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Consumer Products

These new textile dyeing methods could make fashion more sustainable

Large and small suppliers vow to help a resource-intensive, cost-sensitive industry change with the times

by Melody M. Bomgardner
July 15, 2018 | APPEARED IN VOLUME 96, ISSUE 29

Credit: Intech Digital | High-resolution color patterns can be printed directly onto cotton using pigment inks rather than dyes to reduce the use of water and chemicals.

In brief

Shoppers looking for their next great outfit make their selections on the basis of color, cut, style, and price. They may not know that dyeing clothes requires massive amounts of water, energy, and chemicals. Those chemicals are released in wastewater from dye houses and textile mills in places such as China, India, and Bangladesh. Reports of rivers with unnatural hues have inspired government crackdowns and sustainability pledges from international apparel brands. But changing this $3 trillion industry will require innovation that can be scaled up and adopted without cost or disruption for manufacturers. Read on to learn about greener ways to color clothes that may soon be available from your favorite retailer.

In early June, Dalton Cheng realized something big was afoot. Cheng, who is head of technology for the textile printing firm Intech Digital, heard from customers that Chinese government authorities in Jiangsu province had shut down massive factories that produce synthetic dyes used by the textile industry.

It was just the latest in a series of actions that started in the summer of 2017, when tens of thousands of China’s factories were forced to close and undergo environmental inspections.

Overall, as much as 60% of China’s denim-dyeing chemical capacity has been shuttered, Cheng says, equal to roughly 30% of global capacity. And that’s why his phone was ringing. Intech, headquartered in Hong Kong, might be in a position to help apparel industry customers out of a critical supply bind.

Intech’s specialty is digital printing on textiles, including cotton and other cellulosic fabrics like rayon. Printing textiles with pigments rather than dyes uses very little water, Cheng says, and produces much less waste than traditional methods.

Digital printing is one example from a growing list of new, more sustainable fabric-coloring technologies from both major suppliers and smaller chemical and biotech start-ups. The companies see business opportunity in tackling dyeing’s wasteful water and energy practices and its reliance on toxic chemicals that can give rivers shocking hues and harm human health.

But the barriers facing those working to promote a more sustainable textile technology are quite high. The industry’s sheer scale makes it hard to have an impact: Textiles are a $3 trillion-per-year business that employs nearly 60 million workers worldwide, according to economic research firm Euler Hermes and FashionUnited, an industry information resource.

It’s also a manufacturing industry under pressure. Price competition is fierce, and profits are shrinking thanks to volatile raw material costs and rising wages. Despite public commitments by apparel brands to become more sustainable, suppliers contacted by C&EN say their customers will not buy anything that could raise the cost of a finished garment by as little as a penny.

The factory shutdowns have disrupted the textile supply chain, says Holger Schlaefke, global marketing manager at Huntsman’s textile effects segment. Huntsman, Archroma, and DyStar are the world’s largest suppliers of dyes and textile chemicals.

09629-cover-dyefactoryCXD.jpg
Credit: Lu Guang/Greenpeace
Greenpeace's Detox My Fashion campaign brought attention to pollution and health hazards of dye and other chemicals used in textile manufacturing, including at this plant in Tianjin, China.

“Shutdowns are a concern for companies like Huntsman and also for retailers,” Schlaefke says. “You can imagine retailers have contracted with a fabric-producing mill—they negotiated six months ago and agreed on a price—but suddenly that price is not certain anymore. It’s not a crisis, but it makes business a little more complicated for everyone.”

The largest impact of the factory shutdowns has been in the supply and price of so-called disperse dyes, which are used to color synthetic fibers like polyester, a specialty of Chinese producers, Schlaefke says. Availability of reactive dyes, which are used on cotton, was also reduced, though manufacturers in cotton-rich India are likely to take up the slack.

In India as well, the government is taking steps to reel in the textile industry to save precious water resources. “In India, a trend is huge investment in wastewater treatment for liquid discharge,” Schlaefke says. It’s now common for factories to reuse 90% of their water.

While both cotton and polyester are normally colored with synthetic dyes, dyeing cotton is a more water- and heat-intensive process. The surface of cotton fibers is negatively charged and doesn’t readily react with negatively charged dye compounds.

Even with an assist from salts and alkali added to the dye solution, cotton takes up only about 75% of the dye. To ensure colorfastness, dyed fabric or yarn is washed over and over again in hot water, creating large amounts of wastewater.

All told, about 200 L of water is used to produce 1 kg of fabric. A review of wastewater treatment steps found that textile effluent contains high concentrations of dyes and chemicals, including chromium, arsenic, copper, and zinc. Dyes and chemicals released into waterways also block sunlight and increase biological oxygen demand (J. Chem. Eng. Process Technol. 2014, DOI: 10.4172/2157-7048.1000182).


Learn the textile industry's lingo

Bleeding and crocking: Two components of colorfastness. Bleeding happens when dye comes off a fabric in contact with liquid. Crocking occurs when a dye on a dry fabric rubs off on another dry fabric.

Colorfastness: The ability of a dye to preserve the original color during industrial processing and subsequent customer use. The American Association of Textile Chemists & Colorists provides several dozen test methods to ensure colorfastness of dye products.

Digital textile printing: Directly printing colors and patterns onto fabric using design software, large-format printers, and specialty inks made with pigments or dyes. Digital printing is an alternative to standard screen printing, which uses a constrained color palette and requires separate stencils and production steps for each color.

Dye: Soluble chemicals that contain chromophores, or color-containing compounds. Dyes are mixed with other additives in a color solution. They can be derived from natural sources, such as plants, but are more commonly human made. Different classes of dyes are used for different fibers and stages of the textile production process.

Direct dye: A class of dye that can be applied directly to cotton or other cellulosic fabrics such as rayon, silk, and wool. Direct dyes are applied in a neutral or alkaline bath of hot water. They do not require mordant or fixatives for fastness; instead, they attach with hydrogen bonds and van der Waals forces. Direct dyes are soluble salts of complex sulfonic acids, including diazo or polyazo chemicals.

Disperse dye: A category of nonionic dyes used to color synthetic yarns and fabrics such as polyester. These organic chemicals, mostly monoazo dyes, are nonsoluble and rely on dispersing agents to spread the color molecules in water.

Reactive dye: A class of colored synthetic organic chemicals that attach to textile fibers via a chemical reaction that forms a covalent bond. Reactive dyes are the most permanent of all dye types and are the most common type of dye used on cotton and other cellulose fibers. They are categorized by their functional group, such as dichlorotriazine or vinyl sulfone.

Dye exhaustion or dye fixation: The mass of dye taken up by the yarn or fabric divided by the total initial mass of dye in the water bath. Once the dyeing process reaches equilibrium, a portion of the dye remains in the dye bath and becomes part of the dye process wastewater. The exhaustion ratio depends on the quality of the dye and the characteristics of the fiber.

Leveling agent: Used in disperse dyeing to regulate or slow the uptake of dye onto synthetic fibers to ensure that the color level is uniform. Leveling agents are often nonionic surfactants that increase the solubility of the dye and slow adsorption.

Mordant: Also called a dye fixative, a substance used to chemically bond a dye to natural fibers to ensure fastness. Mordant chemicals include alum, caustic soda, and metal salts. The mordant forms a coordination complex with the dye, increasing its molecular weight and making it insoluble.

Pigment: Insoluble materials, usually in powder form, that add color to inks, paints, plastics, cosmetics, and foods. When used on textiles, they require binders or other additives to attach to the fibers. Pigments can be derived from minerals but can also be made synthetically. Because they are not soluble in water, they can last longer than dyes.


To reduce this burden, Huntsman has developed a line of dyes for cotton called Avitera that bonds to the fiber more readily. According to the company, the colors require one-quarter to one-third less water and one-third less energy. Three reactive groups are attached to the dye formula’s chromophore—or color-providing molecule—compared with the one or two reactive groups common for cotton dyes. Thanks to these extra reactive groups, the dye step lasts about four hours, compared with seven hours for conventional dyes.

Still, it takes a lot of legwork to sell customers on a new suite of dyes. “It can be hard to show cost savings when the savings comes from water use or energy,” Schlaefke says. Different regions and countries have different cost structures, he says. For example, Bangladesh is now the biggest cotton-producing country, “and as we know, they have no shortage of water,” he notes.

Another way to improve the bond between dyes and cotton fibers is a process called cationization. In North Carolina, textile industry veteran Tony Leonard is taking that approach. Leonard is the inventor and technical director behind ColorZen, a start-up that has developed a cotton pretreatment step.

 

There are beautiful colors in the ocean, in insects—you can crack open a wide palette of colors.”
David Nugent, cofounder, Colorifix

“With conventional cotton dyeing, salt is used to negate the charge on the surface of the cotton,” Leonard explains. “ColorZen technology uses a quaternary ammonium compound to permanently attach a positively charged amino site on the cellulose molecule.” That makes for a natural attraction between dye and fiber, he says.

ColorZen treats raw cotton fiber right from the field after the seeds are removed. “North Carolina is still the heart of the cotton and textile industry here in the United States, and there are ready supplies of baled U.S. cotton here that our customers are tapping into,” Leonard notes. After treatment, cotton is spun into yarn at customer facilities.

Leonard contends that ColorZen’s pretreatment makes the dyeing process faster while using 90% less water, 75% less energy, and 90% fewer auxiliary chemicals. It also cuts out almost half the dye compared with processes that call for salts in the dye bath.

The company has a partnership with the manufacturing technology firm Jabil to help it scale up its plant in Mebane, N.C. It is also in a program run by the apparel start-up incubator Fashion for Good. Leonard says the company is developing a supply chain by educating dye houses, spinners, and retailers about ColorZen’s benefits.

Even the best pretreatment process can’t eliminate the health effects of the dyes and the chemicals used to make them. That’s the focus of many of the textile industry’s eco-certification programs.

“With advances in measurement instruments, we’re seeing more evidence of contaminants and degradation products than ever before,” observes John Frazier, technical director at Hohenstein Institute America, a textile research organization. Hohenstein developed Oeko-Tex, a series of standards and tools for certifying nontoxic textiles. The first version of the standard was called Oeko-Tex 100 for the number of chemicals it tracked. Oeko-Tex certification is now up to more than 300 chemicals.

The industry needs to both develop “better chemistry and ensure there is less water going out the back,” Frazier says. He says he’s seeing “a ton of innovation happening. It’s very exciting.”

Schlaefke says Huntsman’s Avitera dyes were formulated to be free from p-chloroaniline (PCA), a hazardous chemical used as an intermediate in the manufacture of azo dyes and pigments. “What we see now is a bit more retailers are looking at PCA,” he notes. Currently, brands including REI and Levi Strauss & Co. restrict the use of PCA along with a list of other amines from colorants.

Synthetic indigo, used to make blue jeans blue, is an example of a dye that can release unreacted chemicals downstream of manufacturing. A small number of Chinese manufacturers produce most of the world’s indigo using aniline as a key raw material. Indigo is unlike most dyes in that in its unreduced form it is not soluble. So companies like Archroma upgrade it into easier-to-use, prereduced solutions that are more water soluble.

The company became concerned after seeing published reports that about 400 metric tons of aniline per year escapes the dyeing process from 70,000 metric tons of indigo. Two-thirds of the escaped chemical ends up in wastewater, on workers, and in the air, while one-third stays on the denim that goes to stores, says James Carnahan, Archroma’s global sustainability manager for textiles.

Archroma developed a technology for prereducing indigo to prevent aniline from carrying through as a contaminant. Finished textiles colored with the dye contain a nondetectable amount of aniline, whereas competitor dyes can contain up to 2,000 ppm of the chemical, according to Archroma.

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Brands’ awareness of aniline contamination is growing, and the compound has started to appear on lists that brands send to manufacturers restricting the chemicals they can use.

Carnahan acknowledges differing views about how big a problem aniline is in the textile industry. It has a better reputation than the category 1 carcinogenic amines that cleave off of azo dyes and were an early target for elimination by clothing brands. “Aniline is category 2, instead—which is not good, though,” Carnahan says.

Of course, in the beginning, indigo came from a plant, not a factory. The very first pair of modern-style blue jeans, made by Levi Strauss, debuted in 1873. That was about 25 years before chemists developed the synthetic route to indigo dye—with its unappetizing starting materials of aniline, formaldehyde, and hydrogen cyanide.

The ambition at Stony Creek Colors is to return to those early days. Founder Sarah Bellos says a complete life-cycle review of the production and use of synthetic indigo provides plenty of reasons to look again at indigo from plants.

Environmental hit

Dyeing cotton has more impact than dyeing other fibers.


Cotton

Dyeing: Warm temperature, long process time, requires addition of large amounts of salt and alkali fixatives

Dye fixation: Poor, 75%

Washing: Long, energy- and water-intensive process using multiple baths, with at least one at boiling temperature


Polyester

Dyeing: Hot temperature, short process time, no fixatives required

Dye fixation: Good, 99% or more

Washing: Shorter process requiring less energy, water, and chemicals than cotton. Uses alkali and chemical reducing agent.


Viscose (rayon)

Dyeing: Warm temperature, long process time, requires less salt and alkali than cotton

Dye fixation: Fair, 85–90%

Washing: Similar to cotton but shorter process, possibly due to less unfixed dye to be removed


Wool

Dyeing: Warm temperature, simple process

Dye fixation: Good, 95% or more

Washing: Generally a relatively simple wash-off procedure

 

Source: Natural Resources Defense Council

Stony Creek is developing varieties of leguminous indigo plants that can provide a high-yield, high-profit crop for Tennessee farmers looking for an alternative to tobacco. The company is selling all the dye it can make; its goal is to expand U.S. indigo production to 6,000 hectares in the next five years. That could displace 2.8% of global synthetic indigo production.

The indigo molecule itself is exactly the same as the synthetic version, with one small difference: “Synthetic indigo has a tighter crystal formation that makes it more difficult to reduce,” Bellos says. Dye houses can reduce natural indigo in bacterial fermentation vats or use more common reducing systems, she adds.

Other start-ups have also turned to biology—in particular, engineered microbes—to reduce the use of chemicals in textile dyes. U.K.-based Colorifix and the French firm Pili say microbes can produce high-performance, renewable dyes suitable for mainstream textiles. All that is required to scale up are fermentation tanks and sugar.

The idea for Colorifix came out of a biological sensor program in Nepal and Bangladesh. David Nugent and colleagues were in the region to test drinking water wells for arsenic. They asked local village governments what other substances in their water concerned them. “We got a large list of chemicals,” Nugent recalls. “When we asked, ‘Where do they come from?’ the answer we got was textiles, again and again.”

The team was already using color made by microorganisms to act as a sensor for water contaminants. Soon, Nugent says, it became clear the researchers could engineer them to produce natural colors, including anthocyanins and carotenoids.

“Once you start looking at how nature makes colors, you see a lot of similarities in the sequences of the proteins and enzymes,” Nugent says. With more resources, he’d like to go prospecting to find new molecules. “There are beautiful colors in the ocean, in insects—you can crack open a wide palette of colors.”

Not all the colors that engineered microbes can make meet textile industry requirements for lightfastness and temperature stability. Chlorophyll, the secret to nature’s abundance of green, can turn an unstylish brown in factory conditions, Nugent says.

But microbes that produce stable colors can be adopted by dye houses with very little change to their normal processes. First the microbes go into a solution like a regular dye and get embedded in the textile fiber. Then they are given nutrients that cause them to grow. When heat is applied, the organisms’ membranes burst. That causes the color to chemically attach to the fiber with help from metal ions and salts in the microbes’ cytoplasm.

Nugent says the process works like a very efficient reactive dye that requires only a single finish wash. He claims a water savings of 90% and an energy savings of 20% over standard processes. Colorifix is setting up pilot operations in Italy and France; partner dye houses first have to get a certification to work with genetically modified microbes.

Pili got its start as a biology outreach program. “We were doing workshops with kids, growing bacteria and making colors with them, painting with them,” Chief Science Officer Guillaume Boissonnat recalls. In 2015, he and his partners realized they could make industrially useful colors that way.

Biology is more efficient than the chemical industry at making dye structures, Boissonnat argues. “Dyes are usually the aromatic molecules from heavy fractions of petroleum. We have made some calculations that show to produce 1 kg of dye, you need 100 kg of petroleum, 1,000 L of water, and 10 kg of other chemicals.”

But the major portion of water used for textile dyeing comes after dyeing, when fabrics, particularly cotton, have to be washed over and over again to remove unfixed dye. Instead, manufacturers can skip dyes and use pigments. As at Intech Digital, the enabling technology for that move is large-scale printers that take the place of dyeing vats. The printers use special versions of ink-jet printheads designed to work with textile inks.

The use of digital textile printing is growing rapidly, thanks in large part to demand from fast-fashion purveyors, says Tim Check, a textile product manager at Epson, which makes printers, printheads, and inks for textiles. Check says retailers such as H&M or Zara demand short runs of styles to appear in stores in as little as two weeks, rather than the traditional design schedule of huge runs delivered after several months.

Patterned textiles for such garments were historically made by screen printing, which is expensive to set up, requires custom templates for each color, and uses a limited set of hues. Digital printers, which give designers almost unlimited choices, are taking over some of that market.

“The big reason we’re really excited is it’s having huge growth, well over 20% per year,” Check says. But that increase is from a small base of about 2–3% of total textile output.

Digital printing on polyester uses a two-step dye sublimation process that is almost waterless. The pattern is first printed on transfer paper; heat then turns the color into a cloud of gas, which bonds with the softened polyester.

This process doesn’t work for cotton, silk, and other natural fabrics, Intech’s Cheng points out. For them, his firm offers a new specialty ink made with powdered, insoluble pigments plus a polymer-like binder designed to make the color stick.

Epson’s Check says the digital printing approach can allow apparel manufacturers to operate in regions closer to their customers, such as in North America. “All you need is a printer and a heat system to fix the ink. That means you can do that here in the U.S. without the environmental concerns or cost of managing wastewater,” he says.

 

The textile industry, including retail, is very, very competitive, and in the end, cost matters.”
Holger Schlaefke, global marketing manager, Huntsman’s textile effects segment

Huntsman’s Schlaefke agrees that digital printing is a trend that could have an impact on how much and what types of colorants are used. “The market is moving in the right direction for printing,” he says.

Since Huntsman sells both traditional dyes and specialty inks, it stands to gain whichever way the wind blows. Schlaefke says the segment’s growth will depend in large part on how economical the machines become.

“The textile industry, including retail, is very, very competitive, and in the end, cost matters,” Schlaefke says. He points out that a penny of additional cost adds up to a lot of money when a company is making millions of garments.

For companies that have strong chemistry capabilities, being able to help textile customers meet sustainability goals lends a competitive edge. “If you only see it as a threat and you are getting worried, I think you won’t survive in the long run,” Schlaefke says.

But nothing is straightforward in the textile industry. While China cracks down with environmental inspections, and wages in the country rise, the industry is moving to countries, including Bangladesh and Vietnam, with fewer environmental controls. Innovators with greener dyeing technology will have to work hard to keep their progress from unraveling.

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Comments
Charley Liberko (Thu Jul 19 10:25:47 EDT 2018)
Dyes are one of the oldest areas of research in organic chemistry and it is interesting that there is still more to learn. This is a great story but it left me hungry to know more about the chemical structures of the dyes. Chemists communicate through chemical structures and I would like to encourage C&EN to include more structures in their articles.
Joe Atkinson (Sun Jul 22 14:54:04 EDT 2018)
I strongly second Charley Liberko's request for structures. "A picture is worth a thousand words" and nowhere more so than in chemistry.
Paul C,Li (Mon Jul 23 10:16:53 EDT 2018)
All technical headaches described in papers have very little difficulties for us to get them done one after another in whatever you want to make。 A series of pluripotent intermediate is available on demand to get the job done, I am confident。The chemistry and engineer job work with regulatory agency conscious with cost and performance is in place。

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