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2 History 3 Developments in dyeing technology 4 Chemical properties |
A variety of plants have provided indigo throughout history, but most natural indigo is obtained from plants in the genus Indigofera, which are native to the tropics. In temperate climates indigo can be obtained from woad (Isatis tinctoria) and dyer's knotweed (Polygonum tinctorum), although the Indigofera species yield more dye. The primary commercial indigo species in Asia was true indigo (Indigofera tinctoria, also known as Indigofera sumatrana). In Central and South America the two species Indigofera suffructicosa and Indigofera arrecta (Natal indigo) were the most important.
Natural indigo was the only source of the dye until about 1900. Within a short time, however, synthetic indigo had almost completely superseded natural indigo, and today nearly all indigo produced is synthetic.
In the United States, the primary use for indigo is as a dye for cotton work clothes and blue jeans. Over one billion pairs of jeans around the world are dyed blue with indigo. For many years indigo was used to produce deep navy blue colors on wool.
Indigo does not strongly bond to the fiber, and wear and repeated washing slowly remove the dye.
Indigo is among the oldest dyes to be used for textile dyeing and printing. Many Asian countries, such as India, China, and Japan, have used indigo as a dye for centuries. The dye was also known to ancient civilizations in Egypt, Greece, Rome, Britain, Peru, and Africa.
India is believed to be the oldest center of indigo dyeing in the Old World. It was a primary supplier of indigo to Europe as early as the Greco-Roman era. The association of India with indigo is reflected in the Greek word for the dye, which was indikon. The Romans used the term indicum, which passed into Italian dialect and eventually into English as the word indigo.
The Romans used indigo as a pigment for painting and for medicinal and cosmetic purposes. It was a luxury, however, being imported from India to the Mediterranean by Arab merchants. Indigo remained a rare commodity in Europe through the Middle Ages.
In the late fifteenth century, the Portuguese explorer Vasco da Gama discovered a sea route to India. This led to the establishment of direct trade with India, the Spice Islands, China, and Japan. Importers could now avoid the heavy duties imposed by Persian, Levantine, and Greek middlemen and the lengthy and dangerous land routes which had previously been used. Consequently, the importation and use of indigo in Europe rose significantly. Much European indigo from Asia arrived through ports in Portugal, the Netherlands, and England. Spain imported the dye from its colonies in South America. Many indigo plantations were established by European powers in tropical climates; it was a major crop in Jamaica and South Carolina. However, France and Germany outlawed imported indigo in the 1500s to protect the local woad dye industry.
In 1865 the German chemist Johann Friedrich Wilhelm Adolf von Baeyer began working with indigo. His work culminated in the first synthesis of indigo in 1880 and the announcement of its chemical structure three years later. BASF developed a commercially feasible manufacturing process that was in use by 1897, and by 1913 natural indigo had been almost entirely replaced by synthetic indigo. In 2002, 17,000 tons of synthetic indigo were produced worldwide.
Indigo is a challenging dye to use because it is not soluble in water; to be dissolved, it must undergo a chemical change. When a submerged fabric is removed from the dyebath, the indigo quickly combines with oxygen in the air and reverts to its insoluble form. When it first became widely available in Europe in the sixteenth century, European dyers and printers struggled with indigo because of this distinctive property.
Traditionally, the insolubility of indigo was overcome by using stale urine. Urine reduces the water-insoluble indigo to a soluble substance known as
indigo white or leucoindigo, which produces a yellow-green solution. Fabric dyed in the solution turns blue after the indigo white oxidizes and returns to indigo. Synthetic urea to replace urine became available in the 1800s.
Two different methods for the direct application of indigo were developed in England in the eighteenth century and remained in use well into the nineteenth century. The first method, known as pencil blue because it was most often applied by pencil or brush, could be used to achieve dark hues. Arsenic trisulfide and a thickener were added to the indigo vat. The arsenic compound delayed the oxidation of the indigo long enough to paint the dye onto fabrics.
The second method was known as china blue due to its resemblance to Chinese blue-and-white porcelain. Instead of using an indigo solution directly, the process involved printing the insoluble form of indigo onto the fabric. The indigo was then oxidized in a sequence of baths of ferrous sulfate. The china blue process could make sharp designs, but it could not produce the dark hues possible with the pencil blue method.
Around 1880 the glucose process was developed. It finally enabled the direct printing of indigo onto fabric and could produce inexpensive dark indigo prints unattainable with the china blue method.
Indigo is a dark blue crystalline powder that melts at 390°–392°C. It is insoluble in water, alcohol, or ether but soluble in chloroform, nitrobenzene, or concentrated sulfuric acid. The chemical structure of indigo corresponds to the formula C16H10N2O2.
The naturally occurring substance is indican, which is colorless and soluble in water. Indican can easily be hydrolyzed to glucose and indoxyl. Mild oxidation, such as exposure to air, converts indoxyl to indigo.
The manufacturing process developed in the late 1800s is still in use throughout the world. In this process, indoxyl is synthesized by the fusion of sodium phenylglycinate in a mixture of sodium hydroxide and sodamide.
Several simpler compounds can be produced by decomposing indigo; these compounds include aniline and picric acid. The only chemical reaction of practical importance is its reduction by urea to indigo white. The indigo white is reoxidized to indigo after it has been applied to the fabric.
Indigo treated with sulfuric acid produces a blue-green color. It became available in the mid-1700s. Sulfonated indigo is also referred to as Saxon blue or indigo carmine.
Tyrian purple was a valuable purple dye in antiquity. It was made from excretions of a common Mediterranean sea snail. In 1909 its structure was shown to be 6,6′-dibromoindigo. It has never been produced synthetically on a commercial basis.Sources and uses
History
Developments in dyeing technology
Chemical properties