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- The Art of Wool
- Textile manufacturing
- A Mass Spectrometric Study on Tannin Degradation within Dyed Woolen Yarns
- Our Values
- Project Report on Woollen Yarn Spinning Plant
- Trinity factory. Textile industry in Russia
- Open end spinning plants Manufacturers Panipat
- Trinity factory. Textile industry in Russia
- List of Top Indian Textile Manufacturing Companies
The Art of Wool
The ageing behavior of these dyes is a challenge in conservation science, requiring a thorough knowledge of the textile—mordant-dye system. In this work, we analyzed reference wool yarns dyed with natural tannins from oak gallnuts, walnut Juglans regia , and catechu Acacia catechu , after artificial ageing.
Since conventional reversed-phase RP columns usually show poor retention efficiency of highly polar compounds such as tannins, an RP-amide embedded polar group stationary phase was used to achieve optimal retention of the most polar compounds. Tannins from oak gallnuts showed little degradation after ageing, while a significant increase in the content of hydroxybenzoic acids was observed for tannins from walnut and catechu.
Finally, the analytical procedure was applied to characterize the tannin dyes in historical tapestries from the 15 th to 16 th century, and the results were discussed in comparison with the reference yarns. Tannins are polymeric polyphenols. They are a group of secondary plant metabolites whose primary biological function is protection against bacterial and fungal attacks.
Thousands of different polyphenols have been identified throughout the vegetal kingdom [ 1 ], resulting in a high number of possible structures of tannins, which makes it challenging to define a universal classification method. The most widely accepted classification divides tannins into two main categories [ 2 , 3 ]. The first is constituted by hydrolysable tannins, which are the most common in woody plants. They are composed of gallic acid and ellagic acid units linked to monosaccharides by ester bonds.
The second category consists of condensed tannins, which are made of flavonoid units linked by C—C bonds. Tannins have been used for various purposes throughout history, thanks to their nutraceutical properties and their ability to convert animal skin into leather [ 4 , 5 , 6 , 7 ].
One of the most traditional uses of tannins is as natural dyes or adjuvants in dyeing, providing a wide range of shades going from pale yellow to dark brown [ 8 ].
Wool and silk clothes, tapestries, and carpets colored with tannin-based dyes can be found in many cultures and eras of human history [ 9 , 10 , 11 , 12 ]. They can also be used in the weighting process for silk, after degumming [ 13 ]. Tannins are classified as mordant dyes, as their durability on textiles is significantly improved using metallic ion mordants such as aluminum and iron [ 14 ].
The first reference to a tannin and mordant-based coloring material is relative to iron-gall inks, cited in the Naturalis Historia by Pliny the Elder [ 16 ]. Other common sources of tannins are the bark and fruits of plants from the Juglans genus walnuts , and the wood of Acacia catechu , which has a high content of condensed tannins [ 17 , 18 ]. Tannin dyes usually lack long-term stability, and their resistance to ageing depends on the combination of originating plant, mordant, and textile, besides environmental parameters [ 19 ].
The combination of compositional variability and low fastness of tannin dyes results in complex degradation mechanisms, which are both difficult to study and to reproduce, mainly because they are known to involve the textile matrix and the possible mordant [ 19 ]. A complete rationalization of such mechanisms still requires dedicated studies, which are of particular importance in Heritage Science.
A detailed knowledge of the composition of tannin dyes in historical textiles can provide insights on the source of the dyestuff, the technique used for its application and the conservation state of the object [ 20 ]. These results can also be used to deduce information on the socio-economical context in which the artefacts were produced, as well as the technological level required to produce them. As natural dyes are usually complex mixtures, in-depth characterization requires the use of separation techniques.
Extraction of the dye from the matrix followed by liquid chromatography LC with spectroscopic and mass spectrometric detectors is widely used, as it can provide details on the single components of the dyestuff [ 12 , 21 , 22 , 23 ]. The main issue in LC analysis of tannins is that polar compounds such as polyphenols are poorly retained by common hydrophobic stationary phases.
The efficiency of EPG columns in the analysis of phenolic compounds has already been assessed in the literature [ 24 , 25 ]. Despite these results, scarce information is reported on the use of such stationary phase to analyze tannin dyes. In the present work, high-performance liquid chromatography HPLC with a reversed-phase-amide RP-amide EPG stationary phase coupled with high-resolution tandem mass spectrometry was used to characterize the composition of the extracts of wool yarns dyed with natural tannins.
This approach allowed us to achieve a suitable retention of the most polar compounds, and an excellent efficiency leading to a thorough characterization of the single components of the extracts. A set of mock-ups of woolen yarns dyed with different kinds of tannin vegetal sources gallnut, catechu, and walnut was prepared. To evaluate the effect of the mordant, samples with aluminum or iron mordants were compared to those without any mordant.
Changes in the relative content of the various tannins were evaluated by performing semiquantitative calculations based on integrated peak areas as a function of ageing time. The stability of the dyes was also evaluated by artificial ageing of the samples and by repeating the analyses at different time intervals.
In the end, several historical tapestries were analyzed to assess the nature and state of conservation of their tannin fraction. To the best of our knowledge, this is the first time that RP-amide was used for the analysis of natural tannins dyes in reference textiles and historical tapestries.
Table 1 presents a list of all the compounds that were identified in the reference and historical samples. As will be discussed in the following sections, no qualitative difference in the composition of the extracts was found between the reference samples with or without mordant.
Following this observation, reference samples were grouped in Table 1 only according to the dye. Figure 1 reports the structures of some of the most representative tannins identified in the samples. List of identified compounds in reference and historical samples. For each compound, the chemical formula, molecular weight, molecular ions, and retention times are presented.
In the case of undistinguished isomers, the retention time reported is relative to the first one eluted. The labels G, J, and C indicate reference samples dyed with gallnuts, walnut, and catechu, respectively.
The main peaks in all the collected chromatograms for the yarns dyed with gallnuts were attributed to gallic acid and heavier gallotannins. Meta - and para -galloyl-gallate and a series of galloyl-glycosides were found in all the samples, regardless of the use of mordant. Galloyl-glycosides are the main components of gallnut tannins, where the number of gallic acid units per glucose molecule usually ranges from five to twelve [ 26 ].
In the extracts from the dyed yarns, the number of gallic acid molecules per monosaccharide unit generally ranged from two to seven, implying that a slight modification of the tannin profile already took place during the dyeing process. Monogalloyl-glucose was not found in any chromatogram, possibly due to its high polarity. Ellagic acid was also detected in all chromatograms. Figure 2 presents the extracted ion chromatograms EICs obtained for the unaged wool yarns without mordant using the find by formula algorithm in the data processing software.
The peaks of gallic acid, galloyl-gallate, ellagic acid, and all gallotannins are highlighted. Two peaks labeled as galloyl-gallate can be identified, corresponding to the meta - and para -isomers. Multiple peaks can also be observed for di-, tri-, and tetragalloyl-glucose, corresponding to isomers with different combinations of ester bonds.
After h of artificial ageing, few differences were found in the chromatographic profiles in terms of identified compounds. Nevertheless, as will be discussed in the following paragraphs, some significant differences can be observed from a closer look at the relative peak areas of gallotannins.
Extracted ion chromatograms from the extract of the nonaged yarn dyed with oak gallnuts without mordant. The wool yarns dyed with gallnuts without any mordant or with an iron-based mordant were also analyzed at four intermediate ageing times, to obtain additional insights into the degradation processes. Integrated areas for each species were normalized by the sample amount and extract volume, to estimate the content of the various gallotannins in each sample.
The results are presented in Table 2. The absolute areas of each gallotannin decreased in all cases after h of accelerated ageing. However, the values at intermediate times did not show a monotonic trend, except for a few cases. This result reflects the complex degradation mechanism of these compounds and suggests that the most likely degradation process could be the cleavage of the ester bonds of gallotannins.
In fact, such mechanism would cause the content of each gallotannin species to be determined by a sum of a negative contribution cleavage of the ester bonds to form lighter gallotannins and a positive contribution cleavage of the ester bonds from heavier gallotannins , resulting in the observed complex trends. Normalized peak areas of all identified compounds in the extracts of yarns dyed with oak gallnuts using either no mordant or iron mordant, as a function of ageing time.
The total gallotannins content and the percentage of free gallic acid with respect to total identified compounds are also presented for each sample. Table 2 also presents the percentage of gallic acid, calculated by dividing the normalized area of free gallic acid by the total normalized area of all identified compounds.
This percentage did not show a monotonic trend in any of the samples. This result shows that, although the hydrolysis of the ester bonds in gallotannins is the most likely degradation mechanism, further degradation processes also take place, leading to the depletion of gallic acid and preventing its accumulation. This means that the presence of 3,4-dihydroxy, 4-hydroxy, and 3-hydroxybenzoic acid in the chromatograms of these samples could be due not only to the degradation of wool, but also to the depletion of gallotannins.
Degradation products obtained by decarboxylation of gallic acid could not be found in any chromatogram, possibly due to the low molecular weight of such species. Further information can be obtained by summing the normalized areas of all gallotannins and observing the trend of the total tannin content in the samples as a function of ageing time, as shown in Figure 3 a.
The total content for the yarns without any mordant is higher than that of the yarns mordanted with iron, at all ageing times. However, the results obtained in this work suggest that the presence of iron also affects the uptake of gallotannins during the dyeing process.
The integrated and normalized areas for all gallotannins in the hydrolyzed extracts are presented in Table 2. To compare the efficiencies of the two extraction methods, the ratio between total gallotannins in the samples with and without mordant was calculated in both cases.
Figure 3 b presents the dependence on the ageing time of the total tannin content for each sample, normalized by the content in the corresponding nonaged sample. The plots in this graph show that artificial ageing had very similar effects on both sets of samples. It appears that in our experimental conditions, the presence of the iron-based mordant only reduces the total gallotannins uptake by the fiber during the dyeing process, but has little influence during artificial ageing.
The chromatographic profiles of the yarns dyed with Acacia catechu highlighted the presence of several compounds mostly belonging to the flavonoid family Table 1. The presence of these compounds in catechu extracts has been documented in the literature [ 30 ]. No qualitative differences were disclosed by comparing samples with different mordants or after artificial ageing.
The EICs of the main compounds identified in the nonaged wool yarns without any mordant are reported in Figure 4. Catechin and epicatechin are the main species present in Acacia catechu [ 31 ].
Extracted ion chromatograms from the extract of the nonaged yarn dyed with Acacia catechu and without mordant. Chromatographic areas integrated for each species were converted into percentages, and the results are presented in Figure 5. The areas of hydroxy- and dihydroxybenzoic acids 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 3,4-dihydroxybenzoic acid , and those of the flavonoids quercetin and rhamnetin were summed to aid visual interpretation. A full list of the samples labels is provided in Table 3.
As expected, ageing results in the decrease of catechin, epicatechin, quercetin, and rhamnetin and the increase of benzoic acids [ 27 ]. After h of artificial ageing, flavanols slightly decreased, while flavonols showed a more enhanced depletion, evidencing a different resistance to degradation. Artificial ageing caused an increase in the extracts content of benzoic acids, and the changes were more significant than those observed for the yarns dyed with gallnuts.
Similar variations were observed both in presence and in absence of mordants, revealing that the mordant does not play a fundamental role in the degradation of flavanols and flavonols within catechu extracts in the adopted conditions. In this case, the presence of the mordant does not seem to affect the total dyeing molecules uptake by the fiber, different from what was observed for oak gallnut dye bath. The extracts of yarns dyed with Juglans regia contain several classes of compounds Table 1 in accordance with the composition reported in the literature: flavonols quercetin , flavonol O -glycosides quercetin 3-galactoside, quercetin 3-arabinoside, quercetin 3-xyloside and quercetin 3-rhamnoside , cinnamic acids caffeic acid and 3,4-dimethoxycinnamic acid , hydroxycinnamic acids and esters p -coumaric acid, p -coumaroylquinic acid, 3- O -caffeoylquinic acids and 5- O -caffeoylquinic acids , benzoic acids gallic acid, 3,4-dihydroxybenzoic acid, 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, and vanillic acid , benzoic esters ethyl gallate , as well as ellagic acid [ 33 , 34 , 35 ].
Juglone 5-hydroxy-1,4-naphthoquinone is known as the marker compound of Juglans species [ 36 ], but it is absent in all the reference yarns analyzed.
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A Mass Spectrometric Study on Tannin Degradation within Dyed Woolen Yarns
Throughout history, the complexity and versatility of the unique woollen fibre has led to its amazingly broad range and multi-purpose usage in woollens. Below are a few important mile stones in wool's history. Very quickly wool was being spun and woven in Mesopotamia but also other northern European tribes. Spinning and weaving tools were relatively basic. The mobility of sheep allowed Persians, Greeks and Romans to easily distribute and therefore introduce sheep and their wool across Europe. Throughout the Roman empire wool fleeces became superior through selective breeding. The history of Britain's leading wool manufacturing industry is said to have developed with spinning and weaving around BC. The Romans highly valued the Britons weaving skills. The establishment of the Roman wool plant in Winchester, England in 50 AD helped the Britons to improve their methods.
Every year sheep grow a new fleece, making wool a renewable resource. Woolgrowers actively work to preserve natural resources for generations to come. Scrap and even used wool can be recycled to create new blankets and throws. And unlike synthetics, wool is biodegradable.
Since inception the Company has been committed to achieve high growth through development of niche products to meet increasingly sophisticated demands of the Industry. Today, it possesses the largest product portfolios of spun-dyed, cotton blended and cot Arvind Limited is a textile company.
Project Report on Woollen Yarn Spinning Plant
Textile manufacturing is a major industry. It is based on the conversion of fibre into yarn , yarn into fabric. These are then dyed or printed, fabricated into clothes.
Trinity factory. Textile industry in Russia
As with many discoveries of early man, anthropologists believe the use of wool came out of the challenge to survive. In seeking means of protection and warmth, humans in the Neolithic Age wore animal pelts as clothing. Finding the pelts not only warm and comfortable but also durable, they soon began to develop the basic processes and primitive tools for making wool. By B. People soon began to develop and maintain herds of wool-bearing animals. The wool of sheep was soon recognized as one of the most practical to use.
The Flemings were so expert in making woollen cloth, that it was said of them that their skill in the art of weaving was a peculiar gift conferred by nature. Large numbers of weavers came over from Flanders in the train of the Conqueror, and in the intervals of turmoil prosecuted their calling with success. In course of time they thoroughly established the trade in the country, and in the reigns of Henry I.
Open end spinning plants Manufacturers Panipat
Natural wool is the fiber obtained from sheep and other animals. For example cashmere and the mohair of goats, Qiviut of muskoxen, angora of rabbits, and Camelid wool. Sheep wool is the most preferred because it has important physical properties distinguish it from camel hair, goat hair, and others.
Trinity factory. Textile industry in Russia
We have a friendly relationship with the Hennecke family and were already able to supply mountain sheep wool in recent years. We are currently creating more space and expanding our warehouses so we can process orders faster in the future. Please pay attention to the approximately 90 colors of our Tyrolean mountain sheep wool available. We are happy to send you our wool pattern color chart for free.
Trinity worsted factory is one of the best domestic textile enterprises. A large-scale modernization carried out in the s allowed us to move from the production of army cloth to the production of high-quality smooth woolen fabrics and knitting wool yarn. The company is located in the city of Troitsk near Moscow. The fact that Trinity Factory is one of the oldest Russian textile enterprises is beyond doubt. However, historians and historians disagree when it was founded.
List of Top Indian Textile Manufacturing Companies
Warren Mills is located in the center of Stafford Springs, a small town in the corner of northeastern CT. It was originally settled in by settlers devoted to cultivation of their land. By , the town was famous for its natural mineral springs. In , American Woolen Company launched its first luxury garment collection with a commitment to preserving the craft and defining an authentic American style. We start by dyeing the raw fiber to the desired shade which is the superior way to achieve lasting color.
Mazharul Islam Kiron is a textile consultant and researcher on online business promotion. He is working with one European textile machinery company as a country agent. He is also a contributor of Wikipedia.