Transition from Natural to Early Synthetic Dyes in the Romanian Traditional Shirts Decoration

Abstract

The traditional shirt (“ie”) is the most well-known element of Romanian anonymous textile art. Apart from aesthetic and utilitarian roles, it has strong symbolic significance, mainly through the colours used for decoration. Very recently, the traditional shirt with decoration over the shoulder (“ia cu altiță”) was introduced as a Romanian identity element as part of UNESCO heritage. Depending on the ethnographic area, the traditional shirt with decoration over the shoulder has acquired special expressive particularities over time. Particularly relevant is that from Valea Hârtibaciului, an area of Transylvania in the very centre of Romania. Although sober in appearance with large fields of white plain weave, it is discreetly decorated with elaborated embroidery on the sleeve bracelets, over the shoulders and neck. Even the colour range and decoration motifs remain unchanged in time, evolution in the materials used and a subtle transition from natural hues to more strident alternatives were observed in the late 19th and early 20th centuries. For the present study, samples were taken from representative objects in the collections of the ASTRA Museum, Sibiu and Ethnographical Museum, Brasov, documented as belonging to the area of Valea Hârtibaciului and dated in the museum archives as from the late 19th and early 20th century. The textile materials and the dyes used in the shirts’ embroidery were monitored. Fibre identification was made by optical microscopy and infrared spectroscopy (FTIR-ATR). Dye analysis was performed by liquid chromatography coupled with UV-Vis (diode array) detection, while some of the samples were also analysed by liquid chromatography coupled with mass spectrometric detection (LC-DAD-MS). Dyes were extracted from the fibres by acid hydrolysis. Identification was based on data collected on standards, dyes and dyed fibres. For the early synthetic dyes, a dedicated library of references was built, which includes information relative to the most relevant representatives used between 1850 and 1900, the ‘Helmut Schweppe list’. According to the study, in the last decades of the 19th century, natural dye sources such as dyer’s broom, madder, Mexican cochineal and indigoid dyes were gradually replaced by early synthetic dyes: fuchsine (1856), methyl violet (1861), synthetic alizarin (1871), brilliant green (1879), azo flavine 3R (1880), rhodamine B (1887) and others.

Liquid chromatography as analytical tool for the study of natural and early synthetic dyes in traditional Saxon textiles

“…Fuchsine (also called magenta) was evidenced based on the detection of one or more of the four marker compounds described in literature: pararosaniline (λmax = 544 nm), rosaniline (λmax = 546 nm), methylrosaniline (λmax = 548 nm) and dimethylrosaniline (λmax = 550 nm) [27,35,37] in 7 samples, once on rayon and the others on silk. As stated in literature [37] and also discussed in a previous publication with reference to the use of early synthetic dyes in Romanian traditional textiles [32], two production processes were reported, which would result in the so called "early fuchsine" -characterized by a mixture of the four compounds mentioned above and "late fuchsine" -to give mainly methylrosaniline (also called magenta II) and dimethylrosaniline (new fuchsine). "Early fuchsine" is mentioned as obtained in the late 19-th century by heating an oxidant with a coal tar distillate containing a mixture of aniline and toluidine in various ratios, with or without further inclusion of carbon tetrachloride, while "late fuchsine" would be the result of a later process that involved reaction of 4,4'methylene-di-o-toluidine and o-toluidine [36].…”

“…Madder was used on wool in a bed cover dated 1841, on silk in a 19-th century towel and on cotton embroidery yarns in textiles dated 1802 or not dated. However, detection of madder and putting results in with correlation with earlier data on traditional Romanian textiles [32] would be an argument to date the respective object (1861) in the 19-th century or earlier. Carminic acid was identi ed in 6 samples (3383_P1, 1936_P1, 2075_P6, 2954_P2, 6081_P3, 7515_P1).…”

“…Indigotin was evidenced in DMSO extracted samples by retention, UV-Vis (λmax = 285, 330, 610 nm) and mass spectrometric data ([M-H] − 261), when available. Although there are several biological sources which contain indigotin precursors, two of them may have been used in the traditional Saxon textiles: woad (Isatis tinctoria L.), available in Europe since Neolithic and indigo (Indigofera tinctoria L.) accessible in the area since the 17-th century [29,32]. From the analytical point of view, it is not possible to distinguish between the two species neither to differentiate natural from synthetic indigo, which was rst produced in 1882.…”

“…However, considering that indigo based dyes were identi ed in handmade textiles dated 17-th to 19-th century, on wool (4 cases), silk (3 samples) and cotton (1 sample), it is obvious that one of the natural sources was responsible for the colour. According to previous studies on textiles in Romanian collections [29,30,32], indigo based dyes were the only source of blue in traditional textiles, until synthetic dyes became available.…”

“…Studies performed on traditional textiles in Romanian collections evidenced the use of various colour sources, natural or imported as well as of 'early synthetic dyes' [29,30], which is the name adopted for a selection of about 67 synthetic dyes, the most frequently used between 1856 and 1900 [31]. An in depth survey on materials in traditional Romanian shirts decoration in a rural area of less than 50 km in Transylvania, not far from Sibiu, revealed some phases in the transition from natural to the early synthetic dyes: rst, the three main colours red, yellow and blue were achieved by using natural dye sources such as madder, carminic acid based dyes, dyer's broom, sawwort, tannins and indigo dyes on wool; the colour palette was then enriched with orange or black hues by using mineral pigments lead chromate and Prussian blue; further on, natural dyes were applied on silk; nally, bright pink, violet, orange, blue or green colours were produced exclusively with synthetic dyes on silk [32].…”