Dyeing technology in ancient China
Pei Jinchang, Shanghai Institute of Textile Science
my country has long used mineral and plant dyes to dye fabrics or yarns, and In long-term production practice activities, they have mastered the extraction and dyeing techniques of various dyes and produced colorful textiles, which enriched the material and cultural life of ancient my country.
Application of various mineral and plant dyes
As early as tens of thousands of years ago in the caveman era, our ancestors had used natural hematite powder to dye beaded shells and ribs. rope. In the slave society, the division of labor was fine, and there were special official positions "to dye the grass, to collect and dye the grass in the spring and autumn, to receive it according to the power, and to award it when the time comes"; and there was "dying people's palms to dye silk and silk" ( "Zhou Rites"). Before dyeing, noble silk and silk fabrics also need to undergo "scouring" treatment (equivalent to today's scouring process). In "Kaogong Ji·Yushi", the operation technique of "violent training" was described: first, "wet the silk with Kuang water for seven days, remove it from the ground and soak it", and then "bare it for several days during the day, and stay in various wells at night" , *** "Seven days and seven nights". For silk fabrics, because they are tighter than silk threads, during violent training, one has to "use the fence as ashes and loosen the silk", and then "make all the materials as a material, and use them as a mirage", and the same process is repeated for seven days and nights. Kuangshui and liàn ash are both alkaline plant ash juice (potassium carbonate, etc.), lanhui is the ashes of burned neem wood, and mirage is the more alkaline quicklime (calcium oxide) calcined from shells. ). After the silk threads and silk fabrics are repeatedly treated with alkaline ash juice or ash, most of the sericin on the outside of the fibers is removed, which is beneficial to dyeing. The pretreatment of fabrics before dyeing - "violent training" is mostly carried out in spring ("spring violent training"). After that, large-scale dyeing production of "Xia Haixuan, autumn dyeing and summer" ("Xia" means five colors) began Activity.
The dyes used for dyeing in ancient times were mostly natural mineral or plant dyes, and their extraction and dyeing methods were different.
Mineral Pigments
The natural hematite mentioned earlier was the earliest mineral pigment to be used. During the Spring and Autumn Period and the Warring States Period, it was still used to dye rough linen fabrics. It was called ocher clothing at that time, and it was probably dyed with natural hematite powder. The collarless ocher clothing was used as prison clothing for criminals. In addition, cinnabar (the main component is mercury sulfide) was also an important mineral pigment for dyeing red in ancient times. In "Kaogong Ji·Zhongshi", it was described that feathers were dyed with red pill, which is cinnabar. The linen and embroidery marks unearthed from the Western Zhou Tomb in Rujiazhuang, Baoji, all have traces of dyeing with elixir. Because of its pure red color and long-lasting color, cinnabar was still used as a pigment for dyeing expensive clothing until the Western Han Dynasty. After X-ray diffraction analysis, the vermilion on the vermilion diamond-patterned cotton robe unearthed from the No. 1 Han Tomb in Mawangdui, Changsha, showed that its spectrum was the same as that of red mercury sulfide in hexagonal crystals. Before dyeing, cinnabar or ocher pigments must be ground and glued into a slurry before they can be applied to the surface of the fabric with tools. From the analysis of the unearthed textiles mentioned above, it can be seen that the pigment grinding at that time was quite fine and the dyeing technology was very sophisticated. In addition to cinnabar and ocher dyed red, other natural mineral pigments include sericite dyed white, stone yellow dyed, stone green dyed green, etc.
Plant dyes
There are many types of plant dyes used in ancient my country. According to their chemical properties and dyeing methods, they include direct dyes, basic dyes, mordant dyes and reduction and oxidation dyes.
Direct dyes and alkaline dyes Gardenia is the most widely used direct dye in the Central Plains of my country in ancient times. In "Historical Records", there is "Qianmu Xiaqian..." This person is the same as Qianhu Hou and others. "The records show that gardenia dyeing was very popular during the Qin and Han Dynasties. The main component of gardenia is gardeniposide. This is a yellow pigment that can be dyed directly on natural fibers. The core material of the yellow barberry tree, which is also rich in berberine, can be used to dye silk directly after being boiled. "Qimin Yaoshu" once recorded the cultivation and printing and dyeing uses of cork bark. Berberine is an alkaline dye and is suitable for dyeing animal fibers such as silk and wool. Bao Zhao (about 414-466) during the Northern and Southern Dynasties once wrote a poem about "filing barberry to dye yellow silk", indicating that yellow barberry was used for dyeing at that time. Silk is very popular. This is not only because it is easy to dye, but also because berberine has insecticidal and moth-proof effects.
The mordant dye madder is one of the earliest mordant plant dyes to appear in ancient Chinese written records. The "Book of Songs" once described the planting of madder ("Zheng Feng·Dongmen Zhi?": "Ru■ in Ban ", "Ru■" means madder), and it talks about clothes dyed with madder ("Zheng Feng·Out of the East Gate": "糩衣Ru■"). Madder root contains red alizarin, which cannot directly color the fiber. A mordant must be used to generate an insoluble lake and fix it on the fiber. Most of the mordants used in ancient times were alum (white alum), which contained a relatively large amount of calcium and aluminum. It and alizarin produced a bright crimson lake with good washability. The dark red silk and longevity embroidered robes unearthed from Han Tomb No. 1 in Mawangdui, Changsha, were dyed with alizarin and a mordant containing aluminum and calcium. In addition to madder that can be mordant and dyed red, there is also Su Fangmu recorded in "Tang Materia Medica", which was also the main mordant plant dye in ancient times. This kind of tree wood that was abundant in Guangdong, Guangxi, Taiwan and other places in ancient my country contains the red pigment "Brazilian hematoxylin". Like alizarin, it is reddish-red with aluminum salt.
The "Liocao" (Lithospermum) in "Erya" is a mordant dye used for dyeing purple in ancient times. Comfrey root contains shikonin. There are more mordant plant dyes that can dye yellow. For example, quince grass contains luteolin, which can mordant a bright yellow with green light. The "筭绶" dyed from ancient special quince grass (called 筭(lì) grass in ancient times) ", as an official ornament. Another example is Cotoneaster and Zhe: "The wood is dyed yellow and red, which is called Zhehuang" (Compendium of Materia Medica). The flower buds of the Sophora japonica tree, Sophora japonica rice, was also an important mordant dye for yellowing in ancient times. Mulberry bark "boiled in juice can be stained brown for a long time" ("Dietotherapeutic Materia Medica", "Lei Gong Pao Zhi Lun"). The pigment contained in cotinus and cypress wood is called fisetin. The dyed fabric appears reddish yellow under sunlight and brilliant red under candlelight. This mysterious light color difference makes it the most noble clothing color in ancient times. Regarding dyes, "Liu Dian of the Tang Dynasty" records that "Emperor Wen of the Sui Dynasty made yellow robes to listen to the court, and it has been used as a market to this day." In the Ming Dynasty, it was also "subject to the emperor." This system of clothing and color was later spread to Japan.
In addition to natural alum, the aluminum mordants used in ancient my country also used aluminum salt-rich oak wood and chun wood ash as mordants. In the Song Dynasty, the Dayuling River water dissolved in aluminum salts was also used as mordant. Su Fang's.
The oak tree (that is, the oak tree, called "Pu Qiang" in the "Book of Songs", see "Zhaonan·Yeyoudieqiu") and the gallnut which is a specialty of my country contain pyrogallol tannins; Persimmons, holly leaves, etc. contain catechol tannins. Tannins are directly used to dye fabrics in a light yellow color, but when combined with iron salts, they turn into black. "Xunzi Encouraging Learning Chapter" said that "the white sand is in nirvana, and it is black with it." Nirvana is ferrous sulfate (also known as green vitriol, green vitriol, and soap vitriol in ancient times). Fabrics dyed with tannin are then If dyed with alum, it will become "black". Black was mostly the color of civilian clothing in ancient times. During the Qin and Han Dynasties, "clothes, banners, and festival flags were all black" ("Historical Records: The Chronicles of Qin Shihuang"). Later, more and more iron mordants were needed for dyeing black. By around the sixth century AD, the working people of our country were artificially producing iron mordants. Plants containing tannins include sage, tallow leaves, etc. There are also written records in ancient times that they can be dyed black. Although others, such as oak bark and pomegranate peel, have not been recorded, they were used as black dyes in the vast rural areas of our country until liberation.
Reduced oxidation dyes The indigo grass mentioned in "The Book of Songs Xiaoya · Picking Green" in "The end of the day is to pick blue, and there will be no more than one shade" is a natural reduced oxidation dye. Indigo contains indigo, which can dye fabrics after being soaked in water and then oxidized into blue indigo by air. Before the Zhou Dynasty, fresh indigo grass was used for dipping and dyeing, so the "Book of Rites·Yue Ling" stipulates that "people are ordered not to mow indigo for dyeing in midsummer." During the Spring and Autumn Period and the Warring States Period, due to the fermentation method used to reduce indigo to indigo white, pre-made blue mud (containing indigo) could be used to dye cyan, so there is "green, taken from blue and green from blue" ("Xunzi Encouraging Learning") Chapter") statement. In the sixth century AD, Jia Sixie of the Northern Wei Dynasty described in detail the method of making indigo from indigo grass in ancient my country in his "Qi Min Yao Shu": "Mow indigo and place it upside down in the pit, then put it into the water," suppress it with stones or wood. So that all the bluegrass is soaked in water, the soaking time is "one night when it is hot, and another night when it is cold," and then filtered, and the filtrate is placed in an urn, "take ten stone urns and put one bucket of five liters of lime," "quickly criticize." First, "wait for the indigo dissolved in the water to combine with the oxygen in the air to form a precipitate, and then "clarify and purge the water." Choose another "small pit to store the indigo." After the water evaporates, "like strong porridge," serve it. In the container, "the blue lake is ready". This can be said to be the earliest record of the process of preparing indigo in the world.
By the Ming Dynasty, there were already five kinds of indigo that could be used to make indigo, and people had observed that the "red flame color was faint" after dyeing indigo ("Tiangong Kaiwu"), which shows that the working people of our country at that time had noticed that there were also natural indigo. A small amount of isatin is present.
Other dyes Safflower is one of the plant dyes that can be dyed red in ancient times. During the Qin and Han Dynasties, there were people who "planted red and blue flowers as a career." Red and blue flowers are safflowers, which contain a red pigment called safflower glycoside and a yellow pigment. Safflower glycoside can be leached from safflower with alkali solution and added with acid to turn fluorescent red. The complex physical and chemical process of impregnating and extracting dyes from safflower has been described in detail in "Qi Min Yao Shu". The acids used at that time were organic acids such as "corn rice slurry water" and "vinegar pomegranate" as color-developing agents. In "Tiangong Kaiwu", black plum is added as a hair color agent. The organic acids in pomegranate and plum are polybasic acids, and the color development effect is better than the acetic acid (monobasic acid) in "corn rice slurry water". When neutralized, it precipitates quickly and the color is pure. If you want to peel off the original red color of fabrics dyed with safflower, you only need to "soak the dyed silk" and add dozens of drops of alkaline rice ash water to "remove every trace of red" on the fabric. The washed red water is not thrown away, it is "hidden in the mung bean powder" and can be released again when needed to dye it red, "not a drop is consumed". ("Tiangong Kaiwu")
In addition to safflower, there are also rehmannia glutinosa, holly leaves, etc. that can be used as alkaline dyes ("Qi Min Yao Shu", "Compendium of Materia Medica").
The development of dyeing technology
When dyeing with a certain dye, the color of the fabric becomes darker each time it is dip-dyed. In ancient times, when over-dying madder with red, there were different names and colors from light red to deep red. “The first dye is the 縓, then the 縀, and the third dye is the 纁” (Erya). , and the seven elements are the 缁." ("Kao Gong Ji·Zhongshi")
When over-dyed with two different dyes, a third color can appear. However, due to the masking effect of color and the interaction of the chemical components of dyes and mordants, overdying with different dyes is also carried out regularly. "Huainanzi Shuo Shan Xun" once recorded: "It is OK to dye green first and then black, but not black first and then green." This shows that the ancient working people have mastered the method of over-dying fabrics with various dyes in production practice. effect. In addition, there is a saying in ancient books that "green and yellow are green, and today, garcinia combined with indigo is bitter green." It points out that in three primary color overdying, although cyan (that is, blue) and yellow can be combined to make green, due to the use of cyan, indigo, Different yellow dyes can produce different green colors. Dyes with different chemical properties often encounter difficulties when over-dying. For example, the berberine contained in cork barberry is an alkaline dye. If mixed with other dyes, precipitation will occur and the dyeing effect will be lost; if cork barberry is used first If it is dyed, it cannot be dyed with other dyes. It is usually dyed with other dyes first and then with cork. In addition, the same mordant dye can also be dyed in different colors if the mordant is different. Various dyeing methods have been described in "Duo Neng Shi Shi" of the Ming Dynasty. Take the dyeing of jujube brown as an example: first dye with hematoxylin alum, then add green alum, "Watch the color depth when swirling, too much will be black, less will be red, the combination is the best."
Follow up. With the continuous improvement and development of dyeing technology, the colors of dyed textiles are also constantly enriched. From the Western Zhou Dynasty to the Spring and Autumn Period, only the "Book of Songs" mentioned about the color of fabrics: "Green clothes are beautiful, green clothes are yellow" ("Bei Feng·Lv Yi"), "缁 clothes are suitable" ("Zheng Feng") ·缧衣"), "Qingqing Zijin" ("Zheng Feng·Zijin"), "缷衣綦衣" ("Zheng Feng·Out of the East Gate"), "plain clothes Zhu Xi" ("Tang Feng· "Yangzhi Shui"), "Zai Xuan Zai Huang" ("Bin Feng·July"), etc., as well as wool fabric dyeing "Lao clothes like a teacup", "Lao clothes like a jade" ("Wang Feng·Car"), etc. , it can be said to be colorful. Later, dyeing technology, especially the over-dying technology of different dyes, continued to develop. By the Western Han Dynasty, it can be seen from the textiles unearthed from Han Tomb No. 1 in Mawangdui, Changsha that the color spectrum had been greatly enriched. During the Sui and Tang Dynasties, dyeing technology developed even more. Take the embroidery unearthed from Astana in Xinjiang as an example: the background colors include bright red, yellow, leaf green, emerald blue, sapphire blue, lake blue, purple, lotus root, bronze, etc. . By the Ming Dynasty, the color spectrum of dyeing was more refined, and only red dyeing included scarlet, lotus red, peach red, silver red, water red, wood red, etc. ("Tiangong Kaiwu").
Dyeing production activities also flourished in the Ming Dynasty. In addition to the royal family's "Indigo Institute" to serve the feudal ruling class, various private dyeing workshops were also opened among the people. There were thousands of dyers in Suzhou alone ("Wanli of the Ming Dynasty") "Records" Volume 361), there are different divisions of labor in the dyeing workshop, such as blue workshop, red workshop, red bleaching workshop and variegated workshop.
Types of yellow pigment: In ancient China, yellow was a noble color and was once reserved exclusively for emperors and courts. Today, yellow pigment has become the most widely used pigment variety in building sanitary ceramics. There are many types of yellow pigments, the main types of which include zirconium vanadium yellow, zirconium praseodymium yellow, lead antimonate yellow, titanium yellow, chromium yellow, cadmium yellow and other types. Their operating temperature and atmosphere requirements are as follows.
Zirconium vanadium yellow and zirconium praseodymium yellow: The two have a wide range of use. The applicable temperature is low temperature 800 degrees -1000 degrees; medium temperature 1200 degrees; the maximum operating temperature is 1280 degrees -1300 degrees. The difference between the two is that zirconium vanadium yellow can be used in both oxidizing and reducing flames; while zirconium and praseodymium yellow can only be used in oxidizing flames and not in reducing flames.
Lead antimonate yellow and titanium yellow: are low-temperature pigments. Only limited to low temperature applications. The operating temperature is 800-1000 degrees, and it can only be used for oxidation flame firing, not reduction flame.
Cadmium Yellow: The lowest temperature colorant used in low-temperature ceramic pigments. The operating temperature is 800 degrees. There are no special requirements for flame atmosphere.
[2] Types of red pigment: Red symbolizes enthusiasm and the jump of life. In current building sanitary ceramic products, red ceramic pigment varieties include manganese red, chromium tin red, chromium aluminum red, chromium silver red, iron chromium red and selenium chromium red. The usage temperature and atmosphere requirements for red pigments are as follows.
The three ceramic pigments, manganese red, chromium-aluminum red and iron-chromium red, are fired at the same temperature and flame atmosphere conditions. They can be used in various situations such as the lowest firing temperature of 800 degrees -1000 degrees; the medium temperature of 1200 degrees; the highest firing temperature of 1280 degrees -1300 degrees. These three pigments can only be used in oxidizing flame atmospheres and cannot be used in reducing flame firing conditions.
The firing range of these two ceramic pigments, chromium tin red and chrome silver red, is a minimum temperature of 800 degrees, a medium temperature of 1000-1200 degrees, and a maximum use temperature of 1280 degrees. However, the atmospheres used between the two are different. Chromium tin red can only be used under oxidizing flame firing conditions. The chromium silver red pigment can be used in both oxidizing flame and reducing flame firing.
Selenium-cadmium red is a low-temperature ceramic colorant. Its firing temperature can only be below 800 degrees.
[3] Types of brown ceramic pigments: Brown ceramic pigments are calm and stable in color. The brown pigments currently used include iron chromium zinc brown, iron chromium zinc brown, iron chromium brown and iron chromium zinc aluminum brown. The firing temperatures of these four ceramic pigments range from a minimum firing temperature of 800 degrees. to a medium temperature of 1000 degrees to 1200 degrees, and a maximum temperature of 1280 degrees to 1300 degrees. In terms of firing atmosphere, they can be widely used in oxidizing flame or reducing flame.
[4] Types of green ceramic pigments. The color of green ceramic pigments is fresh and bright, and now it has formed varieties such as chrome green, malachite green, praseodymium vanadium green and so on. Among them, chrome green is also called Victoria green. The use temperature range of it and malachite green ceramic pigment is low temperature 800 degrees, medium temperature 1000 degrees-1200 degrees, and the highest temperature is 1280 degrees. The firing atmosphere is not limited by oxidizing flame or reducing flame.
The firing temperature range of praseodymium vanadium green is wider than the above two. It can not only be used at low temperatures of 800 degrees, medium temperatures of 1000 degrees -1200 degrees, but also can be used at the highest temperature of 1280 degrees -1300 degrees. In terms of the firing atmosphere, oxidizing flame or reducing flame firing conditions can also be met.
[5] Blue ceramic pigment varieties: Among building sanitary ceramic products, blue ceramic pigments are elegant and luxurious in color. At present, the most commonly used types are cobalt blue, deep blue, aquamarine, zirconium vanadium blue and zinc silicate blue. In addition to zinc silicate blue, there are four ceramic pigments, cobalt blue, deep blue, aqua blue and zirconium vanadium blue, with a wide range of firing temperatures, which can meet the firing range from a minimum temperature of 800 degrees to a maximum temperature of 1300 degrees. The highest firing temperature of zinc silicate blue is 1280 degrees. In the firing flame atmosphere, blue ceramic pigments can meet the firing conditions of reducing flame or oxidizing flame.
[6] Types of purple ceramic pigments: There are now varieties such as neodymium silicon violet and neodymium aluminum violet.
Their firing temperature range is between 800 degrees and 1280 degrees. There are no special requirements for the firing flame atmosphere, and they can meet the needs of oxidation flame and reduction flame firing.
[7] Types of gray ceramic pigments: There are two types of pigments: tin antimony gray and zirconium gray. The sintering temperature of tin antimony ash is between 800 degrees and 1280 degrees. The burning temperature range of zirconium ash is between 800 degrees and 1300 degrees. Both are suitable for oxidizing flame firing conditions, but cannot be used for reducing flame firing.
[8] Types of black ceramic pigments: Black pigments and black glazes have the oldest history of use, and their color elements are iron oxide. After improvement, new varieties such as nickel-chromium-iron-cobalt black and iron-chromium-cobalt-manganese black have been formed, so the color is more pure and stable. Nickel-chromium-iron-cobalt black material has a wide range of use temperatures and can meet the firing temperature of 800 degrees to 1300 degrees. But in terms of firing atmosphere, iron-chromium-cobalt-manganese black can be fired in an oxidizing flame or reducing flame atmosphere, but nickel-chromium-iron-cobalt black can only be fired in an oxidizing flame.