Dyes and Dyeing Fathi Habashi

Home , Alizarin, Pierre Jean Robiquet, Substantive dye

Laval University

From the SelectedWorks of Fathi Habashi

November, 2019

Dyes and dyeing Fathi Habashi

Available at: https://works.bepress.com/fathi_habashi/569/

Dyes and Dyeing

When I was a student at Fouad El Awwal University, now Cairo University, in the Department of Chemical Engineering, Faculty of Engineering, I took a course on Dyes and Dyeing in the academic year 1948-49. I also spent the years 1952-53 in the dye industry at Mahalla El Kobra in Egypt at the large Egyptian Textile plant before going abroad. Few years ago, I received invitations from Lupine Publishers to write short articles for their journal Latest Trends in Textiles and Fashion Designing. Although I have changed my career and became a metallurgist long ago, I decided to go back to my experience in dyeing.

Fathi Habashi Latest Trends in Textile and L UPINE PUBLISHERS Fashion Designing Open Access DOI: 10.32474/LTTFD.2018.01.000110 ISSN: 2637-4595 Mini Review

Dyes and Dyeing

Fathi Habashi* Department of Mining, Metallurgical, Materials Engineering, Laval University, Canada

Received: January 19, 2018; Published: January 25, 2018

*Corresponding author: Fathi Habashi, Department of Mining, Metallurgical, Materials Engineering, Laval University, Quebec City, Canada

Abstract

Dyeing in ancient times was conducted from natural animal and vegetable resources till artificial dyes were discovered in the the creation of alumina for the growing aluminum industry at the end of that century. Now inorganic material like asbestos can be middle of the 19th century in coal tar. Mordating using inorganic compounds to fix the dyes on textile material was responsible for dyed with synthetic dyes to render it less toxic and some minerals are dyed to enhance their beauty.

Natural and Synthetic Dyes Kermes is an insect found on the oak kermes was collected by colouring matter alizarin was isolated by European chemists at the the ancient Egyptians, killed by exposure to vapours of vinegar, from the ground, washed, dried, and then finely ground. The beginning of the nineteenth century, its structure elucidated, and and dried. The product was then used as a scarlet dye with alum in 1868 synthesized by Carl Graebe (1841-1927) and Carl Theodor as a mordant. Kermes is from Arabic “qirmis” meaning deep red. Liebermann (1842-1914), and immediately manufactured on large Fifteen hundred years before Christ, the people of Tyre in present scale [1-6].

Indigo has been known in India and Egypt from remote periods day Lebanon produced the famous Tyrian purple from shell fish. of antiquity as indico. It began to be imported to Europe in 1516 by the way of Cape of Good Hope. Around 1587, the monopoly of cochineal dye industry (red dye from the bodies of cochineal bugs of Central America) was controlled by Spain.

The blue dye was obtained by steeping the plant in water to allow fermentation followed by the oxidation in air of the obtained solution. The fermentation is due to enzymes present in the plant which cause hydrolysis of the glucoside and liberation of the precursors of indigo blue. The structure of indigo was elucidated by Adolf von Baeyer (1835-1917) in 1880 and the synthetic product put on the market in 1897 by the Badische Anilin- und Soda Fabrik in Ludwigshafen. Figure 1: William Henry Perkin (1838-1907). The leaves of a shrub known to-day in Egypt as hennah were used by the ancient Egyptians, much as they are to-day, in the form With the discovery of Brazil, a new market for the so-called of a paste to colour red the palms of the hands, the soles of the feet, “brazilwood” came into existence-a bright red wood that became the nails, and hair. The plant is also known as madder and was used popular for cabinet work but also for the extraction of a red dye. in India. About the time of the Crusades the cultivation of madder The logs were rasped to a coarse powder, moistened with water was introduced into Italy and France. The roots were removed

Fathi H. Dyes and Dyeing. Trends in Textile & Fash Design 1(2)-2018. LTTFD. MS.ID.000110. DOI: 10.32474/LTTFD.2018.01.000110. Citation: 43 Trends in Textile & Fash Design Copyrights@ Fathi H, et al.

and allowed to ferment for weeks. The water extract gave bright improves the appearance of low-quality pearls. The process red colour with fabrics mordanted with aluminum or tin salts. has been used for turquoise, lapis lazuli, howlite, nephrite jade, The colouring principle of brazilwood was isolated by the French chalcedony, quartz, emerald, and ruby. For example, howlite is a chemist Michel Eugene Chevreul (1786-1889), who called it calcium borosilicate hydroxide, Ca2B5SiO9(OH)5, discovered in 1868 brazilin. In 1856, William Henry Perkin (1838-1907) (Figure 1), by Henry How (1828-1879), a Canadian mineralogist. Because of its porous texture, howlite can be easily dyed (Figure 2). Heating can remove unwanted inclusions in some amethysts which make it while experimenting with coal tar in the hope of finding artificial dyestuff which he called Mauve. Since then the synthetic dye look opaque. Heating can intensify, or even induce, a blue coloration quinine as a cure for malaria, discovered the first violet synthetic in sapphires. Heating yellowish pink topaz sometimes has the effect of removing the yellowish color component, thereby intensifying industry flourished. Mordanting and the Aluminum Industry the pink color. Most citrine is made by heating amethyst. The Bayer process used today for the production of alumina Asbestos, a hydrated magnesium silicate Mg (Si2O )(OH) , is for the growing aluminum industry was originally discovered in 3 5 4 1888 in Saint Petersburg in Russia in the Tentelev Chemical Plant conducted at Laval University in the 1990’s proved that dyeing the for supplying mordants to the textile industry. Karl Josef Bayer banned today because the fibers proved to be toxic. Research work (1847-1904) prepared aluminum hydroxide by seeding a solution of sodium aluminate obtained by sintering bauxite with sodium fibers in aqueous solutions with certain organic dyes like Thiazol that renders it nontoxic. Unfortunately, it was too late to save the carbonate. In 1889 he eliminated the sintering process and used an Yellow. The dye forms a chelate with the magnesium ion in the fiber industry. On the other hand, dyes are used to enhance the beauty of universally for the treating of bauxite. certain semiprecious stones. autoclave to obtain sodium aluminate. The modified process is used Dyeing of Minerals References 1. Fierz-David HE (1949) Fundamentals Processes of Dye Chemistry. Inter- science New York, USA. 2. Habashi F (2001) Chemisorption of Organic Dyes on Chryostile Asbestos and the Toxicity Issue. European Journal of Mineral Processing and Envi- ronmental Protection 1: 1-9. 3. Habashi F (2002) From Alchemy to Atomic Bombs, Métallurgie Ex- tractive Québec, Québec City, Canada. Distributed by Laval University Bookstore Zone, Canada. Figure 2: Howlite before and after dyeing. 4. Habashi F (2011) Researches on Asbestos, Métallurgie Extractive Qué- bec, Québec City, Canada. Distributed by Laval University Bookstore Minerals can be dyed with organic dyes. It takes few minutes Zone, Canada. at room temperature to dye a porous and a large surface area 5. Habashi F (2017) Industrial Minerals Through the Ages, Métallurgie mineral like asbestos while it takes few weeks to dye a nonporous Extractive Québec, Quebec City, Canada. Distributed by Laval University mineral like quartz, In some cases it is necessary to heat the mineral Bookstore Zone, Canada. then quench it in the dye solution so that the dye can penetrate in 6. Habashi F (2017) Alumina Production and the Textile Industry. Journal of Textile Science & Engineering 7(6): 1-3. the microscopic cracks formed along cleavage planes. Dye often

This work is licensed under Creative Commons Attribution 4.0 License Latest Trends in Textile and Submission Link: Submit Article Fashion Designing

DOI: 10.32474/LTTFD.2018.01.000110 Assets of Publishing with us • Global archiving of articles • Immediate, unrestricted online access • Rigorous Peer Review Process • Authors Retain Copyrights • Unique DOI for all articles

Fathi H. Dyes and Dyeing. Trends in Textile & Fash Design 1(2)-2018. LTTFD. MS.ID.000110. DOI: 10.32474/LTTFD.2018.01.000110. Citation: 44 Addendum: Dyeing of Metals Some metals may be dyed by organic tantalum, titanium, and, zirconium. dyes but before dyeing they must be anodized. The current releases hydrogen at Anodizing involves giving metals an oxide the cathode and oxygen at the anode. The porous film which renders the metals like voltage required by various solutions may textiles. Anodizing is an electrolytic process in range 15 to 21 V. Higher voltages are typically which the part to be treated forms the anode of required for thicker coatings. The anodizing an electrical circuit. Processes exist current varies with the area of being anodized. for aluminum, hafnium, magnesium, niobium,

Dyeing of anodized aluminum

Latest Trends in Textile and Fashion Designing DOI: 10.32474/LTTFD.2019.03.000166

ISSN: 2637-4595 Short Communication Witt and the Theory of Dyeing

Fathi Habashi*

Laval University, Canada

*Corresponding author: Fathi Habashi, Laval University, Quebec City, Canada

Received: September 27, 2019 Published: October 04, 2019

Abstract

Otto N. Witt (1853-1915) was the first to put a theory of dyeing in 1876 based on chromophore and auxochrome. He also conceived vacuum filtration as a method for rapid filtration.

Working in England his degree in 1873. He found a job in a steel works in Duisburg, Otto Nicolaus Witt (1853-1915) was born in Saint Petersburg, Germany but within months was back in Zurich making colors for Russia, the son of a German pharmacy professor. He was in school cotton printers. He then joined Williams, Thomas & Dower in west when the family moved again to Switzerland. He studied chemical London.

technology at the Federal Polytechnic School in Zurich finishing

Figure 1. Back to Germany lab. His thesis in 1875 reported on the reactions of aromatic nitrosamines and their reactions with dichlorobenzene. Developments in the dyeing industry were so interesting that Witt went back to university in Germany to work in Victor Meyer’s

Figure 2.

Vacuum Filtration the plates leaked round the sides and could slip sideways. Almost Witt suggested placing a disc riddled with holes into a funnel, filtration. Witt’s system worked, but it required care to use because immediately the method was improved by Ernst Büchner (1850- 1924) who developed his now funnel in which the plate is integrated a paper in 1886 describing an improved method for vacuum with filter paper laid on top, moistened to create a seal. He wrote into the funnel itself.

Figure 3.

Dyeing at the Time of Witt

Figure 4.

In 1840 when Queen Victoria married her cousin Prince Albert education in England, was able to found a College of Chemistry in London with August Hofmann (1818-1892) as its director. Hofmann had worked with Liebig on separating the components of who was prince of Saxe-Coburg-Gotha, a region near Justus von Liebig’s laboratory, the prince who was active in promoting scientific

Citation: Fathi Habashi 3(4)-2019. LTTFD.MS.ID.000167. DOI: 10.32474/ LTTFD.2019.03.000167. 641 . Witt and the Theory of Dyeing. Trends in Textile & Fash Design Trends in Textile & Fash Design . Volume 3 - Issue 4 Copyrights @ Fathi Habashi. coal tar before being invited to England. The discovery of mauveine Hermann Kolbe’s lab at the University of Marburg, discovered the in 1853 by William Perkin (1838-1907) in Hofmann Laboratory diazotization reaction when he treated anilines with nitrous acid. in London was soon followed by the discovery of other brightly Griess’s discovery opened up the possibility of coupling together a range of aromatic molecules that were being discovered across Europe. colored compounds obtained by the oxidation of mixtures of In 1858, the graduate student Peter Griess (1829-1888), working in anilines. The new colors began to revolutionize the textile industry.

Figure 5.

Griess joined Hofmann’s group in London, where he continued Adolph von Baeyer (1835-1917) Professor of chemistry in Munich to study his coupling reaction. Around the same time, Heinrich Caro researched the synthesis of the ancient dye indigo and determined its structure in 1870. The same year he prepared indigo. The

(1834-1910) working with his employer John Dale in Manchester, Brown. Caro had already returned to Germany to join Badische developed the first two azo dyes: Manchester Yellow and Bismarck result was that German firms like BASF, Hoechst, and Baeyer or Anilin- und Soda Fabrik in Ludwigshafen in Germany known as known as AGFA, steadily undercut the British in both price and the German-Belgian firm Aktiengesellschaft für Anilinfabrikation BASF. Carl Graebe (1841-1927) and Carl Liebermann (1842-1914) working for BASF synthesized the ancient dye alizarin in 1868. quality. The British dye industry faded.

Figure 6.

Theory of Dyeing contains both the chromophre group, NO2, and the salt forming In a paper published in 1876, he speculated that colored that the substance is a useful dye. For example, trinitroaniline compounds were the result of a grouping of atoms – he called a auxochrome group, NH2, but it is not a useful dye because the basic character of the chromophore. On the other hand, trinitrophenol to stick to a fabric. According to Witt, benzene is colorless but character of the auxochrome is neutralized by the strongly acidic chromophore. By adding the auxochrome, the dye could be made (picric acid) is a useful yellow dye. azobenzene is orange colored. Although it is strongly colored it is devoid of dyeing power. Groups such as azo group, -N=N-, are Conclusion called chromogenes. In order to convert them into useful dyes is necessary. Thus, while azobenzene is not a dye both amino- Witt’s theory was later modified when it was discovered that the the introduction of an auxochromes, i.e., a salt-forming groups are normally electron-donating. The two groups are connected by chromophore is usually electron-withdrawing, and auxochromes a conjugated system. azobenzene and hydroxy- azobenzene are useful dyes. The presence of both chromophore and auxochrome does not necessarily indicate

Citation: Fathi Habashi 3(4)-2019. LTTFD.MS.ID.000167. DOI: 10.32474/ LTTFD.2019.03.000167. 642 . Witt and the Theory of Dyeing. Trends in Textile & Fash Design Trends in Textile & Fash Design . Volume 3 - Issue 4 Copyrights @ Fathi Habashi.

This work is licensed under Creative Commons Attribution 4.0 License Latest Trends in Textile and To Submit Your Article Click Here: Submit Article Fashion Designing

DOI: 10.32474/LTTFD.2019.03.000167 Assets of Publishing with us • Global archiving of articles • Immediate, unrestricted online access • Rigorous Peer Review Process • Authors Retain Copyrights •

Unique DOI for all articles

Citation: Fathi Habashi 3(4)-2019. LTTFD.MS.ID.000167. DOI: 10.32474/ LTTFD.2019.03.000167. 643 . Witt and the Theory of Dyeing. Trends in Textile & Fash Design Latest Trends in Textile and L UPINE PUBLISHERS Fashion Designing Open Access DOI: 10.32474/LTTFD.2018.01.000119

ISSN: 2637-4595 Short Communication

Indigo and Bromo Indigo. The Plant and Animal Kingdoms

Fathi Habashi*

Department of Mining, Metallurgical, Materials Engineering, Laval University, Canada

Received: February 13, 2018; Published: February 19, 2018

*Corresponding author: Fathi Habashi, Department of Mining, Metallurgical, Materials Engineering, Laval University, Quebec City, Canada, Tel: ; Email:

Abstract

Natural indigo was used since ancient times for dyeing textiles a blue color. Its structure became later known and has been synthesized by Adolf von Baeyer in 1880 in Germany who got the Nobel Prize in 1905. Bromo-indigo is a purple dye which was also used since ancient times by the Phoenicians in present day Lebanon and known as Tyrian purple obtained from the snails of Murex branderis in the Mediterranean Sea. Its structure became known in 1895 by Paul Friedlander an assistant to Baeyer. Incidentally bromine was discovered in sea weeds France in 1826 by Antoine Balard.

Keywords: Adolf von Baeyer; Paul Friedlander; Murex brandaris; Tyrian purple

Introduction is insoluble in water and to introduce it into fabric the dye must be reduced to a leuco form which is soluble in a dilute alkali Indigo solution. The fabric is immersed in this solution which allows the leuco compound to adhere to the fabric. The fabric is then exposed to air which oxidizes the leuco compound into the dye. By 1289, knowledge of the dye made its way to Europe, when the Venetian traveller Marco Polo reported on it. It began to be imported to Europe in 1516 by the way of Cape of Good Hope.

Figure 1: Indigo Plant. Indigo has been known in India from remote periods of antiquity as indico and was called nila, meaning dark blue. The Figure 2. blue dye was obtained by steeping the plant leaves (Figure 1) in water to allow fermentation followed by the oxidation in air of the obtained solution. The precursor to indigo is indican; a colorless water-soluble glycoside readily hydrolyzes to release glucose and indoxyl (Figure 2). Oxidation by exposure to air converts indoxyl to indigo. The plant’s leaves contain as much as 0.2–0.8% of indican. The precipitate from the fermented leaf solution was mixed with a strong base such as lye, dried, and powdered (Figure 3). Indigo Figure 3.

Citation: Fathi H. Indigo and Bromo Indigo the Plant and Animal Kingdoms. Trends in Textile & Fash Design 1(4)-2018. LTTFD MS.ID.000119. DOI: 10.32474/LTTFD.2018.01.000119. 80 Trends in Textile & Fash Design Copyrights@ Fathi Habashi.

Many compounds like isatin was isolated by the oxidation of involves reacting o-nitrobenzaldehyde with acetone under highly the natural product with nitric acid or aniline by the destructive basic conditions (Figure 5). The same indigo dye but in a lower distillation led to the knowing the structure of indigo. Indigo concentration is also contained in the woad plant (Figure 5) known remained a rare commodity in Europe throughout the middle for a long time as the main source of blue dye in Europe. Woad was Ages till Adolf von Baeyer (1835-1917) (Figure 4) in 1880 at the replaced by true indigo as trade routes opened up through Cape of University of Munich who got the Nobel Prize for synthesising Good Hope although laws were passed in some parts of Europe to indigo in 1905. The synthetic product put on the market in 1897 by protect the woad industry from the competition of the indigo trade. the Badische Anilin- und Soda Fabrik in Ludwigshafen, Germany. It

Figure 4: Synthesis of Indigo.

related to the plant-derived dye indigo, replacing two NH groups with two sulphur atoms (Figures 10-12). Friedländer isolated and analyzed the natural dyestuff of Tyrian purple. He was able to obtain 12,000 Murex brandaris from biologists working at the Mediterranean Sea. In a complicated process, he isolated 1.4g of pure Tyrian purple. Contrary to his expectations, the compound did not contain sulphur, but was bromine substituted indigo.

Figure 5: Woad plant.

Tyrian Purple Fifteen hundred years before Christ, the people of Tyre of Phoenicia in present day Lebanon (Figure 6) produced a purple dye was a Phoenician island city founded around the third millennium (Figure 7) from shell fish known as Murex brandaris (Figure 8). Tyre BC and the word Phoenician is Greek is for dealers in purple. This are seen outside the city (Figure 9). Paul Friedländer (1857–1923) dye was known as Tyrian purple. Today, piles of broken shell fish was assistant to Baeyer in 1883 and in 1895 he accepted a position at the Technologische Gewerbemuseum in Vienna. During that time Figure 6: Tyre in Phoenicia- today’s Lebanon. he discovered the thioindigo which is an organosulfur compound

Citation: Fathi H. Indigo and Bromo Indigo the Plant and Animal Kingdoms. Trends in Textile & Fash Design 1(4)-2018. LTTFD MS.ID.000119. DOI: 10.32474/LTTFD.2018.01.000119. 81 Trends in Textile & Fash Design Copyrights@ Fathi Habashi.

Figure 12: Tyran blue or Bromo Indigo.

Discovery of Bromine Figure 7: Tyrian Purple. Bromine was discovered in 1826, when the French chemist Antoine Balard (1802-1876) isolated it from chlorine. Its name was

its disagreeable smell. Bromine is a highly volatile reddish-brown derived from the ancient Greek βρῶμος (bad smell) referring to liquid at room temperature. It is abundant in nature as bromide salts or as organobromine compounds, which are produced by many types or marine organisms. Sea water contains bromine in Figure 8: Snail of Murex Brandaris. about 65ppm but bromine is found in much higher concentrations (2500 to 10,000 ppm) in inland seas and brine wells. The major areas of bromine production in the world are from salt brines found in the United Stated and China, from the Dead Sea in Israel and Jordan (Figure 13). Balard found bromine chemicals in the ash of seaweed from the salt marshes of Montpellier. The seaweed was used to produce iodine, but also contained bromine. Balard distilled the bromine from a solution of seaweed ash saturated with chlorine. Bromine was not produced in large quantities until 1858, when the discovery of salt deposits in Stassfurt enabled its production as a Figure 9: Piles of crushed Murex brandaris in Tyre. by-product of potash. Bromine present in minerals substituting for chlorine is very rare. Note that iodine is found in Chile nitrates in Salar de Atacama.

Figure 10: Paul Friedländer (1857–1923).

Figure 13: Antoine Balard (1802-1876). Conclusion While natural indigo occurs solely in plant kingdom, natural bromo-indigo occurs in Murex brandaris in the animal kingdom. Figure 11: Thioindigo. Bromine was also discovered in sea weeds.

This work is licensed under Creative Commons Attribution 4.0 License Latest Trends in Textile and Fashion Designing To Submit Your Article Click Here: Submit Article Assets of Publishing with us DOI: 10.32474/LTTFD.2018.01.000119 • Global archiving of articles • Immediate, unrestricted online access • Rigorous Peer Review Process • Authors Retain Copyrights • Unique DOI for all articles

Fathi Habashi Laval University, Quebec City, Canada [email protected]

Madder root Alizarin is 1,2-dihydroxy anthraquinone also known as Mordant Red and Turkey Red that has been used throughout history as a red dye. The roots of Rubia tinctorum known as madder, are the source of a natural dye. The name Rubia derives from the Latin ruber meaning "red". The plant's roots contain an anthracene compound called alizarin that gives red color to textiles. Madder has been cultivated as a dyestuff since antiquity in central Asia and in Egypt and was widely used as a dye in Western Europe in the medieval centuries. Alizarin is present in madder root in only small quantities as a glycoside, i.e, attached to a sugar molecule. The glycoside could be hydrolyzed by acids, alkalies, or enzymes.

Madder plant Madder root

Robiquet In 1826, the French chemist Pierre-Jean Robiquet (1780-1840) was at first a pharmacist in the French armies during the French Revolution years then became a professor at the École de Pharmacie in Paris, found that madder root contained two colorants, the red alizarin and the more rapidly fading purpurin. He is also best known for his discovery of caffeine and codeine.

Alizarin Purpurin Pierre-Jean Robiquet

Extraction of red dye For the production of a dye preparation from madder, the glycoside should be dried, and pulverized, then hydrolysed, and filtered. Madder is not a substantive dye and therefore needs chemicals to help the dyestuff bond with the fibers. These soluble chemicals are called mordants and they facilitate the bonding of the fiber and dye. Mordants can be obtained from naturally occurring alum which is aluminum sulfate soluble in water. Over the years, it was found that salts containing copper, iron, tin, and chromium, could be used in place of alum to give madder-based pigments different shades.

Red lake formed by reaction of alizarin and aluminum ion. The ion has three covalent Mordanted with none, alum, copper sulfate, bonds and a fourth dative bond ferrous sulfate

Synthesis of alizarin The alizarin component became the first natural dye to be synthetically duplicated in 1868 when the German chemists Carl Graebe (1841–1927) and Carl Liebermann (1842-1914), working for Badische Anilin- und Soda Fabrik in Ludwigshafen in Germany known as BASF, found a way to produce it from anthracene. The principal synthesis was based on oxidation of anthraquinone-2- sulfonic acid with sodium nitrate in concentrated sodium hydroxide. The subsequent discovery by J. Brönner and H. Gutzhow in 1871 that anthracene could be extracted from coal tar made the production more economical. The synthetic alizarin could be produced for a fraction of the cost of the natural product, and the market for madder collapsed.

Carl Graebe Carl Liebermann