution, the reproducibility of shades can be better assured even with the extract of varying concentration of colored extract of such selective natural dyes.
Fastness properties: Only a few natural dyes and pigments possess a good rating of the overall color fastness satisfying consumers’ needs. As mordants with objectionable metal salts such as Cr, Cu, Sn, etc. are not permitted or allowed under eco-norms of different countries (ecomark scheme of India or OTN-100 norms of the UK, etc.), the overall color fastness rating of natural dyed textiles is sometimes poor to medium only. However, recent approaches of a suitable pre-treatment with natural bio-mordants containing tannic acid residues or pre-treatment with natural cationic agents like acid-extracted soya bean seed waste [23] and post-treatment with chitin (natural cationic agent) or post-treatment with natural UV absorber agents (like orange peel, eucalyptus leaves, etc.) are being used for enhancing the color fastness rating for wash and light to an acceptable level.
The present scenario shows that an approximately 1% share of textiles is only being dyed with natural dyes that are used mostly in the cottage sector by traditional artisans and small-scale textile dyers. The reasons for not using natural dyes in the large-scale textile sector were, however, lack of availability of ready extracted and purified dye powder, lack of standardized dyeing processes with assurance of reproducible and uniform shades and non-warranty of the required level of color fastness to achieve. Natural dye application processes cannot be easily implemented by large-scale textile mills as machine dyers. However, recent effort of people, understanding environmental friendliness of natural dyes and finishes with growing demands of customers for such eco-friendly products, ready availability of extracted and purified natural dye powder by certain newer natural dye manufacturers along with their recommendation of standardized mordanting and natural dyeing and finishing processes have partly overcome these issues for machine dyeing viable in large-scale textile sector. The natural bio-indigo dyeing on cotton denim [24] to produce bio-denim using natural reducing agents, as developed by Ama Herbal Lab Pvt Ltd, Lucknow and use of earth colour from plant waste developed by Archoma, Mumbai has become a commercial success in India for large scale industry.
However still natural dyeing industry is a labour-intensive industry concentrating in the small-scale sector of handloom textiles and khadi (hand spun and handloom woven) sector in developing countries like many South-East Asian countries providing livelihoods by creating job opportunities for all those engaged in cultivation, extraction and application of these natural dyes on textiles. Cultivation of natural dye plant is also an alternative cash crop to the cultivators. For the promotion of natural dyeing and natural finishing of textiles including the khadi sector, the availability of extracted and purified natural dye and pigment powder as ready soluble colorants has to be assured to promote such eco-friendly natural dyed textiles in the khadi sector. Some work [19] in this endeavor by Mahatma Gandhi Institute for Rural Industrialization (MGIRI), Wardha, Maharashtra, India, is worth mentioning for the cotton khadi sector. As the small-scale khadi and handloom sectors of textiles lack the resources to install and operate expensive effluent treatment plants needed to bring the synthetic dye’s effluent within the eco-limits set by regulatory authorities, they will be more benefitted by adopting standardized dyeing methods with natural dyes and natural finishes on specific natural fiber-based textiles, by mitigating its major problems.
To promote natural dyed textiles, there is an essential need of establishing proper identification methods and test protocols with suitable national and international test standards of identifying natural dyes from the dyed textiles followed by establishing proper certification protocols for natural dyes from the natural dyed textiles in the form of natural dye mark protocol, which would definitely improve consumers’ confidence and would benefit both producers and users. In this attempt BIS, India, and also ISO/TC-38 have been working on it since 2015, and till date few such test standards are finalized and published [25, 26] by BIS, India, and ISO/TC-38 has framed a special working group—WG-31—on natural materials for textiles for finalizing such global standards for worldwide consumers and producers benefit, so that both large- and small-scale sectors of textile industries can get benefitted.
1% aqueous solution of each purified individual natural dye powder was separately prepared and was subjected to a wavelength scan in a UV-VIS absorbance spectrophotometer for 200–700 or 1100 nm wavelength range to identify the predominant lambda maximum with specific peaks in UV region and specific peaks in visible region in order to understand the UV-absorbing nature of the dye. Absorbance peaks of UV-VIS spectrum of a dilute aqueous solution of few individual purified natural dyes have been shown in Table 1.
Purified natural dyes | Wavelengths (nm) for major UV-VIS peaks with λmax |
---|---|
a. Marigold (MG) | 250, 598 (λmax) |
b. Babool (BL) | 242, 372, 550, 602 (λmax) |
c. Jackfruit wood (JFW) | 250, 540 (λmax) |
d. Sappanwood (SW) | 242, 373, 610 (λmax) |
e. Red sandalwood (RSW) | 250, 370, 540, 602 (λmax) |
f. Manjistha/madder (MJ) | 380, 540, 610 (λmax) |
g. Tesu (TS) | 250 (very small negligible peak), 385 (small trough), 490 (λmax) |
UV-VIS absorbance peaks at different wavelength for few purified natural dyes.
In the UV-VIS spectrum of each natural dye, if there are predominating sharp peaks in the UV region, the dye has a reasonable UV-absorbing character, indicating that the said particular dye may have a higher UV absorption rate enhancing the UV-fading rate due to its more UV-absorbing character, and hence specific cares and after-treatments with more stronger UV absorber compounds [8, 13] are necessary for improving light fastness of particular dyed textiles, by additional treatment with more stronger UV absorber compounds having preferential UV absorption, leaving the dye with UV absorber character to absorb less UV light.
It may be observed from the wavelength scan of UV-VIS spectrum of tesu extract (Figure 1) in an aqueous medium that in the UV region (190–380 nm), there is hardly any preferential absorbance peak in this UV region, but in the extended UV zone, it shows a small broad hump at 250 nm and a small trough at 385 nm along with showing negative absorbance in a particular wavelength (190–250 nm). Thus, there is almost no preferential UV absorption which occurs in tesu colorant (extracted in the aqueous medium), and hence the light fastness of tesu dye is not to be affected much by UV light exposure, showing predominating hue by large peak at λmax-490 nm for tesu.
UV-VIS spectra of the extract of color component of tesu as natural dyes.
UV-VIS spectrum of few selective natural dyes and their peaks is shown in Figure 2 and Table 1, which shows that these selective natural dyes (except tesu) show UV-absorbance peaks either at 242–250 nm or at 370–380 nm in UV region, where it is found to be dominating in 242–250 nm in UV zone for babool and marigold, whereas madder (Rubia/manjistha) has no such preferential UV-absorbance peak in 242–370 nm zone except a small but sharp peak at 380/390 nm, which is possibly due to absorbance of the keto or more specifically for quinone group in anthraquinone structure present in madder/manjistha (Rubia) containing manjisthin, alizarin, etc. [8]. Besides these peaks, the other characteristic peaks in the visible region (400–700 nm), in the UV-VIS spectrum of corresponding solutions of the said natural dyes, are the peaks for the predominating hue of the main color component of the corresponding dye. In some cases (as in madder, red sandalwood, babool, etc.), there are more than one or multiple peaks in the visible region that indicates the presence of more than one color component as a mixture which shows multiple peaks at the visible region closely differing from λmax for predominating hues for each of them [8, 11, 13].
UV-VIS spectra of the extract of color component of few natural dyes other than tesu (x- and y-axes: Absorbance values in y-axis are −3.0 to +3.0 and wavelength values are 190–1100 nm).
The purified dye powder was further washed in distilled water followed by washing in 100% acetone before final drying and was then subjected to FTIR spectroscopy in a double-beam spectrophotometer (in Perkin Elmer spectrum-II FTIR spectrophotometer) using a KBr disc technique. The FTIR spectrum for each purified selective natural dye powder has been shown in Figure 3 for tesu, Figure 4 [spectra (a)–(e) for red sandalwood, jackfruit wood and madder/manjistha (Rubia)] and Figure 5 [spectra (d)–(f) for marigold, babool and sappanwood]. The characteristic FTIR bands/peaks (absorption band, type and made of vibrations, nature and appearance of bands/peaks along with the description of responsible bonds and associated chemical functionalities) for each of the purified natural dyes observed have been marked with corresponding wave number (cm1) for each spectrum [8, 11] in Figures 3–5 and are also tabulated in Tables 2–4 [8, 11].
FTIR spectra of purified tesu as natural dyes (transmittance values are 25–100%).
FTIR spectra of purified natural dyes: (a) red sandalwood, (b) jackfruit wood and (c) manjistha/madder (Rubia) (transmittance values are 25–100%).
FTIR spectra of purified natural dyes (d) marigold, (e) babool and (f) sappanwood (transmittance values are 25–100%).
Absorption band, wave number in cm1 | Nature of bands/peaks | Bond and its mode of vibration with associated responsible functional groups |
---|---|---|
For TS (TESU) | ||
608–668 (avg. 647) and 1350 | Small | −OH out-of-plane bending and −OH in-plane bending |
1210–1296 (avg. 1257) | Small | −C−O−C and −C=O stretching combination |
1376–1487 cm−1 (avg. 1381) | Medium | −CH and −CH2 bending |
1540–1557, 1582, 1589 and 1630 | Small and doublet | –C=C stretching in nonconjugated –C=C– |
1680–1750 | Medium sharp | –C=O stretching attached with aromatic ring structure |
2359, 2810 and 3008 | Weak but intense | –C–H stretching in aromatic ring |
3288 and 3563–3650 | Small | –O–H stretching in free –OH of phenolic structure |
Spectroscopic data for FTIR peaks of a purified extract powder of tesu as natural dyes.
Absorption band, wave number in cm1 | Nature of bands/peaks | Bond and its mode of vibration with associated responsible functional groups |
---|---|---|
a. For RSW | ||
993 | Small | –C–H deformation in benzene ring |
1338–1397 | Doublet | –C–O–H bending in primary and secondary alcohol |
1540–1557 | Small and doublet | –C=C stretching in nonconjugated –C=C |
1680 | Small | –C=C stretching in nonconjugated –C=C |
1716 | Small | –C=O quinone to aromatic ring or –C=O stretching in ring ketone in aromatic ester and 6C ring ketone |
2354 and 3008 | Weak but intense | –C–H stretching in aromatic/benzene ring |
2815 | Small | –C–H stretching in –O–CH3 group |
3288 | Small | –O–H stretching in bonded H–bonds |
3563–3650 | Small | –O–H stretching of phenolic –OH |
b. For JFW | ||
744–883 | Multiplet | –C–H out-of-plane deformation in benzene ring |
940 | Weak but intense | –C–O stretching vibration in higher cyclic ether linkages (as present in morol for jackfruit wood) |
993 | Weak but intense | –C–H deformation in benzene ring |
1049 | Medium | –C–O stretching in primary or secondary alcohol |
1135–1234 | Multiplet and sharp | –C–O stretching and –OH in-plane deformation in phenol |
1394 | Small | –C–H bending in methyl ketone or methyl groups |
1486 | Sharp but small | –C=C stretching in aromatic ring |
1540–1557 | Small doublet | –C=C stretching in aromatic ring |
1718 | Small | –C=O stretching of quinone to aromatic ring or –C=O stretching of ring ketone in aromatic ester and 6C ring ketone |
2341 | Small but sharp | –C–H stretching in benzene ring |
3008 | Small | –C–H stretching in aromatic ring |
3230 | Medium intense | Hydrogen bond –OH stretching in phenolic structure |
3563–3650 | Weak but intense | –OH stretching for aromatic phenolic –OH groups |
Spectroscopic data for FTIR bands/peaks of other selective purified natural dyes.
Absorption band, wave number in cm1 | Nature of bands/peaks | Bond and its mode of vibration with associated responsible functional groups |
---|---|---|
c. For madder/MJ, also known as Rubia | ||
618–900 | Multiplet | –C–H out-of-plane deformation in benzene ring |
997 | Sharp | –C–H deformation in benzene ring |
1011–1047 | Medium | –C–O stretching in primary or secondary alcohol |
1130–1232 | Very strong | –C–O stretching and –OH in-plane deformation in phenol |
1474 | Small | –C=C stretching in aromatic ring |
1500–1540 | Sharp | –C=C stretching in aromatic ring |
1615 and 1718 | Small and sharp | –C=O stretching in aromatic ring and ring ketone |
2355–2351 | Doublet | –C–H stretching in –O–CH3 group |
3008 | Small | –C–H stretching in aromatic/benzene ring |
3653–3650 | Small | –O–H stretching in phenolic –OH groups |
d. For MG | ||
720 | Small but intense | –C–H bending in polymethylene (as present in xanthophyll esters present in MG) |
744–883 | Multiplet and sharp | –C–H out-of-plane deformation in benzene ring |
940 | Tiny | –C–O stretching vibration in higher cyclic ether linkages |
970 | Small and sharp | –C–H deformation in aromatic ring |
1049 | Sharp and intense | –C–O stretching in primary or secondary alcohol |
1130–1232 | Multiplet | –O–H in-plane deformation in phenols |
1390–1477 | Sharp | –C=C stretching in aromatic ring |
1590 | Sharp and intense | –C=C stretching in aromatic ring |
1730 | Small | –C=C stretching and –C=O stretching in nonconjugated–C=C |
2354, 2647 | Small | –C–H stretching in –O–CH3 or methyl ether |
3022–3012 | Doublet | –C–H stretching in aromatic ring |
e. For BL | ||
720 | Small but intense | –C–H bending in polymethylene (as present in xanthophyll) |
778–882 | Sharp multiplets | –C–H out-of-plane deformation in benzene ring |
940 | Sharp | –C–O stretching vibration in higher cyclic ether linkages |
972 | Small and sharp | –C–H deformation in aromatic ring |
1049 | Sharp and intense | –C–O stretching in secondary or primary alcohol |
1130–1232 | Sharp multiplets | –OH in-plane deformation for phenolic structure |
1400–1500 and 1500 | Multiplet or tiny | –C=C stretching associated with aromatic ring structure |
1730 | Small | –C=C stretching in nonconjugated structure |
2354–2312 | Doublet | –C–H stretching in benzene/aromatic ring structure |
3640 | Small | Vibration of free phenolic –OH groups |
f. SW | ||
627 | Small | –C–H out-of-plane deformation in benzene ring |
720 | Small | –C–H bending in (CH2)n, i.e. polymethylene |
776–882 | Sharp multiplets | –C–H out-of-plane deformation in benzene ring |
940 | Sharp | –C–O stretching vibration in higher cyclic ether linkages |
971 | Sharp | –C–H deformation in aromatic ring structure |
1049 | Sharp | –C–O stretching in primary or secondary alcohol |
1130–1232 | Sharp multiplets | –OH in-plane deformation phenols |
1400–1500 | Multiplet | –C=C stretching in aromatic ring |
1532–1590 | Multiplet | –C=C stretching in aromatic ring |
1840 | Very small | |
2354 | Broad trough | –C–H stretching in benzene ring |
3010 | Small | –C–H stretching in aromatic ring |
3230 | Small | Hydrogen bonded –OH stretching in phenol |
Spectroscopic data for FTIR bands/peaks of selective other purified natural dyes.
The FTIR spectral scan analysis is presented in Tables 2–4, which are easy to understand for confirming the type of chemical groups indicating types of bonds present therein in the main color components for each purified natural dye mentioned there. The known chemical structures of the major color components of each of these natural dyes have been reported in the earlier literature [7, 8]. The FTIR bands of each purified natural dye are found to be matching with the earlier reported chemical structures of major color components of each individual natural dye mentioned here.
The purified dye powder for each selective natural dye (except tesu) was further repeatedly washed in distilled water twice followed by washing with ethyl alcohol followed by washing again in 100% acetone and was then subjected to final drying under a vacuum oven. Then 2 mg of each individual dye powder was placed in the aluminium crucible of differential scanning calorimeter (DSC) console (using Shimadzu differential scanning calorimeter Model-DSC-50) and started heating and running it by usual method under flowing nitrogen (N2 gas flow rate was at 50 cm3/min), and heating rate was maintained at 10 °C/min over a temperature range from ambient (about 28–30°C) to 490–500°C and obtained DSC thermograms are plotted as shown in Figure 6.
DSC thermograms of purified natural dyes: (a) babool, (b) jackfruit wood, (c) red sandalwood, (d) sappanwood, (e) marigold and (f) manjistha/madder (Rubia).
In each case, the thermal transition temperatures are marked in each thermogram (a) to (f) in Figure 6, and the corresponding data on the maximum peak for thermal transition temperatures, nature and appearance of DSC peaks and probable reasons [8, 11] of the observed thermal transitions are tabulated in Table 5, except tesu, as tesu is considered in the earlier literature to contain normal heat-resistant butein [29] as the color component (hence, there was no need to study the thermal stability of tesu at dyeing temperature zone of 60–100°C).
Compound dyes | Thermal transition temperatures, °C | Nature and appearance of DSC peaks | Probable reasons for observed thermal transitions |
---|---|---|---|
a. BL | 56 | Small wide hump (exothermic) | Combined effects of breaking of H-bonds and moisture evaporation |
178 | Broader crest (exothermic) | Decomposition of other minor constituents | |
239 | Broader trough (endothermic) | Decomposition of some other minor constituents | |
279 | Sharp peak (exothermic) | Thermal decomposition of gallic acid | |
300 | Deep trough (endothermic) | Decomposition of epicatechin | |
347–421 | Flat plateau region (exothermic) | No effects | |
435 | Deep trough (endothermic) | Thermal decomposition of catechin | |
487 | Small sharp peak (exothermic) | Thermal decomposition of theoflavones or other minor constituents present | |
b. JFW | 56 | Small hump (Exothermic) | Combined effects of breaking of H-bonds and moisture evaporation |
80–178 | Flat plateau region | No effects | |
250 | Wide trough (endothermic) | Thermal decomposition of morol | |
c. RSW | 82 | Sharp peak (exothermic) | Breaking of strong H-bonds of deoxysantalin |
95 | Sharp trough (endothermic) | Thermal decomposition of deoxysantalin | |
102 | Sharp peak (exothermic) | Breaking of more strong H-bonds of santalin (A and B) | |
129–378 | Flat plateau region (endothermic) | No effects | |
411 | Small trough (endothermic) | Thermal decomposition of santalin (A and B) | |
436–500 | Flat plateau region (exothermic) | No effects | |
d. SW | 72 | Small transition (endothermic) | Moisture evaporation |
350 | Small trough with sharp transition (endothermic) | Thermal decomposition of brazeline | |
353–500 | Flat plateau region (exothermic) | No effects | |
e. MG | 35 | Tiny peak (exothermic) | Breaking of H-bonds |
56 | Medium trough (endothermic) | Moisture evaporation [7] | |
120 | Small trough (endothermic) | Thermal decomposition of xanthophyll ester | |
127 | Sharp trough (endothermic) | Thermal decomposition of quectrol (flavanol) [7] | |
157 | Tiny trough (endothermic) | Decomposition of other minor constituents | |
250–500 | Flat plateau region (exothermic) | No effects | |
f. MJ or madder (Rubia) | 37 | Tiny peak (exothermic) | Breaking of H-bonds |
56 | Deep trough (endothermic) | Moisture evaporation | |
74–120 | Flat plateau region (exothermic) | No effects | |
125 | Small and sharp trough (endothermic) | Thermal decomposition of purpuroxanthin | |
137 | Sharp trough (endothermic) | Thermal decomposition of manjistha | |
157 | Tiny trough (endothermic) | Thermal decomposition of purpurin | |
177 | Tiny trough (endothermic) | Thermal decomposition of pseudopurpurin | |
250–500 | Flat plateau region (exothermic) | No effects |
DSC thermal transition temperatures of extracted and purified natural dyes.
The frequently asked question (FAQ) for this study arises: why DSC study of natural dyes is necessary? By DSC thermogram analysis, the thermal degradation temperature of any color components present in any natural dye molecules is indicated for heating under nitrogen at different temperature zones, which very well identify and reveal lower-temperature degradable components, if present in that sample. If any lower-temperature degradable components are there in a specific natural dye extracted sample, then its dyeing should be done below that temperature, i.e. dyeing temperature should not exceed above that temperature at all. Otherwise, if one of the color components degrades thermally at dyeing temperature in dye bath, this will cause some loss of color component and less shade depth. To avoid this, it is also essential to study the DSC parameters for natural dyes also. For example, in DSC thermogram—c for red sandalwood—there is an exothermic sharp thermal degradation peak at 82°C, and hence it should not be dyed above 80°C, i.e. preferably dyed below 80°C or preferably at 70°C. Similarly for DSC thermogram—f for madder—there is also an exothermic broader hump for thermal degradation of one of its component starting at 74°C and continuing up to 125°C, indicating that madder dyeing should be done below 74°C, i.e. preferably around 60–65°C only (not at the water boiling temperature).
A number of test methods developed for different commercially used natural dyes for textiles to test those natural dye powder and natural dyed clothes for the identification of specific natural dyes from such dyed textiles have been adopted by the BIS as IS standards [25, 26], some of which are under favorable consideration of ISO/TC-38 also for global standardization of these test methods as per the ISO format. For example, one such method of test of identification for madder/manjistha (Rubia) as natural dye is discussed here to understand the process.
Purified natural and synthetic counterparts of similar two red dyes (madder/Rubia known as manjistha containing manjisthin and synthetic alizarin considered being used instead of madder) were taken and weighed separately (0.1 gm) and dissolved in 1000 ml dichloromethane and scanned through UV-VIS spectrophotometer for wavelength scan. For the visible spectrum these two solutions were further diluted five times and were used for UV spectrum study for identification by comparison of the peaks and UV-VIS spectrum with lambda maxima and optical density (OD) values of natural madder (Rubia) and synthetic alizarin red colors, as shown in Figure 7 and Table 6.
UV-VIS spectrum of madder (Rubia) and synthetic alizarin dyes.
Peak shown at nm | In synthetic red alizarin | In natural madder (Rubia) | Comments for distinguishing peaks and lambda max values for identification (describing difference with reason) |
---|---|---|---|
250 nm (1.38 OD) and 426 nm (0.309 OD) | 250 nm(OD, 0.954) and 491 nm (OD, 0.171) | The pattern of the peaks and optical density at lambda max values in UV and visible region are very different for the two dye samples as per Figure 7 |
Identification of peaks and lambda max values from UV-VIS spectrum of natural madder (Rubia) and synthetic alizarin.
It is observed that in the visible region (400–700 nm) of the UV-VIS spectrum, characteristic peaks found are at 426 and 491 nm for synthetic alizarin, and corresponding peaks for natural madder (Rubia) dye containing manjisthin are at 398 nm (OD 0.801) and 426 nm (OD 0.838) as distinguishing characteristic peaks and their optical densities for differentiating natural madder containing manjisthin and synthetic alizarin by UV-VIS spectral analysis as shown in Figure 7.
While in the UV region of the UV-VIS spectrum, optical density at same lambda max. Values for peaks in UV region for natural madder (Rubia) and synthetic alizarin dyes are different. In the UV region (200–380/399 nm) of the UV-VIS spectrum, although both shows the lambda max peaks in UV region at same wavelength, i.e. at 250 nm, but their optical densities values at 250 nm for both the red colors are different (corresponding data are provided in Table 6).
The purified extracted dye powder of natural madder (i.e. Rubia containing manjisthin) and synthetic alizarin as two different red dye samples were analyzed by HPLC method [27]. Both the natural madder and synthetic alizarin purified and washed dye powder were weighed separately (0.1 g) and were dissolved in 1000 ml of methanol. 1 μL of the prepared solution of both one by one was injected to the C-18 reverse phase column of HPLC with UV detector and eluted in HPLC column. The base line showed response within a run of 15 min for natural madder (Rubia) and synthetic alizarin. The parameters of this assay were made to be such that a clean peak of the both the samples are observed. Clear observation was made from these two red dye samples as shown in the two chromatographs given in Figures 8 and 9, that for synthetic alizarin, one main peak is at 1.6 min and no peak after 3.5 min, while natural madder (Rubia) has main peak at 1.8 min and another peak at 11.3 min, as per data provided in Table 7.
Chromatogram of synthetic alizarin.
Chromatogram of natural madder (Rubia) containing natural alizarin.
Peak shown at nm | In synthetic alizarin | In natural Rubia | Comments for distinguishing main peaks and time in min for identification (with reason for differences) |
---|---|---|---|
255 nm | One main peak is at 1.6 min and no peak after 3.5 min | 1.8 min main peak, small peaks at 2.5 and 11.3 min | One main peak is at 1.6 min and no peak after 3.5 min while natural Rubia has a main peak at 1.8 min and a characteristic peak at 11.3 min |
Chromatogram analysis data of natural madder (Rubia) and synthetic alizarin.
Thus, natural madder (Rubia) and synthetic alizarin show clear differences in their characteristic peaks, retention times and peak heights. Natural madder (Rubia) always shows two equivalent peaks as compared to synthetic alizarin which shows three peaks due to un-purified sample of the latter; this is a mark of identification factor between natural madder (Rubia) and synthetic alizarin by HPLC method with a UV detector.
This method of identifying Rubia (madder) as a natural dye to identify from its dyed textiles has been standardized and adopted as Indian standard—IS-17085-2019, January 2019 [25]—and many more such natural dye test standards for the identification [25, 26] of specific natural dyes from dyed textiles are adopted as Indian standards by the BIS.
The study of optimization of extraction conditions, mordanting, and dyeing process variables of few natural dyes on different textiles is available in the literature [6, 10, 28, 29], but the study of dyeing process standardization of madder (Rubia tinctorum-Indian madder was obtained from M/s AMA Herbals Lab Pvt Ltd, Lucknow, India) applied on cotton is reported here. In this part of study, initially the optimization of conditions of extraction of madder (manjistha/Rubia) as a natural dye/colorant is reported in Item 2.2.1. Later, bleached cotton fabrics were dyed after a sequential double natural pre-mordanting [10% myrobalan (harda) + 10% natural potash alum, i.e. 20% overall application of harda + natural Potash alum in 50:50 ratio], and then dyeing process variables (such as mordant concentration, dye concentration/shade %, pH, dyeing temperature, dyeing time, material-to-liquor ratio (MLR) and electrolyte/Salt concentrations) are reported using madder (Rubia/manjistha) extract as a natural dye to optimize the dyeing process conditions, and the observed results are discussed in Item 2.2.2.
For optimizing the extraction conditions, a colored aqueous extract liquor was obtained from madder (Rubia) dried powder under differently varying conditions of MLR 1:20–1:60, pH 4–10, extraction time period 15.0–90.0 min and extraction temperature 50–90°C for optimizing the conditions of extractions of color components of madder/Rubia (manjisthin and purpurin) from its natural source materials. The optical absorbance or OD values of the filtered aqueous extracts of the madder/Rubia were measured at λmax of 540 nm (i.e. maximum absorbance wavelength) using Hitachi-U2000 UV-VIS absorbance spectrophotometer. Results of optical density (color value of dye solution) of aqueous extraction of madder under varying conditions have been shown in Table 8. The maximum values of OD [30] at λmax of 540 nm wavelength are identified and marked in bold letters (for corresponding maximum color yield) as shown in Table 8 and are considered as optimum or best extraction conditions, i.e. MLR at 1:30, pH at 5, extraction temperature at 60°C and extraction time at 30 min.
Extraction variables | OD/absorbance for madder at λmax. 540 nm | Extraction variables | OD/absorbance for madder at λmax. 540 nm |
---|---|---|---|
MLR | Temperature (°C) | ||
1:20 | 0.238 | 50 | 0.198 |
1:30 | 0.279 | 60 | 0.278 |
1:40 | 0.266 | 70 | 0.132 |
1:50 | 0.252 | 80 | 0.164 |
1:60 | 0.236 | 90 | 0.177 |
Time (min) | pH | ||
15 | 0.241 | 4 | 0.192 |
30 | 0.273 | 5 | 0.281 |
45 | 0.188 | 6 | 0.188 |
60 | 0.173 | 8 | 0.193 |
90 | 0.182 | 10 | 0.205 |
OD or absorbance values of aqueous extract of madder (manjistha/Rubia) (λmax of 540 nm) extracted under varying conditions of aqueous extraction*.
*Values in bold indicate the optimum values considered while studying the effect of extraction parameters for madder. When one parameter was varied, say for MLR variation of 1:20–1:60, time was 30 min, temp was 60°C, and pH was 5. For time variation of 15–60 min, MLR was 1:30, temp was 60°C, and pH was 5; for temperature variation of 50–90°C, MLR was 1:30, time was 30 min, temp was 60°C, and pH was 5; and for pH variation 4–10, MLR was 1:30, temp was 60°C, and time was 30 min.
Table 9 shows the effect of concentrations and types of mordanting (as single or as double pre-mordanting technique) on surface color depth and other color interaction parameters of cotton fabric dyed with 4% aqueous extract (extract of purified 4% dry powder of madder obtained from M/s AMA Herbals Lab Pvt. Ltd., Lucknow) as colored dye solution used in this natural dyeing. Amongst all the single and double pre-mordanting done (Table 9), a combination of 20% overall application of harda and natural potash alum (50:50 ratio), i.e. 10% harda and 10% natural potash alum applied in sequence, satisfies the most desirable required stoichiometric ratio for effective complexing showing maximum surface color strength (K/S value) than that obtained by using either any of the said single pre-mordants or any other double pre-mordants studied for dyeing bleached cotton fabric with madder/Rubia. This may be an important fact that myrobalan (harda) acts as a mordanting assistant or dyeing additive, when used in conjunction with metallic salts. Myrobalan (harda) contain chebulinic acid/tannic acid moieties (having mordantable –COOH/–OH groups) in it, which thus is useful for a higher color yield when used along with the metal salts as second mordant forming insoluble metal tannates/chebulinate (containing tannic/chebulinic acids) utilising multiple nos of carboxylates (for chebulinic acid)/multiple -OH groups (having high coordinating power) present in harda/myrobalan helping to enhance more fixation of such natural mordantable/anionizable dye molecules forming giant coordinating complex of fibre-harda-metallic mordant-natural dye to fix with –OH groups of cellulosic (cotton) fibers [19]. But it still has enough free adjacent hydroxyl/carboxylic acid groups to form mordant-dye complex to fix the anionizable/mordantable selective natural dye like madder/Rubia on the said harda and alum double pre-mordanted bleached cotton fibers. However, that is why the application of harda alone containing chebulinic acid is not found to provide sufficient color yield and color fastness for these natural dyes, which however when applied with the combination of metallic salts together (here, it is potash alum containing aluminum) give such an encouraging result on the subsequent dyeing with madder as an anionizable/mordantable natural dye. A similar result and higher color yield of anar peel dyeing on cotton were referred in the earlier literature for use of myrobalan/harda and alum double pre-mordanting [19].
Mordant concentration and dye concentration | K/S at λmx | ΔE* | ΔL* | Δa* | Δb* | ΔC* | ΔH* | BI | MI | CDI | CV% of K/S |
---|---|---|---|---|---|---|---|---|---|---|---|
(10% harda + 10% potash alum) only mordanted cotton | 1.53 | ||||||||||
Harda (H) + KAl2(SO4)2(Pa)*, overall 20% application with ratio | |||||||||||
0:100 [harda (H): KAl2(SO4)2] + 4% madder | 1.66 | 4.54 | −3.70 | 2.12 | 1.55 | 2.59 | 0.45 | 22.08 | 0.95 | 0.86 | 1.50 |
25:75 [harda (H): KAl2(SO4)2] + 4% madder | 2.53 | 2.95 | 2.55 | 0.47 | 1.39 | 1.31 | 0.67 | 19.85 | 0.36 | 2.46 | 2.32 |
50:50 [harda (H): KAl2(SO4)2] + 4% madder | 3.67 | 1.49 | 1.23 | 0.76 | 0.36 | 0.32 | 0.78 | 15.22 | 0.33 | 3.03 | 2.05 |
75:25 [harda (H): KAl2(SO4)2] + 4% madder | 3.40 | 3.49 | 3.05 | 0.91 | 1.43 | 1.66 | 0.34 | 16.34 | 0.48 | 4.26 | 4.15 |
100:0 [harda (H): KAl2(SO4)2] + 4% madder | 2.05 | 1.53 | 1.06 | 0.13 | 1.09 | 1.08 | 0.19 | 29.83 | 0.31 | 2.78 | 2.99 |
Effect of different single and double natural bio-mordants on color strength and other colour interaction parameters of cotton fabric dyed with 4% madder extract (λmax of 540 nm).
*H, harda, and Pa, potash alum. Note: K/S, ΔL*, Δa*, Δb*, ΔE*, ΔH*, ΔC*, etc. are all color parameters as per the latest CIE formula [30].
Data on color fastness properties of dyed cotton fabric samples pre-mordanted with varying types of single mordant and different ratio of double pre-mordanted samples (with overall 20–40% mordant application combining Harada and potash alum in 50:50 ratio) subsequently dyed with 4% madder extract has been reported in Table 10.
Mordant concn. Used and dyed with madder (manjistha) | Color fastness | ||||
---|---|---|---|---|---|
Washing | Light | Rubbing | |||
LOD | Staining | Dry | Wet | ||
10% harda and dyed with 4% madder | 3 | 4 | 2/3 | 4 | 3 |
10% KAl2(SO4)2 and dyed with 4% madder | 3 | 4 | 3/4 | 4 | 3 |
10% of harda +10% of KAl2(SO4)2 and dyed with 4% madder | 3–4 | 4/5 | 4 | 4 | 4 |
20% of harda +20% of KAl2(SO4)2 and dyed with 4% madder | 2/3 | 4 | 4 | 3–4 | 2/3 |
Effect of different single and double mordants on color fastness properties of madder- (manjistha/Rubia) (λmax of 540 nm) dyed cotton fabric.
It is evident from the color fastness data in Table 10 that applications of single mordant and also higher mordant concentration (above overall concentration of 20%) do not show better or higher color fastness to wash. However, light fastness appears to be independent on mordant concentration and is steadily always moderate to good to UV light exposure. Fastness to dry rubbing (crocking fastness) of the dyed samples remains relatively higher, whereas fastness to wet rubbing (crocking) becomes a bit lower irrespective of the concentration of harda and natural potash alum (mordant) used.
Moreover, there is little difference in color fastness to washing, light and rubbing for the different single mordants used, but there are some clear differences on color fastness ratings when the double mordanting system with overall 20% application of harda + natural potash alum in 50:50 ratio is used. Amongst the different combinations of double pre-mordanting systems used, 20% overall application of harda and natural potash alum (in 50:50 ratio) applied in sequence shows better color fastness rating amongst all combinations of mordant tried. This may be presumed to be due to some synergistic effects of this particular combination of natural potash alum with harda as a mordanting assistant due to additional coordinating power of chebulinic acid of harda as a mordanting assistant applied, which perhaps facilitates more number of strong and giant bigger complex formation amongst the said fibre (cotton)-mordanting assistants (harda)—metallic mordant (natural alum)—natural dye (madder) system in the presence of both myrobalan (harda) containing chebulinic acid residue and potash alum containing aluminum in combination in equal proportion. This may be noted that the application of 20% harda and 20% potash alum in combination impairs the colour fastness to washing and crocking, and hence 10% harda and 10% potash alum combination applied in sequence as a double mordant is found to be the better option in this case.
Results of the effect of different dyeing process variables such as (a) dyeing time in min; (b) dyeing temp in °C; (c) dye bath in pH; (d) dye concentration in %; and (e) salt concentration in % which have been studied to optimize the dyeing conditions for maximum and uniform color yield (in terms of K/S value) for overall application of 20% harda + KAl2(SO4)2 in 50:50 ratio pre-mordanted and dyed cotton fabric are shown in Table 11. From relevant data in Table 11, it is found that when all other variables are kept fixed, with the increase in time of dyeing (15–120 min), the K/S value initially increases up to 60-min dyeing time and then starts decreasing on further increase in dyeing time from 60 to 120 min, whereas there is hardly any change of the K/S value from that obtained in 60-min dyeing time. Thus, the K/S value is maximum for 60-min dyeing time. This may be explained by the possibility of achieving dyeing equilibrium at a medium faster rate for synergistic action of harda and potash alum both as pre-mordanting agents, and hence within 30–60 min, the dye uptake rate may be maximum for a double pre-mordanted cotton with high coordinating capacity of mordantable natural dyes like madder. However, the final dyeing rate depends on the diffusion rate (being the slowest step in dyeing operation) besides transportation, absorption, diffusion and fixation of any dye like madder/Rubia extract. There are also chances of desorption/breaking of dye-fiber-mordant complex at either higher temperature or higher dyeing time which may lead to a dropping trend above the said 60 min of dyeing time.
Dyeing conditions | K/S at λmax | ΔE* | ΔL* | Δa* | Δb* | ΔC* | ΔH* | BI | MI | CDI |
---|---|---|---|---|---|---|---|---|---|---|
10% harda and 10% KAl(SO4)2pre-mordanted cotton fabric dyed with 4% purified madder dye | 1.53 | — | — | — | — | — | — | 19.85 | — | — |
Time, min | ||||||||||
15 | 2.29 | 2.33 | −1.65 | 0.30 | 1.62 | 1.23 | 1.10 | 20.34 | 0.42 | 2.43 |
30 | 2.95 | 4.46 | −3.31 | 2.94 | 0.58 | 2.75 | −1.20 | 18.59 | 1.04 | 3.89 |
60 | 3.18 | 9.34 | −8.55 | −3.28 | −1.84 | −3.73 | 0.44 | 15.13 | 1.29 | 1.96 |
90 | 2.34 | 2.45 | −1.35 | 1.36 | 1.53 | 1.99 | 0.48 | 18.40 | 0.43 | 1.69 |
120 | 2.19 | 3.24 | −2.91 | 0.21 | 1.40 | 1.04 | 0.95 | 16.77 | 0.44 | 5.35 |
Temp °C | ||||||||||
40 | 2.01 | 3.76 | 1.42 | 0.90 | 0.05 | 0.71 | 0.56 | 18.25 | 0.71 | 4.33 |
50 | 2.21 | 5.65 | −4.35 | 3.60 | −0.20 | 3.06 | −1.91 | 17.73 | 1.39 | 4.36 |
65 | 3.04 | 4.22 | −3.38 | 2.20 | −1.22 | 0.95 | −2.33 | 21.38 | 0.90 | 3.79 |
80 | 2.10 | 2.05 | 0.72 | 0.49 | 0.59 | 0.77 | 0.02 | 24.89 | 0.19 | 4.81 |
95 | 1.81 | 2.66 | −2.05 | 1.69 | 0.06 | 1.16 | −1.24 | 22.22 | 0.57 | 5.84 |
pH | ||||||||||
6 | 2.14 | 0.88 | −0.74 | −0.21 | 0.43 | 0.14 | 0.45 | 19.04 | 0.14 | 9.58 |
8 | 2.35 | 1.51 | −1.14 | 0.56 | 0.81 | 0.96 | 0.21 | 18.28 | 0.18 | 4.81 |
10 | 2.58 | 1.12 | −1.34 | 0.37 | 0.97 | 0.24 | 0.38 | 16.37 | 0.15 | 8.24 |
12 | 2.96 | 2.89 | −0.30 | −0.71 | −0.44 | −0.81 | 0.21 | 18.50 | 0.27 | 6.17 |
14 | 2.74 | 2.88 | −2.84 | 0.38 | 0.36 | 0.52 | 0.40 | 16.16 | 0.27 | 4.31 |
MLR | ||||||||||
1:10 | 2.82 | 2.27 | −1.74 | −0.01 | 1.45 | 1.09 | 0.97 | 22.70 | 0.32 | 5.39 |
1:20 | 2.80 | 2.05 | −0.72 | 0.49 | 0.59 | 0.77 | 0.02 | 24.89 | 0.19 | 4.81 |
1:30 | 2.15 | 3.59 | −2.17 | 2.67 | 1.02 | 2.59 | −1.23 | 21.22 | 0.87 | 4.10 |
1:40 | 2.09 | 5.01 | −4.21 | 2.58 | 0.84 | 2.40 | −1.27 | 21.06 | 0.93 | 2.45 |
1:50 | 2.22 | 1.83 | −1.66 | 0.75 | 0.17 | 0.67 | −0.38 | 19.61 | 0.28 | 2.39 |
Dye concn.,% | ||||||||||
3 | 2.60 | 1.27 | 0.20 | −0.06 | 1.25 | 0.65 | 1.07 | 16.96 | 0.23 | 3.79 |
4 | 2.82 | 5.45 | −4.36 | 3.24 | 0.38 | 2.90 | −1.50 | 15.78 | 1.16 | 3.44 |
5 | 2.57 | 2.93 | −1.81 | 1.91 | 1.27 | 2.30 | −0.08 | 17.55 | 0.55 | 2.26 |
6 | 2.61 | 2.19 | −1.64 | 1.33 | 0.60 | 1.42 | −0.29 | 17.61 | 0.52 | 0.17 |
7 | 2.69 | 4.71 | −3.66 | 2.86 | 0.77 | 2.81 | −0.95 | 16.41 | 0.98 | 4.23 |
Salt concn., gpl | ||||||||||
5 | 3.12 | 3.31 | −2.48 | 1.94 | 1.02 | 2.18 | −0.17 | 13.22 | 0.70 | 2.99 |
10 | 3.37 | 4.31 | −3.69 | 2.15 | 0.63 | 2.14 | −0.66 | 13.36 | 0.83 | 3.24 |
15 | 3.22 | 5.45 | −5.01 | 2.13 | 0.26 | 1.93 | −.093 | 11.74 | 0.94 | 4.69 |
20 | 3.13 | 0.75 | −0.72 | 0.19 | 0.07 | 0.20 | −0.04 | 12.45 | 0.11 | 2.78 |
Color strength, brightness index (BI), metamerism index (MI), CDI value and related color parameter for variation of dyeing process variables* for dyeing of 10% Harda and 10% KAl(SO4)2 pre-mordanted cotton fabric subsequently dyed with 4% madder/Rubia.
*Values in bold indicate the optimum values considered while studying the effect of process variables of dyeing of madder. When one dyeing parameter was varied, other dyeing parameters were kept constant, say for MLR variation of 1:10–1:50, dye (madder) concn. Was 4%, time was 60 min, temp was 65°C, pH was 12, and salt concn. Was 10 gpl; similarly, for time variation of 15–120 min, MLR was 1:20, dye (madder) concn. Was 4%, time was 60 min, temp was 65°C, pH was 12, and salt concn. Was 10 gpl; for temperature variation of 40–95°C, MLR was 1:20, dye (madder) concn. Was 4%, time was 60 min, salt concn. Was 10 gpl, and pH was 12, and for pH variation of 6–14, MLR was 1:20, dye (madder) concn. Was 4%, time was 60 min, salt concn. Was 10 gpl, and temp was 65°C; for salt concn. Variation of 5–20, MLR was 1:20, dye (madder) concn. Was 4%, time was 60 min, temp was 65°C, and pH was 12. λ max for K/S data of madder was taken as 540 nm from UV-VIS scan in all cases. Note: K/S, ΔL*, Δa*, Δb*, ΔE*, ΔH*, ΔC*, etc. are all color parameters as per the latest CIE formula [30].
For variation of dyeing temperature, on increase of the dyeing temperature (40–95°C), keeping other variables constant, the surface color strength (K/S values) is found to show a slow increase to a small extent from 40 to 65°C whereafter it almost remains same or at par up to 80°C, after which there is a further decrease beyond 80°C up to 95°C. An increase in temperature of dyeing inevitably supplies more energy for the transportation of dye molecules, thus facilitating the higher rate of dye sorption and diffusion up to 65°C, and thereafter this dyeing rate does not alter much even after increasing temperature up to 95°C, i.e. the desorption starts at relatively high temperature above 80°C and maybe one of the components of madder starts degrading above 74°C and the color value, i.e. K/S value, decreases noticeably. However, dyeing of cotton with madder extract at warm conditions, i.e. at 50–65°C, is considered to be best suited and cannot be excluded fully for the decentralized sector for energy-saving purpose.
The corresponding data in Table 11 show almost a similar level of dye uptake in terms of surface color strength (K/S value) with the variation of dye concentration (keeping other variables constant) for purified madder dye concentration from 3 to 7%, showing a maximum K/S value for 4% dye concentration of purified madder extract. For the variation of pH from 6 to 14 (keeping other variables constant), the surface color strength (K/S value) starts increasing slowly showing a maximum K/S value at pH 12, after which color value further reduces. Thus, pH 12 may be considered optimum, though here pH is to be treated as a critical variable for relatively higher differences of color difference index (CDI) values (showing higher differences of maximum CDI and minimum CDI values amongst the results of varying pH of dye bath). However, considering the corresponding color fastness data, as reflected in Table 12, it is further clear that pH 12 renders a better overall balance of all types of color fastness data and shows even sometimes better than that obtained at pH 14. So, pH 12 is considered as the optimum value for this dyeing in this case of cotton fiber-(alum + harda) mordant-dye (madder/Rubia) system. It may be fact that at pH 12, as it is found to be alkaline, there are higher chances of ionization of phenoxy hydroxyl groups of color component of madder/Rubia (containing alizarin, manjisthin and purpurin) and hence provide better chances of complex formation with mordant like natural alum and mordanting assistant like harda forming a giant coordinated complex amongst them for better fixation and higher anchoring by formation of the said fibre-mordanting assistant + mordant-dye system in this case.
Varying dyeing conditions 10% harda + 10% potash alum pre-mordanted cotton fabric dyed with 4% purified madder dye | Overall color fastness properties | ||||
---|---|---|---|---|---|
Washing colour fastness at 50°C | Light | Rubbing | |||
Loss of depth | Staining | Dry | Wet | ||
Varying parameters of dyeing | |||||
Time, min | |||||
15 | 3/4 | 5 | 3 | 4/5 | 4 |
30 | 3/4 | 4 | 3 | 4 | 4 |
60 | 3/4 | 4/5 | 3/4 | 4/5 | 4 |
90 | 2/3 | 4 | 4 | 4/5 | 4 |
120 | 3 | 4 | 4 | 4/5 | 4 |
Temp °C | |||||
40 | 2 | 4/5 | 3 | 4/5 | 4 |
50 | 2/3 | 4/5 | 3 | 4/5 | 3 |
65 | 3/4 | 5 | 3/4 | 5 | 4/5 |
80 | 2/3 | 5 | 3 | 4/5 | 4 |
95 | 1/2 | 4/5 | 3/4 | 4/5 | 4 |
pH | |||||
6 | 2/3 | 4 | 3 | 4/5 | 3/4 |
8 | 2/3 | 4 | 3 | 4/5 | 3/4 |
10 | 1/2 | 4/5 | 3 | 4/5 | 3/4 |
12 | 3/4 | 4/5 | 3/4 | 4/5 | 3/4 |
14 | 2/3 | 5 | 3 | 4/5 | 3/4 |
MLR | |||||
1:10 | 3 | 4/5 | 3/4 | 4/5 | 4 |
1:20 | 3–4 | 4/5 | 3/4 | 4/5 | 4 |
1:30 | 3 | 4 | 3 | 4/5 | 4 |
1:40 | 3 | 4 | 3 | 4 | 3/4 |
1:50 | 2 | 4/5 | 3 | 4/5 | 4 |
Dye concn.,% | |||||
3 | 2 | 4 | 3 | 4 | 4 |
4 | 3–4 | 5 | 3/4 | 4/5 | 3/4 |
5 | 3 | 4/5 | 3 | 4/5 | 3/4 |
6 | 2/3 | 4/5 | 3 | 4/5 | 3/4 |
7 | 2/3 | 4/5 | 3/4 | 4/5 | 3/4 |
Salt concn., gpl | |||||
5 | 3 | 5 | 3/4 | 3 | 4/5 |
10 | 3–4 | 5 | 3/4 | 4/5 | 4 |
15 | 3/4 | 4/5 | 3 | 3/4 | 4/5 |
20 | 2/3 | 4/5 | 3 | 3/4 | 3 |
Color fastness data against the variation of dyeing process variables* for dyeing 10% Harda +10% potash alum pre-mordanted cotton fabric subsequently dyed with 4% madder/Rubia.
*When one dyeing parameter was varied, other dyeing parameters were kept constant, say for MLR variation of 1:10–1:50, dye (madder) concn. Was 4%, time was 60 min, temp was 65°C, pH was 12, and salt concn. Was 10 gpl; similarly, for time variation of 15–120 min, MLR was 1:20, dye (madder) concn. Was 4%, time was 60 min, temp was 65°C, pH was 12, and salt concn. Was 10 gpl; for temperature variation of 40–95°C, MLR was 1:20, dye (madder) concn. Was 4%, time was 60 min, salt concn. Was 10 gpl, and pH was 12, and for pH variation of 6–14, MLR was 1:20, dye (madder) concn. Was 4%, time was 60 min, salt concn. Was 10 gpl, and temp was 65°C; for salt concn. Variation of 5–20, MLR was 1:20, dye (madder) concn. Was 4%, time was 60 min, temp was 65°C, and pH was 12.
Bold values are optimum results.
Keeping other variables constant, with the variation in MLR from 1:10 to 1:50 (Table 11), the K/S value is maximum for MLR at 1:10, and then there is a slow decrease after MLR 1:20, after which the K/S value continues decreasing slowly in small quantum with further increase for MLR at 1:50. Though MLR 1:10 shows the highest K/S value as compared to any other MLR used, MLR 1:20 gives the same value of K/S and better wash and other color fastness results. Hence the optimum MLR may considered to be 1:20 instead of 1:10. From color fastness data in Table 12, it is indicated that except wash fastness results for MLR 1:50, all other MLR used show almost medium to good overall color fastness data. However, amongst all these, overall color fastness data for all types of color fastness results are found to be quiet acceptable for MLR 1:10 and 1:20 only. Thus, considering both color yield and color fastness data, MLR 1:20 gives a better balance having a more uniform dyeing and hence may be considered as optimum dyeing conditions with respect to MLR.
The addition of an electrolyte (common salt) to the dyeing liquor expectedly increases the exhaustion of the dyeing case of most of the anionizable dyes. Common salt (electrolyte) is dissolved completely in the aqueous liquor in the dye bath at a specific temperature of dyeing, thereby positive sodium ion is attracted to –ve cellulosic surface in water and neutralizes the –ve charge of cellulose and thereby anionic natural dye ions are able to be attracted to cellulose increasing exhaustion. But excessive amount of electrolyte/salt above a certain limit, causes a retardation effect in the dye absorption vis-à-vis color yield and renders lower color depth. From the relevant data in Table 11, a similar trend is observed that with the increase in salt/electrolyte concentration from 5 to 20 gpl, the color yield in terms of K/S value is increased for the application of 5–10% salt concentration and starts decreasing for use above 15% salt concentration. Moreover comparing overall color fastness properties for the corresponding part, the overall round color fastness properties are found best for 10% salt concentrations, and fastness results for use of 15% salt concentration are a bit inferior. Considering all the above matter, the optimum concentration of common salt for dyeing cotton fabric with madder is selected to be 10 gpl.
Thus, the observed optimum conditions of dyeing of the double pre-mordanted with 10% concentration of harda and 10% concentration of natural potash alum in sequence for bleached finer cotton fabric with aqueous extract of purified madder (manjistha/Rubia) are as follows: dyeing time, 60 min; dyeing temperature, 65°C; MLR, 1:20; pH, at 12; dye concentration, 4% (on weight percentage of dried purified color extract powder); and common salt concn., 10 gpl, considered as optimum.
Table 11 also shows the effects of different process variables on K/S values and other latest CIE color measurement parameters [30], including total color difference (ΔE*), change in hue (ΔH*), change in chroma (ΔC*), general MI, BI and CDI values [13]. It is interesting to observe that amongst the varying dyeing conditions (time, temperature, pH, MLR, mordant, dye concentration and salt concentration), the most important and predominating variables are identified as pH of the dye bath, dyeing time and dye concentration. Therefore, for uniform dyeing using madder (manjistha/Rubia) extract for cotton fabric, special care is to be taken for the control of pH, dyeing time and concentration of dye solution of madder (manjistha/rubia).
The said other color parameters like ∆E*, ∆L*, ∆a* and ∆b* indicate the variation in color strength and related parameters for varying dyeing conditions in each case, as compared to standard undyed pre-mordanted control cotton fabric. Changes in hue (ΔH*), in most of the cases, are found to be small negative values (Table 11), and in very few cases, there are small positive values, indicating that there is a minor change in the predominating hue in each case. However, the maximum ∆H* value is observed in the case of the variation in temperature from 40 to 95°C which further indicates the high sensitivity of color strength parameter for this particular natural dye for the variation in temperature of dyeing, indicating it as also a critical parameter. The brightness index of dyed products depends on reflectance value of the dye and its orientation along the fiber axis after fixation. However, interestingly it may be noted that at lower pH of 6–10, lower concentration of dye (30–40%) and lower temperature (50–65°C), the reduction in BI values is much lower than that observed in other conditions of dyeing. Expectedly the reduction in brightness index is found to be higher when the application of dye concentration and/or dyeing temperature are higher, due to disorientation of dye molecules during fixation, for either use of higher concentration of dye molecules or higher dyeing temperature. Results of general MI indicates the metameric effect on the madder- (manjistha/rubia) dyed cotton fabric for different conditions of dyeing. In all these cases, the MI varies from 0.11 to 1.39 (Table 11) and it is observed that these MI data are not much widely dispersed within a particular condition being varied, but varies to a noticeable degree from one condition to other, indicating its potential metameric nature for varying one condition to the other. Therefore, use of standardization of conditions of dyeing is a must to minimize metamerism for achieving least metameric dyed products like fibre-mordant-dye system for natural dyeing of cotton with madder/rubia.
Moreover, the ecotoxicology property of madder is available in the literature that the hepato-protective [31] activity of an aqueous-methanol extract of Rubia cordifolia/Rubia tinctorum was investigated earlier against acetaminophen and CCL4-induced damage. Acetaminophen produced 100% mortality at a dose of 1 g/K in mice, while pre-treatment of animals with plant extract reduced the death rate to 30%, proving its ecocompatibility. This is just one example by how after a series of lab experiments, dyeing process parameters are standardized to ensure reproducibility, dye uniformity, etc. and critical dyeing process variables are identified, but for the application of a specific natural dye to any specific textiles, this standardized process parameters are to be made available for each dye-fiber combination separately to the dyers as ready-made guide like synthetic dye application manuals supplied by dye manufacturers or suppliers.
Similarly, it has also been revealed from our earlier lab study that the optimized conditions for dyeing of 15% overall harda + alum (50:50) double pre-mordanted cotton fabric with tesu as natural dye are: dye concentration of 30% (aqueous extract based on the weight of dry powder of natural tesu flower petal (Butea monosperma or commonly known as palash or flame of the forest)), pH of 12, MLR of 1:30, time of 60 min for dyeing and 90 min for simultaneous dyeing and finishing and dyeing temperature of 90°C with salt concentration of 10 gpl (though the detailed study and results of the optimization of conditions of dyeing process variables for tesu as natural dye applied on the said 15% overall application of alum + harda pre-mordanted cotton are not mentioned here considering its duplication).
Few studies on UV-protective and antibacterial characteristics of some natural materials including few natural dye extracts are sparingly reported [32, 33, 34, 35, 36, 37, 38, 39, 40, 41]. Hence, an attempt for such natural dyeing-cum-finishing is studied in the present work as reported below.
The antibacterial characteristics of many natural resource materials are explored by many researchers [21, 22, 35, 36, 37, 38, 39, 40, 41], which include the antibacterial property of eucalyptus, curcumin, banana peel and few natural dyes like catechu, rheum emodi, etc. All the required natural resource materials and tesu as natural dye were obtained from the M/s AMA Herbals Lab Pvt. Ltd., Lucknow, India. A recent accounting of the present status and advanced studies on natural dyeing and natural finishing of textiles including modern techniques of dyeing processes and analyses in different angles have been compiled comprehensively by Vankar [42]. In this part of report, eucalyptus leaf extract has been used as a natural antibacterial agent applied on tesu-dyed cotton. Effects of few different post-treatments on cotton fabric dyed with aqueous extract of 30% (based on the weight of dry powder of natural solid source) tesu flower petal (Butea monosperma or commonly known as flame of the forest) with 10% of both aqueous and MeOH extracts of eucalyptus leaves by a pad-dry-cure technique (by a two-dip-two-nip padding process, followed by drying at 100°C for 15 min and curing at 120°C for 3 min) after dyeing or by simultaneous dyeing and finishing process with or without suitable catalyst system (like citric acid, 5 gpl). mainly for improving the antimicrobial properties of tesu-dyed cotton fabric after pre-mordanting with 15% overall harda + alum (50:50) have been discussed.
For simultaneous dyeing and finishing, predetermined percentages of eucalyptus leaf extract along with citric acid were added to the dye bath, and dyeing-cum-finishing was carried out simultaneously at 90°C for 90 min. Relevant results in the change in surface color strength and other related parameters along with fastness properties are tabulated in Tables 13 and 14.
Treatments | K/S | ΔE | ΔL | Δa | Δb | ΔC | ΔH | BI | MI | CDI |
---|---|---|---|---|---|---|---|---|---|---|
Standard bleached cotton control fabric | 0.01 | 92.11 | 0.91 | — | ||||||
15% overall application of harda + alum (50:50) (no dyeing) | 0.16 | 6.12 | −1.15 | −0.91 | 5.85 | −0.044 | −5.92 | 44.65 | 3.43 | — |
15% harda + alum (50:50) and 30% tesu aqueous extract dyed | 2.65 | 17.77 | −4.58 | −1.062 | 17.13 | 11.20 | −13.01 | 15.93 | 7.26 | 2.84 |
Post-treatment with 10% extract of eucalyptus leaves on 30% tesu aqueous extract-dyed cotton after pre-mordanted with 15% harda + alum (50:50) pre-mordanted in sequence | ||||||||||
(10%) Eucalyptus leaf aqueous extract + citric acid (5 gpl) | 5.49 | 15.40 | 3.18 | −0.727 | 4.31 | 4.37 | 11.05 | 18.61 | 6.44 | 5.90 |
10% Eucalyptus leaf MeOH extract + citric acid (5gpl) | 7.49 | 20.40 | 3.19 | −0.824 | 4.11 | 5.33 | 12.00 | 19.61 | 6.75 | 6.80 |
Post-treatment with 10% extract of eucalyptus leaves on 30% tesu aqueous extract-dyed cotton after pre-mordanted with 15% alum pre-mordanted cotton fabric | ||||||||||
10% Eucalyptus leaf MeOH extract + citric acid (5gpl) (15% alum pre-mordanted) | 4.49 | 14.60 | 3.00 | −0.676 | 5.36 | 5.71 | 11.70 | 16.33 | 6.02 | 4.97 |
Simultaneous dyeing and finishing with 15% harda + alum (50:50) pre-mordanted cotton fabric with extract of tesu and eucalyptus leaves with citric acid | ||||||||||
Tesu (30%) extract + eucalyptus leaf aqueous extract (10%) + citric acid (5 gpl) | 4.85 | 14.42 | 2.38 | −0.52 | 3.68 | 3.72 | 12.01 | 17.56 | 5.61 | 8.29 |
Effect of post-treatment with eucalyptus leaf extract by a pad-dry technique and by simultaneous dyeing and finishing technique using a suitable catalyst for natural dyeing and finishing of cotton fabric with tesu extract after pre-mordanting with 15% overall dosage of Harda + alum (50:50).
Treatments | Wash fastness | Rubbing fastness | Light fastness | |
---|---|---|---|---|
Variation in dyeing and finishing treatments | LOD | Cotton (staining) | Dry | |
15% harda + alum (50:50) and 30% tesu aqueous extract dyed | 4 | 3–4 | 4–5 | 3 |
Post-treatment with 10% extract of eucalyptus leaves on 30% tesu aqueous extract-dyed cotton after pre-mordanted with 15% harda + alum (50:50) pre-mordanted in sequence | ||||
(10%) eucalyptus leaf aqueous extract + citric acid (5 gpl) | 4–5 | 4–5 | 4 | 4 |
10% eucalyptus leaf MeOH extract + citric acid (5gpl) | 4–5 | 4 | 4 | 4 |
Post-treatment with 10% extract of eucalyptus leaves on 30% tesu aqueous extract-dyed cotton after pre-mordanted with 15% alum pre-mordanted cotton fabric | ||||
10% eucalyptus leaf MeOH extract + citric acid (5gpl) | 3–4 | 3–4 | 3 | 3 |
Simultaneous dyeing and finishing of cotton fabric dyed with 30% tesu aqueous extract and 10% eucalyptus aqueous extract on 15% harda + alum (50:50) pre-mordanted cotton fabric | ||||
Tesu (30%) extract +10% eucalyptus leaf aqueous extract + citric acid (5 gpl) | 4–5 | 4–5 | 4 | 4 |
Color fastness to washing, rubbing, light after post-treatment of tesu-dyed double pre-mordanted cotton fabric with eucalyptus as well as simultaneous dyeing and finishing.
In Table 13, relevant data indicates that when a post-treatment of eucalyptus leaf extract is carried out in the presence of a suitable catalyst (citric acid) on the above said double pre-mordanted and 30% tesu-dyed cotton fabric by a pad-dry-cure technique, its color strength value is found to be higher as compared to the simultaneous dyeing and finishing technique with the same agents/compounds. Also the fabric samples post-treated with 10% of both aqueous and MeOH extracts of eucalyptus leaves by a pad-dry-cure technique are found to be much yellower and darker in case of similar post-treated fabric produced by the simultaneous natural dyeing and finishing process.
However, taking the color fastness results into consideration, data in Table 14 indicate that light fastness rating obtained for simultaneous natural dyeing and finishing process is slightly better than the similar sample produced by natural dyeing followed by separate finishing process by a pad-dry-cure technique of separate post-finishing of tesu-dyed cotton fabric using 10% extract of eucalyptus, as the natural finishing agent. The washing and rubbing fastness obtained are more or less found to be similar between the two processes. Moderate fastness to washing of only 30% tesu natural dyed cotton can be attributed to the fiber-metal-tannin-dye complex formation between color components of tesu (containing butrin, butein, flavonoids) and alum as a metallic mordant along with harda (containing chebulinic acid) as a mordanting assistant. Darker shades are obtained after 10% eucalyptus extract post-treatment as a finishing treatment on tesu-dyed cotton fabric, which is considered to be due to the addition of active constituents of eucalyptus containing tannins, polyphenols and an active coloring substance called quercetin which has the brightest yellow shade. Hence, in case of post-finishing treatment by a pad-dry-cure technique, the K/S value is found to be higher than that of simultaneous dyeing-finishing treatment owing to the of formation of giant bigger molecule size of complex formed with eucalyptus component in the presence of citric acid used as a catalyst during the finishing process. In case of simultaneous process, a bigger molecular size of citric acid preferably starts crosslinking with cellulose of cotton reducing and preventing an effective fiber-mordant-dye complex formation with the cotton fabric, resulting in a less color yield.
Ten percent eucalyptus post-treatment on 30% aqueous extracted tesu-dyed [after the said double pre-mordanted with 15% overall mordant application with harda and alum (50:50)] and 10% eucalyptus post-treated or finished cotton fabric as well as simultaneous dyeing and finishing (adding 30% tesu and 10% eucalyptus and 5 gpl citric acid and heated at 90°C for 90 min) of the said pre-mordanted cotton fabric were subjected to the standard antimicrobial test as per the American Association of Textile Chemists and Colorists (AATCC)-100–2012 method in terms of bacterial reduction (%) as shown in Table 15.
Treatments | Bacterial reduction (%) as per AATCC-100-2012 | |
---|---|---|
Variation in dyeing and finishing treatments | Klebsiella pneumoniae: ATCC 4352 (Gram-negative bacteria) | Staphylococcus aureus: ATCC 6538 (Gram-positive bacteria) |
Standard bleached cotton control fabric | No reduction | No reduction |
15% overall application of harda + alum (50:50) (no dyeing) | 99.98 | 99.43 |
15% [harda + alum (50:50)] and 30% tesu aqueous extract dyed | No reduction | 68.88 |
Post-treatment with 10% extract of eucalyptus leaves on 30% tesu aqueous extract-dyed cotton after pre-mordanted with 15% harda + alum (50:50) pre-mordanted in sequence | ||
10% eucalyptus leaf aqueous extract + citric acid (5 gpl) | No reduction | 93.01 |
10% eucalyptus leaf MeOH extract + citric acid (5 gpl) | 99.97 | 99.99 |
Post-treatment with 10% extract of eucalyptus leaves on 30% tesu aqueous extract-dyed cotton after pre-mordanted with 15% alum pre-mordanted cotton fabric | ||
10% MeOH extract of eucalyptus +citric acid (5 gpl) | 99.79 | 99.52 |
Simultaneous dyeing and finishing of cotton fabric dyed with 30% tesu aqueous extract and 10% eucalyptus aqueous extract on 15% harda + alum (50:50) pre-mordanted cotton fabric | ||
Tesu (30%) extract + eucalyptus leaves aqueous extract (10%) + citric acid (5 gpl) | No reduction | 54.02 |
Results of the antimicrobial test as per AATCC-100-2012 for pre-mordanted 30% tesu extract-dyed and eucalyptus extract finished cotton fabric after pre-mordanted with 15% total application of Harda + alum (50:50).
As per the results shown in Table 15, for both Klebsiella pneumoniae and Staphylococcus aureus bacteria, there is 99% reduction of bacterial growth on cotton fabric for double pre-mordanted with alum and harda, i.e. after 15% overall application of harda + alum (50:50) only without any dyeing (no dyeing). This can be attributed to the presence of the natural alum (also known as Fitkari) as mordant, which contributes to the prevention of bacterial growth. However, a remarkable increase of bacterium can be observed when mordanted fabrics were subsequently dyed with 30% tesu extract as natural dye, from which it can be concluded that after dyeing with tesu extract, as potash alum is ionized during dyeing and all aluminium present in alum are consumed for complexion of fibre-mordant-dye complex formation and hence, prevention of bacterial growth by alum is reduced and antibacterial property is reduced partly to Gram-positive bacteria (showing results of 68.88% or approx. 69% bacterial reduction only) and reduced fully to Gram-negative bacteria (showing results –No bacterial reduction at all). However, when the said double pre-mordanted and 30% tesu extract-dyed cotton fabric samples is post-treated or finished with 10% aqueous extract of eucalyptus with citric acid catalyst, there is no bacterial reduction against Gram-negative bacteria (showing results—no bacterial reduction at all), but shows 93.01 bacterial reduction against Gram-positive bacteria. While when a similar pre-treated and tesu-dyed sample of cotton fabric is post-treated with 10% MeOH extract (instead of an aqueous extract of eucalyptus leaves as antibacterial natural finishing agents), it shows the highest bacterial reduction results for against both Gram-positive bacteria (showing a bacterial reduction of 99.99%) and Gram-negative bacteria (showing a bacterial reduction of 99.97%).
Simultaneous dyeing and finishing show antibacterial test results in much similar fashion or quite similar to the only pre-mordanted and subsequently 30% tesu-dyed cotton fabric samples, showing there is no reduction in bacterial growth against Gram-negative bacteria (showing results of no bacterial reduction at all) and antibacterial property is reduced partly to Gram-positive bacteria (showing results of 54.02% or approx. 54% bacterial reduction only). But only 15% alum pre-mordanted (without harda) and 30% tesu extract-dyed cotton fabric sample, post-finishing application of 10% MeOH extract of eucalyptus leaves render it highly antibacterial in nature showing almost at par or similar level of bacterial reduction results that obtained for said 15% application of harda + alum (50:50) same fabric samples dyed with tesu and post finished with 10% MeOH extract of eucalyptus, for both against Gram-positive bacteria (showing bacterial reduction of 99.79%) and Gram-negative bacteria (showing bacterial reduction of 99.52%).
All corresponding pictures of petri plates for the said antimicrobial tests as per AATCC-100-2012 against Gram-negative and Gram-positive bacteria are also given in Figure 10 with petri plate numbers being 1–7, where 1A–7A are samples incubated for 0 h, 1B–7B are samples incubated for 24 h with Gram-negative bacteria and 1C–7C are samples incubated after 24 h with Gram-positive bacteria, against the corresponding samples; the photographs of petri plates are almost matching with bacterial reduction (%) results shown in Table 15, which are self-explanatory.
Pictures of petri plates for antimicrobial test as per AATCC-100-2012 against gram-negative and gram-positive bacteria.
Hence, in case of simultaneous dyeing and finishing, the antibacterial property results obtained are not fully satisfactory as compared to the said double pre-mordanted and tesu dyed and post-treated/finished with 10% aqueous extract of eucalyptus, but that effect of antibacterial property is highly enhanced if, the same percentage, i.e. 10% MeOH alcohol-extracted eucalyptus leaves, is applied instead of its aqueous extract. So, in order to improve the fullest/highest bacterial reduction finish with a natural agent, the said double pre-mordanted cotton fabric after dyeing with tesu natural dye, the dyed fabric is to be finished separately by pad a dry-cure technique using 10% MeOH alcoholic extracted eucalyptus leaves for good results in the reduction of bacterial growth for both Gram-positive and Gram-negative bacteria. In case of cotton fabrics dyed with methanol (alcohol) aided extracted eucalyptus leaves post-treatment, they give a very darker color depth/shade as well as excellent antimicrobial finishing properties.
Few reports are available in the literature on the role of natural dyes and other natural resource materials, when applied on textiles for UV-protective properties [19, 32, 33, 34, 43]. Finishing of textiles with vegetable oil is also reported in the literature [44].
But nowadays, UV protection in textiles has become also equally important for the protection of the human skin. Considering this in view, reddening of the skin under any barrier like textiles or other materials can be judged by UPF or sun protection factor (SPF) values. The classification of performance-based UPF value grading/rating is given below.
Performance-related UPF rating and classification | |
---|---|
UP F value | UV protection rating/category |
15–24 | Good protection |
25–40 | Very good protection |
40–50+ | Excellent protection |
So, as a case study, UV-protective finish on 30% aqueous extract of tesu-dyed cotton fabric (pre-mordanted with 15% overall application of harda + alum (50:50)) was imparted as a finishing post-treatment by a pad-dry-cure technique with aqueous extract of eucalyptus, MeOH extract of eucalyptus and emulsified coconut oil in the presence of citric acid as a catalyst for finishing with these two types of natural UV absorber for imparting UV-protective finish. Relevant data of UV protection factor values before and after the said treatments are measured as per AATCC-183-2010/2014 and are tabulated in Table 16. Double pre-mordanted with 15% overall application of harda + alum (50:50) and 30% tesu aqueous extract-dyed cotton fabric samples are when post treated with both aqueous or alcoholic extract of eucalyptus leaves and also with emulsified coconut oil in presence of citric acid as catalyst (in all the cases), UV protection performance are much enhanced as compared to said double pre-mordanted and tesu-dyed cotton fabric (without any post-treatment). Relevant results of UPF values from Table 16 indicate that best result, i.e. UPF value of 40, is obtained when the said double pre-mordanted cotton fabrics dyed with tesu extract (as natural dye) is finished with MeOH alcoholic 10% extract of eucalyptus leaves in the presence of citric acid (5 gpl) by a pad-dry-cure technique as compared to UPF value obtained as 30 for post-treatment with equal dosages of emulsified 10% coconut oil in the presence of citric acid (5 gpl) under comparable conditions of treatment. However, when cotton fabrics are subjected to simultaneous dyeing and finishing process with the said two types of natural UV-protective agents (emulsified coconut oil and aqueous extract of eucalyptus leaves applied simultaneously in dye bath), the said enhancement of UPF values for simultaneous dyeing and finishing process are much less showing a UPF values 20 for emulsified coconut oil and UPF value is 25 eucalyptus leaves aqueous extract, i.e. UPF values in case of simultaneous dyeing and finishing treatment are not shown to be as high as it shows by sequential post-treatment process by pad-dry-cure process in both the cases respectively. UPF values of 15–24/25 are considered to be moderate to good protection, and hence UPF values 20 and 25 in these two cases of simultaneous dyeing and finishing using either emulsified coconut oil and eucalyptus leaves aqueous extract as natural finishing agents applied simultaneously in the dye bath can be considered to provide a moderate to good UV protection, but not as good as the UPF value of 40 obtained for post-treatment with MeOH extracted eucalyptus leaves by a pad-dry-cure process on the said double pre-mordanted with 15% overall application of harda + alum (50:50) and 30% tesu aqueous extract-dyed cotton fabric samples. While without any after-treatment or simultaneous treatment with eucalyptus or coconut oil, 15% overall harda + alum (50:50) and 30% tesu aqueous extract-dyed cotton fabric sample shows a UPF value of 12 only as compared to a UPF value of 5 for the standard bleached control cotton fabric (un-mordanted and undyed).
Samples/type of post-treatments with UV absorbers | UPF | UV-A (%) | UV-B (%) |
---|---|---|---|
Standard bleached cotton control fabric (un-mordanted and undyed cotton) | 5 | 29.67 | 22.10 |
15% overall application of harda + alum (50:50) (no dyeing) | 10 | 19.56 | 11.01 |
15% [harda + alum (50:50)] and 30% tesu aqueous extract dyed | 12 | 10.15 | 7.89 |
Post-treatment with 10% extract of eucalyptus leaves and 10% coconut oil with citric acid as a catalyst on 30% tesu aqueous extract-dyed cotton after pre-mordanted with 15% harda + alum (50:50) pre-mordanted cotton fabric | |||
10% coconut oil + citric acid (5 gpl) post-treatment | 30 | 2.76 | 2.02 |
10% eucalyptus leaves aqueous extract + citric acid (5 gpl) | 25 | 4.16 | 3.60 |
10% eucalyptus leaves alcoholic (MeOH) extract + citric acid (5 gpl) | 40 | 2.08 | 1.81 |
Post-treatment with 10% extract of eucalyptus leaves on 30% tesu aqueous extract-dyed cotton after pre-mordanted with only 15% alum single pre-mordanted cotton fabric | |||
10% eucalyptus leaf alcoholic (MeOH) extract +citric acid (5 gpl) | 30 | 2.66 | 2.89 |
10% coconut oil + citric acid (5 gpl) | 25 | 5.37 | 8.22 |
Simultaneous dyeing and finishing of cotton fabric dyed with 30% tesu aqueous extract and 10% eucalyptus leaf aqueous extract or 10% coconut oil emulsion on 15% harda + alum (50:50) pre-mordanted cotton fabric | |||
Tesu (30%) extract + eucalyptus aqueous extract (10%) + citric acid (5 gpl) | 25 | 4.49 | 4.56 |
Tesu (30%) + coconut oil (10%) + citric acid (5 gpl) | 20 | 3.94 | 6.08 |
Result of UPF test as per AATCC-183-2010 for 15% Harda + alum (50:50) pre-mordanted or only 15% alum pre-mordanted cotton fabric dyed with 30% aqueous extract of tesu and post-treatment with natural UV absorbers (aqueous and alcoholic (MeOH) extract of eucalyptus leaves and coconut oil).
Thus, according to the data in Table 16, cotton samples treated with methanol-extracted eucalyptus leaves post-treatment by a pad-dry-cure system provide an excellent UV protection factor against exposure to ultraviolet rays since their UPF value is 40, which lies in the range of UPF category between 40 and 50.
However, when an emulsified coconut oil is treated in the presence of citric acid, it is hydrolysed forming lauric acid (approx. 46–47% content) and α-tocopherol. So during post curing of cotton fabric treated in the presence of citric acid, the hydrolysed emulsified coconut oil (10%), possibly is attached by reaction of –COOH group of lauric acid with hydroxyl group of cellulose forming ester linkage and possible also helps to attach α-tocopherol forming an ether linkage by reaction between hydroxyl group of α-tocopherol and hydroxyl group of cotton cellulose under heat (curing) and acidic catalyst (citric acid). The attachment of eucalyptus to cotton is not yet referenced in any current research, which needs to be further explored by research in this field. However, from compositional analysis, it is known that essence oil parts of eucalyptus contain volatile chemical constituents in MeOH extract of the eucalyptus leaf having 1,8-cineole, benzene, nerolidol, limonene, alpha-pinene and beta-pinene, which can participate in crosslinking with cellulosic-OH groups in the presence of citric acid and heat showing a better result for protecting bacterial growth and protection against UV rays also, while any type of extract of eucalyptus contain eucalyptol, alpha-pinene, beta-pinene, alpha-phellandrene, gamma-terpinene, caffeic acid, linaool, geraniol and thymol, which are strongly responsible for reducing and blocking the bacterial growth as well. Thus, the eucalyptus leaves MeOH extract can be used as a natural resource-based multiple finishing agent for textiles.
The important scientific and technological aspects of natural dyeing on cotton, jute and silk fabrics in terms of extraction and purification, characterization of purified extracted natural dyes by different scientific and instrumental analyses, case studies on the effect of use of different bio-mordanting on color strength, case studies on the standardization of dyeing process variables for optimizing dyeing conditions to get reproducible shades, etc. have led to the generation of scientific ways and means for practising a precise technological control during such processing with variable natural materials, over the traditional and conventional artisan-based natural dyeing processes of textiles.
Similarly the worldwide current research interest on natural resources has improved knowledge of concern textile dyers and other related persons on the use of plant-based bio-mordants, bio-dyes/natural dyes and natural finishing agents, part of which has ultimately come into practice for its commercial utilization and exploitation for eco-friendliness and environmental advantages. Hence, the above said scientific analyses and case studies presented here in brief with natural resource materials for textile dyeing and finishing, may lead to generate further interest of concern readers towards more and more use of these natural resource materials for textile dyeing and finishing like use of blue natural indigo for creating bio-denim, i.e. natural indigo dyeing by natural reduction process applied on cotton has several environmental safety and advantages. A detailed scientific characterization and index-based ingredient identification of such natural dyes and finishes have been also felt essential to formulate test standards for the identification of natural dyes from such natural dyed textile materials for consumers’ protection. All effort towards this goal should be encouraged.
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\\n\\nBook Chapters and Monographs
\\n\\nBook Chapters and Monographs
\\n\\nBook Chapters and Monographs
\\n\\nBook Chapters and Monographs
\\n\\nBook Chapters and Monographs
\\n\\nMonographs Only
\\n\\nLITHUANIA
\\n\\nBook Chapters and Monographs
\\n\\n\\n\\nBook Chapters and Monographs
\\n\\n\\n\\nBook Chapters and Monographs
\\n\\n\\n\\nSWITZERLAND
\\n\\nBook Chapters and Monographs
\\n\\nBook Chapters and Monographs
\\n\\n\\n\\nBook Chapters and Monographs
\\n\\nBook Chapters and Monographs
\n\nMonographs Only
\n\nBook Chapters and Monographs
\n\n\n\nBook Chapters and Monographs
\n\n\n\nBook Chapters and Monographs
\n\nBook Chapters and Monographs
\n\nBook Chapters and Monographs
\n\nBook Chapters and Monographs
\n\n\n\nBook Chapters and Monographs
\n\nBook Chapters and Monographs
\n\n\n\nMonographs Only
\n\n\n\nLITHUANIA
\n\nBook Chapters and Monographs
\n\n\n\nBook Chapters and Monographs
\n\n\n\nBook Chapters and Monographs
\n\n\n\nSWITZERLAND
\n\nBook Chapters and Monographs
\n\n\n\nBook Chapters and Monographs
\n\n\n\nBook Chapters and Monographs
\n\n