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Nylon Fiber

Nylon Fiber

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What Is Nylon?

A manufactured fiber in which the fiber forming substance is any long chain synthetic polyamide having recurring amide groups (-NH-CO-) as an integral part of the polymer chain (FTC definition). The two principal nylons are nylon 66, which is polyhexamethylenedianime adipamide, and nylon 6, which is polycaprolactam. Nylon 66 is so designated because each of the raw materials, hexamethylenediamine and adipic acid, contains six carbon atoms. In the manufacture of nylon 66 fiber, these materials are combined, and the resultant monomer is then polymerized. After polymerization, the material is hardened into a translucent ivory-white solid that is cut or broken into fine chips, flakes, or pellets. This material is melted and extruded through a spinneret while in the molten state to form filaments that solidify quickly as they reach the cooler air. The filaments are then drawn, or stretched, to orient the long molecules from a random arrangement to an orderly one in the direction of the fiber axis. This drawing process gives elasticity and strength to the filaments. Nylon 6 was developed in Germany where the raw material, caprolactam, had been known for some time. It was not until nylon 66 was developed in the United States that work was initiated to convert caprolactam into a fiber. The process for nylon 6 is simpler in some respects than that for nylon 66. Although nylon 6 has a much lower melting point than nylon 66 (a disadvantage for a few applications), it has superior resistance to light degradation and better dyeability, elastic recovery, fatigue resistance, and thermal stability. Two other nylons are: (1) nylon 11, a polyamide made from 11-aminoundecanoic acid; and (2) nylon 610, made from the condensation product of hexamethylenediamine and sebacic acid. Nylon 610 has a lower melting point than nylon 66 and the materials for its manufacture are not as readily available as those for nylon 66. Experimental work has been conducted on other. Nylon was the first truly synthetic fiber to be commercialized (1939). Nylon was developed in the 1930s by scientists at Du Pont, headed by an American chemist Wallace Hume Caruthers (1896-1937). It is a polyamide fiber, derived

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from a diamine and a dicarboxylic acid, because a variety of diamines and dicarboxylic acids can be produced, there are a very large number of polyamide materials available to produce nylon fibers. The two most common versions are nylon 66 (polyhexamethylene adiamide) and nylon 6 (Polycaprolactam, a cyclic nylon intermediate). Raw materials for these are variable and sources used commercially are benzene (from coke production or oil refining), furfural (from oat hulls or corn cobs) or 1,4-butadiene (from oil refining).

Federal Trade Commission Definition for Nylon Fiber:
A manufactured fiber in which the fiber forming substance is a long-chain synthetic polyamide in which less than 85% of the amide-linkages are attached directly (-CO-NH-) to two aliphatic groups.

Nylon — The “Miracle” Fiber
In September 1931, American chemist Wallace Carothers reported on research carried out in the laboratories of the DuPont Company on “giant” molecules called polymers. He focused his work on a fiber referred to simply as “66,” a number derived from its molecular structure. Nylon, the “miracle fiber,” was born. The Chemical Heritage Foundation is currently featuring an exhibit on the history of nylon. By 1938, Paul Schlack of the I.G. Farben Company in Germany, polymerized caprolactam and created a different form of the polymer, identified simply as nylon “6.” Nylon's advent created a revolution in the fiber industry. Rayon and acetate had been derived from plant cellulose, but nylon was synthesized completely from petrochemicals. It established the basis for the ensuing discovery of an entire new world of manufactured fibers. An American Romance: DuPont began commercial production of nylon in 1939. The first experimental testing used nylon as sewing thread, in parachute fabric, and in women's hosiery. Nylon stockings were shown in February 1939 at the San Francisco Exposition — and the most exciting fashion innovation of the age was underway.

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American women had only a sampling of the beauty and durability of their first pairs of nylon hose when their romance with the new fabric was cut short. The United States entered World War II in December 1941 and the War Production Board allocated all production of nylon for military use. Nylon hose, which sold for $ 1.25 a pair before the War, moved in the black market at $10. Wartime pinups and movie stars, like Betty Grable, auctioned nylon hose for as much as $40,000 a pair in war-effort drives. During the War, nylon replaced Asian silk in parachutes. It also found use in tires, tents, ropes, ponchos, and other military supplies, and even was used in the production of a high-grade paper for U.S. currency. At the outset of the War, cotton was king of fibers, accounting for more than 80% of all fibers used. Manufactured and wool fibers shared the remaining 20%. By the end of the War in August 1945, cotton stood at 75% of the fiber market. Manufactured fibers had risen to 15%.

A Short History of Manufactured Fibers
For thousands of years, the use of fiber was limited by the inherent qualities available in the natural world. Cotton and linen wrinkled from wear and washings. Silk required delicate handling. Wool shrank, was irritating to the touch, and was eaten by moths. Then, a mere century ago, rayon — the first manufactured fiber — was developed. The secrets of fiber chemistry for countless applications had begun to emerge. Manufactured fibers now are put to work in modern apparel, home furnishings, medicine, aeronautics, energy, industry, and more. Fiber engineers can combine, modify and tailor fibers in ways far beyond the performance limits of fiber drawn from the silkworm cocoon, grown in the fields, or spun from the fleece of animals. The Early Attempts The earliest published record of an attempt to create an artificial fiber took place in 1664. English naturalist Robert Hooke suggested the possibility of producing a fiber that would be “if not fully as good, nay better” than silk. His goal remained unachieved for more than two centuries.

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The first patent for “artificial silk” was granted in England in 1855 to a Swiss chemist named Audemars. He dissolved the fibrous inner bark of a mulberry tree, chemically modifying it to produce cellulose. He formed threads by dipping needles into this solution and drawing them out - but it never occurred to him to emulate the silkworm by extruding the cellulosic liquid through a small hole. In the early 1880's, Sir Joseph W. Swan, an English chemist and electrician, was spurred to action by Thomas Edison's new incandescent electric lamp. He experimented with forcing a liquid similar to Audemars solution through fine holes into a coagulating bath. His fibers worked like carbon filament, and they found early use in Edison's invention. It also occurred to Swan that his filament could be used to make textiles. In 1885 he exhibited in London some fabrics crocheted by his wife from his new fiber. But electrical lamps remained his main interest, and he soon abandoned work on textile applications.

First Commercial Production
The first commercial scale production of a manufactured fiber was achieved by French chemist Count Hilaire de Chardonnet. In 1889, his fabrics of “artificial silk” caused a sensation at the Paris Exhibition. Two years later he built the first commercial rayon plant at Besancon, France, and secured his fame as the “father of the rayon industry.” Several attempts to produce “artificial silk” in the United States were made during the early 1900's but none were commercially successful until the American Viscose Company, formed by Samuel Courtaulds and Co., Ltd., began production its production of rayon in 1910. In 1893, Arthur D. Little of Boston, invented yet another cellulosic product — acetate — and developed it as a film. By 1910, Camille and Henry Dreyfus were making acetate motion picture film and toilet articles in Basel, Switzerland. During World War I, they built a plant in England to produce cellulose acetate dope for airplane wings and other commercial products. Upon entering the War, the United States government invited the Dreyfus brothers to build a plant in Maryland to make the product for American warplanes. The first commercial textile uses for acetate in fiber form were developed by the Celanese Company in 1924.

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In the meantime, U.S. rayon production was growing to meet increasing demand. By the mid-1920's, textile manufacturers could purchase the fiber for half the price of raw silk. So began manufactured fibers' gradual conquest of the American fiber market. This modest start in the 1920's grew to nearly 70% of the national market for fiber by the last decade of the century.

The Post-War Industry After the war, GI's came home, families were reunited, industrial America gathered its peacetime forces, and economic growth surged. The conversion of nylon production to civilian uses started and when the first small quantities of postwar nylon stockings were advertised, thousands of frenzied women lined up at New York department stores to buy. In the immediate post-war period, most nylon production was used to satisfy this enormous pent up demand for hosiery. But by the end of the 1940's, it was also being used in carpeting and automobile upholstery. At the same time, three new generic manufactured fibers started production. Dow Badische Company (today, BASF Corporation) introduced metalized fibers; Union Carbide Corporation developed modacrylic fiber; and Hercules, Inc. added olefin fiber. Manufactured fibers continued their steady march. By the 1950's, the industry was supplying more than 20% of the fiber needs of textile mills. A new fiber, “acrylic,” was added to the list of generic names, as DuPont began production of this wool-like product. Meanwhile, polyester, first examined as part of the Wallace Carothers early research, was attracting new interest at the Calico Printers Association in Great Britain. There, J. T. Dickson and J. R. Whinfield produced a polyester fiber by condensation polymerization of ethylene glycol with terephthalic acid. DuPont subsequently acquired the patent rights for the United States and Imperial Chemical Industries for the rest of the world. A host of other producers soon joined in. Today

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Innovation is the hallmark of the manufactured fiber industry. Fibers more numerous and diverse than any found in nature are now routinely created in the industry's laboratories. Nylon variants, polyester, and olefin are used to produce carpets that easily can be rinsed clean — even 24 hours after they've been stained. Stretchable spandex and machine-washable, silk-like polyesters occupy solid places in the U.S. apparel market. The finest microfibers are remaking the world of fashion.For industrial uses, manufactured fibers relentlessly replace traditional materials in applications from super-absorbent diapers, to artificial organs, to construction materials for moon-based space stations. Engineered non-woven products of manufactured fibers are found in applications from surgical gowns and apparel interfacing to roofing materials, road bed stabilizers, and floppy disk envelopes and liners. Non-woven fabrics, stiff as paper or as soft and comfortable as limp cloth, are made without knitting or weaving. As they always have, manufactured fibers continue to mean, “life made better.”

The chemical reactions
The chemical reactions are as follows.

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Nylons are also called polyamides, because of the characteristic amide groups in the backbone chain. Proteins, such as the silk nylon was made to replace, are also polyamides. These amide groups are very polar, and can hydrogen bond with each other. Because of this, and because the nylon backbone is so regular and symmetrical, nylons are often crystalline, and make very good fibers.

The nylon in the pictures on this page is called nylon 6,6, because each repeat unit of the polymer chain has two stretches of carbon atoms, each being six carbon atoms long. Other nylons can have different numbers of carbon atoms in these stretches. Nylons can be made from diacid chlorides and diamines. Nylon 6,6 is made from the monomers adipoyl chloride and hexamethylene diamine.

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This is one way of making nylon 6,6 in the laboratory. But in a nylon plant, it's usually made by reacting adipic acid with hexamethylene diamine:

Another kind of nylon is nylon 6. It's a lot like nylon 6,6 except that it only has one kind of carbon chain, which is six atoms long.

It's made by a ring opening polymerization form the monomer caprolactam. Nylon 6 doesn't behave much differently from nylon 6,6. The only reason both are made is because DuPont patented nylon 6,6, so other companies had to invent nylon 6 in order to get in on the nylon business.

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MODEL OF MOLECULAR ARRANGEMENT:

In essence, cold drawing stretches chains in amorphous regions, but molecular folds are restricted and the molecules orient themselves along the fiber axis direction, resulting in enhanced orientation and high crystallinity. In the case of nylons, which have sheet-like crystal structures, drawing may enable the hydrogen-bonded polyamide sheets to slip past each other and form more oriented structure [4]. Hot drawing is a procedure using high temperature during drawing and annealing under restraint after drawing. Exposure to high temperature helps to

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increase the draw ratio, and higher moduli and tenacity can be achieved.. Ultra drawing of solidified crystalline material induces a high degree of chain extension (Figure 2), which leads to very high tensile strength and modulus. This results in a so-called high-performance fiber.

THE MODEL OF MOLECULAR CHAINS:

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A skin-core structure, mostly depending on spinning speed, is generally formed within melt-spun fibers. At a constant feeding rate, higher spinning speeds will produce more extended chains in the melt and form a finer filament. Therefore, the finer fiber usually has higher modulus and tenacity. Fine filament cannot be drawn as much as a coarse filament, because partial orientation on the outer parts of the filaments is formed when the molten fluid is drawn over the sides of the orifice. As a result, finer filaments have a greater proportion of 'skin' to bulk,

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i.e., better orientation has already been formed. Naturally, there is not much space for an improvement by cold drawing within fine filaments. The filaments become lustrous and strong.

NON-CONVENTIONAL SPINNING TECHNIQUES
Alternative to conventional melt spinning, various solution-spinning techniques have been introduced. Solution spinning techniques (gel, wet, dry) enable the spinning of high molecular weight polyamides, leading to high tenacity filaments (tenacity 100cN/tex). As an innovation on fiber formation, new technologies producing micro fibers have been developed and reported. Primarily direct spinning and mechanical and solvent splitting produce micro fibers. Electro spinning represents another approach to fiber spinning, when electrical forces on polymer melt or solution surface overcome the surface tension and cause an ejection from an electrically charged jet. The diameter of the fibers produced by this technique is of the order of nanometers. Frequently, there are produced fibers that are electrically charged.

CRYSTALLINE STRUCTURE
Both nylon 6 and nylon 66 are semi-crystalline polymers. These linear aliphatic polyamides are able to crystallize mostly because of strong intermolecular hydrogen bonds through the amide groups (Figure. 3), and because of Vander walls forces between the methylene chains. Since these unique structural and thermo-mechanical properties of nylons are dominated by the hydrogen bonds in these polyamides, quantum chemistry can be used to determine the hydrogen bond potential . The left side of the figure shows hydrogen-bonding planes, and the right side shows the view down the chain axis. For the -form of nylon 6, adjacent chains are ant parallel and the hydrogen bonding is between adjacent chains within the same sheet (bisecting the CH2 angles). For the -form of nylon 6, the chains are parallel and the hydrogen bonding is between chains in adjacent sheets. . In nylon 66, the chains have no directionality. Research results have shown that the stable crystalline structure is the -form comprised of stacks of planar sheets of hydrogenbonded extended chains. It also appears that Young's modulus of the -form is higher than the γ-form.

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Mechanical, thermal and optical properties of fibers are strongly affected by orientation and crystallinity. Basically, higher fiber orientation and crystallinity will produce better properties. Crystallinity of nylons can be controlled by nucleation, i.e., seeding the molten polymer to produce uniform sized smaller spherulites. This results in increased tensile yield strength, flexural modulus, creep resistance, and hardness, but some loss in elongation and impact resistance. Another important benefit obtained from nucleation is decrease of setup time during processing .

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PROPERTIES OF NYLON 66
-Tenacity-elongation at break ranges from 8.8g/d-18% to 4.3 g/d-45%. Its tensile strength is higher than that of wool, silk, rayon, or cotton. - 100% elastic under 8% of extension -Specific gravity of 1.14 -Melting point of 263oC -Extremely chemically stable -No mildew or bacterial effects -4 - 4.5% of moisture regain -Degraded by light as natural fibers -Permanent set by heat and steam -Abrasion resistant -Lustrous- Nylon fibers have the luster of silk -Easy to wash -Can be pre colored or dyed in wide range of colors; dyes are applied to the molten mass of nylon or to the yarn or finished fabric. -Resilient -Filament yarn provides smooth, soft, long lasting fabrics -Spun yarn lend fabrics light weight and warmth

PROPERTIES OF NYLON 6
The main difference between nylon 6 and nylon 6,6 is nylon 6 has a much lower melting point than nylon 66. This is a serious disadvantage, as garments made from it must be ironed with considerable care.

Fibre Production
Polymerisation
The term polymerisation defines the process of macromolecules formation through repetition of basic units: it of course applies only to synthesis fibres. In general, polymerisation reactions are activated and controlled during the process by various parameters, as temperature, pressure, catalysers, reaction stabilizers. The number of repetitive units is termed degree of polymerisation and is a parameter of great significance for fibre properties setting. As the length

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of the single molecules is not constant, but varies according to a statistical model, the degree of polymerisation or the correspondent molecular weight has to be considered as an average value. Depending on the various fibre typologies, the degrees of polymerisation may ran ge from some hundred units in the case of polymers obtained through condensation (PA, PES) to someUnder a production and application point of view, the degree of polymerisation is controlled by measuring following parameters: There are basically two mechanisms of chemical reaction available for the synthesis of linear Polymers:

A.Poly-condensation:

B.Poly-addition:

Fig. Poly-addition

Polymerisation techniques
From a processing point of view, the polymerisation can be carried out by mass treatment, solution or dispersion (suspension, emulsion). From the engineering point of view, the process can be:

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discontinuous, where reagents are entirely pre-loaded into the reactor and, as soon as the polymerisation is completed, the products are completely unloaded. The “batch” technique is used in particular for the production of small lots or of specialty items. continuous, where reagents are introduced from one end and reaction products come out from the other (this process is used especially for large productions). The reaction can also take place within a stationary phase (as typical for poly-additions) or at subsequent stages (as in poly-condensations). Whichever polymerisation method is applied, the reaction products (polymers) can appear as follows: n form of a solution to be conveyed to the spinning department; i in form of a melted polymer to be conveyed directly to the spinning department or to be transformed into grains (chips) for subsequent use ; in form of a suspension, from which the polymer is separated and conveyed to the spinning department; Along with the chemical reactants (monomers and possible catalysts) during the polymerisation stage or anyway in a stage preceding spinning, other additives can be added in order to provide the fibre with certain properties: a product of particular importance is a white dulling agent (titanium dioxide in grains), which is added in small quantities in order to give the fibres a “dull” appearance, which distinguishes them from the untreated fibres which, owing to their brighter and “synthetic” appearance, are named “bright”. Under this point of view, the fibre is termed on the basis of the added quantity of titanium dioxide (dullness degree) as follows: bright fibre: a fibre without or with minimal quantities of titanium dioxide;19 semi-bright fibre: a slightly delustred fibre semi-dull fibre: usually terms delustred fibres with 0,25-0.5% titanium dioxide contents dull fibre: fibre with 0,5-1% titanium dioxide superdull fibre: fibre with 1-3% titanium dioxide

Making nylon-6,6 industrially
Nylon-6,6 is made by polymerising hexanedioic acid and 1,6diaminohexane. Because the acid is acidic and the amine is basic, they first react together to form a salt. That is then converted into nylon-6,6 by heating it under pressure at 350°C.

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The two monomers can both be made from cyclohexane.

Oxidation of the cyclohexane opens the ring of carbon atoms and produces a -COOH group at each end. That gives you the hexanedioic acid. Some of that can then be converted into the 1,6-diaminohexane.

The acid is treated with ammonia to produce the ammonium salt.

The ammonium salt is heated to 350°C in the presence of hydrogen and a nickel catalyst. This both dehydrates the salt and reduces it to the 1,6-diaminohexane.

Making nylon-6,6 in the lab
In the lab, it is easy to make nylon-6,6 at room temperature using an acyl chloride (acid chloride) rather than an acid. The 1,6-diaminohexane is used just as before, but hexanedioyl dichloride is used instead of hexanedioic acid.

If you compare the next diagram with the diagram further up the page for the formation of nylon-6,6, you will see that the only difference is that molecules of HCl are lost rather than molecules of water.

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In the lab, this reaction is the basis for the nylon rope trick. You make a solution of the hexanedioyl dichloride in an organic solvent, and a solution of 1,6-diaminohexane in water. You carefully float one solution on top of the other in a small beaker, taking care to get as little mixing as possible. Nylon-6,6 forms at the boundary between the two solutions. If you pick up the boundary layer with a pair of tweezers, you can pull out an amazingly long tube of nylon from the beaker.

Spinning
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The term spinning defines the extrusion process through bored devices (spinnerets) of fluid polymer masses which are able to solidify in a continuous flow. The spinning process is sometimes designated as “chemical or primary spinning” to distinguish it from the “textile or mechanical or secondary spinning”. The polymer processing from the solid to the fluid state can take place with two methods: 1. By melting: This method can be applied on thermoplastic polymers which show stable performances at the processing temperatures (this method is used by 70% of the fibres) 2. By solution: The polymer is solved in variable concentrations according to the kind of polymer and of solvent, anyhow such as to produce a sufficiently viscous liquid (dope) (this method is used by 30% of the fibres). Spinning via melting is definitely preferable as it entails a simple transformation of the physical state, however it can be applied only to polymer having a melting temperature (PA 6 an Pa 6.6, PES, PP), whereas spinning by solution is used in case that the polymers attain a thermal degradation at a temperature lower than melting temperature (cellulose fibres, PAN). This last method is evidently more complicated than melt spinning, owing on one hand to the necessity of dissolving the polymer in a proper solvent, and on the other to the necessity of removing and recovering the polymer after extrusion. In the case of melt spinning, the extruded polymer, owing to its fast cooling, is transformed directly into a filament while keeping substantially unchanged the form of the cross-section resulting from the filament geometry; on the contrary, in the case of solution spinning the extruded filaments are subject to considerable structural changes brought about by the process for solvent extraction from the polymer mass. Solvent removal can take place in two ways:

Dry spinning:
Solvent is removed through flows of warm gas suitably directed to the extruded filaments; gas temperature should be higher than the boiling temperature of the solvent, which will be extracted from the filaments, recovered and recycled. Filament solidification proceeds according to the extent of solvent evaporation; it takes place faster on the external yarn layers (thus creating a crust or skin), and successively slows down while proceeding towards the interior. As a consequence of the mass exchange, the original (round) cross-section of the filamentundergoes a contraction, thus generating cross-sections which characterize the various kinds of

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fibres and spinning processes.

Wet spinning
This spinning method is based on the introduction of an extruded polymeric viscose into coagulation baths where the liquor, usually water, behaves as a solvent towards the polymer solvent and as a non-solvent towards the polymer mass. Practically the solvent which is contained in the fibre in amorphous state (gel) is spread towards the liquor and at the same time the liquid of the bath is spread towards the interior of the fibre. The processing speeds are dependent on several parameters, as type and concentration of the polymeric solvent and of the liquor, which bring about structural variations in the fibre. In particular the formation of an outer, gardened and more compact cortex (skin), similarly to what happens in dry spinning, slows down the coagulation mechanism of the inner filament portion (core), thus creating unevenness with a more or less porous structure (voids formation). The fibre cross-sections result more or less modified, from the original round form to a lobated form, with a wrinkled surface.

General flowchart of the spinning process
The flowchart which applies to the various kinds of spinning methods is the following: The fluid polymer mass (melted or solution mass) is guided, through distribution lines, to the metering pumps (gear system), which guarantee a constant flow rate to the spinning positions, composed of a series of filters which purify and distribute the polymer; these are coupled with perforated plates of stainless steel (for melt spinning), but also of precious metals or of vitreous material (for solution spinning). The holes (capillaries), the number of which on the plate varies depending on the kind of fibre and can reach several thousands, can have circular or special cross-sections (shaped or hollow sections).The filaments extruded from the spinnerets, after being converted back to their original state of solid polymer, are interrupted and taken up in suitable packages (bobbins, cans) or conveyed directly to subsequent processing phases. In the case of melt spinning, if the polymer does not derive already in melted state from polymerisation, the fluid polymer mass is obtained through melting of the solid polymer grains (chips). This operation was originally carried out inside containers (pipes) which were

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electrically heated and equipped with grids to separate solid grains from the polymer during melting (grid melting device). The use of such system is at present limited only to few applications and has been replaced by more reliable and efficient devices (screw extruder). The relations which connect some spinning parameters one another (and are calculated for melted polymers) are the following: Polymer flow rate: mF = VF Tsp/10,000 where: mF = polymer quantity for each yarn (g/min) VF = take-up speed (m/min) Tsp = linear mass of taken-up yarn (dtex) If we know the linear mass of the drawn yarn (Td) and the draw ratio R, the relation becomes: mF = VF Td R/10,000 Extrusion speed of the melted polymer VB = 4 mB/πd2ρ VB = extrusion speed at spinneret hole (m/min) mB = polymer quantity per spinneret hole (g/min) d = hole diameter (mm) ρ = density of melted polymer (g/cm3) Spinning ratio Q = VF/VB

Spinning systems for nylon fibres

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fig: Solution spinning

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Fig. Spinning systems for nylon fibres

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Round cross-section of melt-spu thermoplastic fibres

Multi-lobal cross-section of wet-spun viscose

Lobed (dog-bone-shaped) cross-section of dry-spun acrylic fibre

Melt spinning Lobed (kidney-shaped) cross-section of wet-spun acrylic fibre

Fig. 14 Typical cross-sections of fibres produced with different spinning processes.

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Solution spinning
Round cross-section of melt-spu Multi-lobal cross-section of thermoplastic fibres wet-spun viscose Lobed (dog-bone-shaped) cross-section Lobed (kidney-shaped) cross-section of dry-spun acrylic fibre of wet-spun acrylic fibre

Drawing
The polymer extruded by the spinnerets in form of filaments has not yet the properties which are typical of a textile fibre: in fact the polymer mass (solidified through cooling or solvent removal) is characterized by a mass of disorderly placed molecular chains (in amorphous state) which provides the material with poor thermal and chemical stability, low resistance to ageing, high plasticity and deformability and consequently insufficient physical/textile properties. If we take natural fibres as models, we need to orientate the molecular chains (orientation phase) in the direction of the fibre axis and at the same time or successively activate or increase the ordered arrangement of the intermolecular structure (crystallization phase). This process can be partly activated during spinning by increasing the ratio between the take-up speed and the extrusion speed (spinning ratio) but, excepted the case of high speed spinning of continuous filament yarns, the process needs to be completed by an additional operation of mechanical drawing. The process entails winding the yarns on rollers or cylinders running at high speed and can be carried out continuously on filaments coming from the spinning room (single-phase process) or on filaments coming from a phase subsequent to spinning (two-phase process). The speed ratio between the delivery or drawing rollers and the feeding rollers is the draft ratio The mechanical configuration of the rotating devices and the filament path are designed in order to ensure the equivalence of fibre speed with the speed of contact organs.

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Pre-orientation and partial Drawing crystallization Fig. Molecule orientation during drawing Feed rollers Drawing zone R=V2/V1 Delivery roller or draft roller Heating plate (if available)

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Fig. 16 Drawing principle Draft ratio levels are variable and depend on the fibre typology, on the production process and on the end-use characteristics: they can fluctuate between values slightly higher than 1 (≈ 1,2 for traditional cellulose fibres) and max. 10 (for acrylic fibres). Usual ratios for thermoplastic fibres are situated between 3 and 5; higher values identify fibres for technical applications. Optimal conditions for fibre drawing are attained when the molecular chains show high mobility and creep; this result is in practice attained by increasing temperature to levels higher than glass transition and by introducing plasticizers which can make the structure more deformable and can reduce glass transition temperature (generally by acting upon the system water/humidity or using spinning solvents). From an operational point of view, the draft zone can operate at room temperature (cold drawing) or at heated conditions (warm drawing) and consists of rollers, contact plates, heated air chambers or steam chambers and of immersion baths. In order to provide the drawn fibres with thermal stability, usually these fibres undergo also a treatment at temperature higher than drawing temperature, under controlled tensions or in a free state, with the objective of eliminating internal tensions through readjustment of intermolecular chemical links and of the crystallization degree.

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Technologies for the production of continuous filament yarns and of discontinuous fibres (staple fibres)
As already mentioned, from a morphological point of view fibres can be divided into discontinuous fibres and into continuous filaments. This distinction applies also to natural fibres, although they have only one single case of continuous filament: silk, which is moreover available in nature only as monofilament and is available in limited quantities. Only with the coming of manmade fibres, continuous filaments took on a great importance by giving rise to innovative transformation processes and application sectors; at present the market of man-made fibres is roughly divided equally between the two forms of fibre. Theoretically, every fibre can originate continuous filaments or staple fibres; actually however production and application reasons have conditioned the use of one fibre form or of the other: elastane is produced exclusively as continuous filament, and nylon mostly in this form; polyester, polypropylene and viscose are produced in both forms, that is as continuous filament and as staple, whereas acrylic is produced almost exclusively in staple form. Although the production principles are identical for continuous filament and for staple fibre, the two processes differ considerably in terms of plant engineering.

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A) Continuous filament yarns B) Tow for staple fibre productio a) mixer b) extruder screw c) main extruder d) hopper e) chip feeding line

f) side extruder g) rotary gear pump h) continuous filter i) distribution line (manifold) k) spinning position l) cooling chamber m) take-up head n) tow for staple production

Fig. 17 Melt spinning lines for continuous filament and staple fibre

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EXTRUDER

ROTARY GEAR PUMP

SPINNING AGGREGATE

CRIMPING CHAMBER

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CRIMPING CHAMBER

Fig. Mechanical elements characterizing a production process

Continuous filament yarns
Continuous filament yarns can be composed of a single filament (monofilament yarns) or of several filaments (multifilament yarns) and are described through abbreviations, the first figure of which indicates the total linear mass (expressed in dtex or, less usually, in den), the second figure indicates the filament number and a third figure if any shows the twists per length unit (turns/m) imparted to the yarn. Monofilaments for traditional textile uses have linear masses ranging from 10 to 50 dtex approximately; monofilaments with larger linear masses find on the contrary use in technical applications and are identified with their thickness expressed by the diameter of the round crosssection (0.06≠2 mm).

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Multifilaments have variable filament number (up to 300 filaments for traditional textile uses, up to 1000-2000 for technical uses and floorcovering) and the linear mass of each filament ranges from 0.4 to 5 dtex. A yarn can be declared as microfilament when its linear mass is lower than 1 dtex; as a rule, the number of filaments in a microfilament is higher than the linear mass of the yarn (e.g.: 200 dtex/220 filaments). The yarn extruded by the spinneret presents smooth and parallel filaments (flat and parallel yarn). Owing to processing and application requirements, parallel filaments are mostly tied together by means of entangling points (entangled yarns) or of twists (twisted yarns); on the other hand there are flat filaments, characterized by rigidity and poor covering power, which can be converted into curly or crimped yarns (textured yarns). The spinnerets which produce continuous filament yarns have usually a number of holes equal to the number of filaments composing the yarn; there are however also some cases in which the spinneret produces several yarns, which are successively wound on separated bobbins (multibundle spinnerets), or cases in which several spinnerets produce a single yarn which is wound on a single bobbin. The general scheme of a spinning line for thermoplastic polymers (Fig. 17A) consists of:   one or more units, each composed of a screw extruder distribution system (manifold) spinning head or spinning position metering pumps spinnerets (up to 8 or 8x2 per position) spinning chimneys take-up units (winders for up to 8 bobbins) In a first zone placed upright under the spinnerets, the filaments are struck crosswise by flows of cold and controlled air (cooling zone), to be cooled and solidified; then a second zone follows, where the filaments are assembled, lubricated by contact or spray devices and, if necessary, linked one another through entanglement points (produced by air nozzles) and wound on cylindrical bobbins. The take-up speed plays a role of primary importance in establishing yarn haracteristics. As far as traditional spinning is concerned, spinning speeds vary, depending on the fibre, from 1000 to 1800 m/min; under these conditions, the polymer remains substantially amorphous, scarcely oriented, with high propensity to degradation and ageing, and requires consequently to be quickly (i.e. within few days) processed.

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By increasing spinning speed, the yarn is subjected to an increasing stress (due essentially to air resistance and to force of inertia) with consequent higher level of orientation and crystallization. Therefore, depending on the various speed levels, fibres with different characteristics can be produced; these are identified with English acronyms which are conventionally used to distinguish the single processes: Type of yarn Speed (basis PES) LOY (Low Oriented Yarn) 1000-1800 m/min MOY (Medium Oriented Yarn) 1800-2800 m/min POY (Partially or Pre-oriented Yarn) 2800-4000 m/min HOY (High Oriented Yarn) 4000-6000 m/min FOY (Fully Oriented Yarn) > 6000 m/min

Fig. 19: Basic configurations of different spinning technologies for continuous filament yarns Yarns produced with high speed spinning (HOY and FOY) show some qualitative and technological problems and found therefore up to now a limited diffusion at processing and application level. An advanced form of LOY, which needs to be submitted to a drawing process in order to be usable, is POY, a yarn characterized by about 100-120% elongation at break. This yarn is widely used thanks to its good stability to ageing and, although not directly usable in the production of textile items, to its suitability to intermediate processes which combine a specific process (warping, sizing, etc.)

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with a complementary drawing process; in fact this yarn finds wide use in drawtexturization, but also in draw-warping and in draw-sizing. Yarns originated by a specific drawing process performable either directly in spinning or successively in a separate phase, are named “fully drawn yarns” (FDY).

Drawing process
Flat yarns resulting from a drawing process are named FDY (Fully Drawn Yarns). The drawing process can be carried out with two different techniques: Two-stage-process This technique can be applied to yarns which are not fully drawn (LOY, MOY, POY). With the old traditional plants, the bobbins of LOY yarns were drawn in a suitable department by machines named “draw-twisters”. On these machines the yarn runs along a vertical path composed by the feeding system (with bobbins in upper position), by the draft zone and by a winding device similar to the one of a ring twister (Fig. 22 a). During the winding on a stiff tube, the yarn is provided with a light twist originated by the rotation of the ring around the spindle. The speed of current machines can range between 600 and 1500 m/min depending on the yarn type, and the weight of the yarn packages (cops) can reach up to 4 kilos; in order to increase productivity and to reduce costs, the machines can be equipped with automatic doffing device. The 1980’s recorded the development of a new type of drawing frame (draw-winder), in which the winding on spindles was replaced by a take-up system on bobbins with cross-winding (Fig. 22 b). This system permits a higher winding speed (up to 2000 m/min), the production of packages with higher weight (10-15 Kg) and, from the quality point of view, of a yarn with more uniform properties thanks to a more accurate control of the variations in the winding tensions (the winding frame with spindle winding can cause tension peaks). Yarns wound on spindle present a twist which binds together and protects the filaments; on the contrary the filaments of yarns wound on bobbins are parallel so that, to make up for this deficiency, an intermingling device (a nozzle with intermittent flow of compressed air) placed before the winding device can be envisaged. Polymer chips – masterchips (e.g. dyestuffs) Extrusion module Individual metering system on each working position Melted polymer Individual spinning and take-up system 10 position module For some applications as technical uses, additional cylinders (some of which heated) are positioned after the main drawing zone, for the scope of stabilizing the yarn and of fixing a prearranged thermal retraction (Fig. 22 c).

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Fig. 22 Principles of two-phase drawing Single-phase process

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The increase of spinning speeds (4000-5000 m/min) set itself as additional goal, besides rising productivity, the drawing of the continuous filament yarn right during the spinning process (Fig. 19 – FDY configurations). The spinning configuration may be modified on the basis of the various fibre typologies and technologies; in any case the yarn needs, before its take-up, to be submitted to a drawing unit Feeding Feeding roller Heating plate (if available) Drawing or delivery roller Cops Bobbins Drawing Stabilization Setting Intermingling nozzle composed of one or more drawing zones placed between godets and moreover of heating sources (the heated cylinders themselves, or steam/air heated tubes, or chambers positioned before or after the cylinders). The requested yarn characteristics (tenacity, elongation, tensile modulus, thermal retraction) can be modified to a large extent through various adjustment possibilities. Usually yarns coming from the same spinning position are drawn by just one drawing unit, and are then again separated during winding on the various packages composing the winding unit. A comparison between the two drawing processes highlights the fact that the single-phase process is an integrated process characterized by high productivity, low labour costs and reduced space requirements, whereas the twophase process presents a simpler technology and higher flexibility in terms of product range extension and of productivity.

Discontinuous fibres (tow and staple fibre)
This production takes place in plants which have a conception completely different from those designed for the production of continuous filaments.The basic concept is to obtain from spinnerets a high number of parallel filaments (spinning tow or tow) to be delivered to subsequent textile processes (Fig. 17B). The tow must therefore be considered as an intermediate step in the production line of discontinuous fibres which are designed to feed subsequent textile processes (spinning and nonwoven sectors); it is characterized by a considerable linear mass (up to 150 ktex) and is composed of filaments with the same range of counts as the standard range for staple fibres (from a 0,4 dtex micro-fibre to 17 dtex staple fibre for carpeting). Production lines The transformation process is, excepted variations due to the different nature and typology of the fibre, essentially made up of following processes: spinning, drawing, heat-setting, oiling, crimping, drying, cutting into staple if necessary, baling (in form of tow or of staple fibre). The processes can be carried out by means of production lines which transform without break the fibre delivered by the spinnerets as far as the end-phases (continuous single-phase lines) or by means of lines in which the flow of the fibrous material is interrupted after

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spinning and is fed in a subsequent step (as from drawing) as far as the lines of final conversion (discontinuous two-phase lines). Continuous single-phase lines Continuous single-phase lines are used for the production of fibres, in which the flow speed of the material can be balanced through the various transformation phases; a typical application of these lines is the wet spinning process (for acrylic and viscose fibre spinning), but their use has also been recently extended to the compact spinning process for thermoplastic polymers.The limited spinning speeds of these processes are compensated by the high flow rates of the spinnerets. The final speeds of the lines (composed of 1 or more tows) can reach 50-200 m/min. Discontinuous two-phase lines These lines are used when there are differences of operating speeds between the different phases. This occurs in processes in which spinning speeds are higher than in subsequent processing stages. Such is the case of processes traditionally used for thermoplastic fibres and dry spinning processes, in which spinning speeds (over 1000 m/min for hermoplastic polymers, 400-600 m/min for PAN dry spinning) are higher than speeds of downstream processes (final speeds, resulting from initial speeds and from drawing ratio of about 200-300 m/min). One of the most specific technological differences between staple fibre spinning and filament spinning is to be found in the characteristics of their spinnerets. In fact, in the case of continuous filaments the number of holes per spinneret is relatively low and closely connected with the number of filaments in the yarn, whereas in the case of tow production the spinnerets are bigger and have a higher number of holes. The nature of the material and the configuration of the spinnerets must anyway take into account the rheological properties (viscosity) of the polymer mass as well as the spinning typology. Spinning parameters must ensure an even solidification of the polymer mass after extrusion, without varying textile properties and originating physical imperfections (drops, badly drawn yarn pieces, stuck together fibres, broken filaments, etc.) in the filaments. Concerning wet spinning (PAN, CV), owing to the low extrusion speed and to the coagulation process, spinnerets with round cross-section are usually employed; these spinnerets, which can be made of different materials, show thousands of holes (even more than 100.000). As to spinning from melted polymer, considering the high speeds and the necessity of a quick and uniform cooling of the extruded filaments, different technologies are used which, as far as traditional discontinuous processes, fall within following criteria (Fig. 23): Rectangular spinnerets with lateral cooling flow This structure shows holes positioned on parallel rows of rectangular plates made of special steel, designed in a way that the flow of cooled air comes only from one direction and consequently

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does not hit uniformly the various filament rows; this fact involves a limit in increasing the number of holes; moreover the system does not ensure an efficient removal of spinning steams (monomers). Ring spinnerets (round spinnerets with a large central hole) Cooling is carried out by adjusting air flow (coming from the bottom of the chimney) on the whole filament bundle by means of a flow which is addressed from the outside to the inside of the filament bundle or from its inside to its outside. This system guarantees a more uniform solidification and a more effective removal of steams and impurities, thus enabling a higher production capacity (up to 4,5-5 kg/min). In the case of mass productions, the holes per spinneret attain a number of 5,0006,000 (5,250 holes for standard fibres, 6,000 holes for micro-fibres). The bundles of cooled yarns are successively oiled (by means of spray or roller devices), conveyed in horizontal direction by diverting pulleys, combined with other yarn bundles in order to obtain a tow of larger size (or sub-tow) which, in the case of the two-stage process, is collected into cans; these are placed in a certain number on the creel to feed the drawing line.

Fig. 23 Technologies of staple fibre spinning

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Fabric Production
Fabric Production With Circular Knitting Machines
Introduction
All over the world, the majority of knit fabrics are manufactured on circular knitting machines. The high performance level of these machines, the different materials and the range of yarn counts that they are able to process, the wide variety of designs and stitches are some of the reasons which have granted circular machines the market leadership in the knitting sector. The variety of knit fabrics that can be manufactured with these machines can meet the needs of a very large end user market; from the traditional outwear and underwear sectors to hosiery, household and car interiors, without forgetting technical textile applications.

Basic Structure of a Large-diameter Circular Knitting Machine
Circular knitting machines include a number of fundamental elements, based on similar mechanical principles with some small changes according to the different models:- The machine base. The most recent trend among circular machine manufacturers is to build knitting machines with a solid yet smaller base and an architecture that facilitates access to the machine components for routine operations to be carried out during setting up procedures and production; - The “core” of the machine, which includes the needle-bed area and all the systems operating during the knitting process. The feed systems are placed along the circumference of the circular needle-bed. Circular knitting machines can be divided into two basic models: in the first one the needle-beds rotate and the cam frame stands still, while in the other one the needle-beds stand still and the cam frame revolves. - The yarn spools holder. If the system is attached to the upper part of the machine, it is a circular rack; if arranged at the machine side, it is a lateral creel. - The yarn feeding system, made up by the yarn feeding unit which must ensure a smooth and steady yarn feeding, and a thread guide system which provides the needles with the yarn necessary for the stitch formation

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.- The fabric take-down and winding system housed in the lower part of the machine; depending on the machine model, the fabric take-down and winding motion can rotate together with the needle-beds or stand still. - The drive, usually an inverter drive, i.e. a motor with electronic variation of speed for optimum acceleration and slow-down ramps and optimum throughput speed in all conditions. Lastly, several machine manufacturers (above all of single-bed machines) tend to build convertible machines, which have the same basic structure and are equipped with special conversion kits which allow the change of stitch formation motions such as cams, cam frames and thread guides to generate different styles. The cost of these machines is extremely advantageous compared to the investment costs necessary for buying a complete series of machines each one producing a single article.

Picture – Overall view of a circular knitting machine

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The Yarn Feeding System
Yarn Feeders
Yarn feeders can be divided into “positive” or “negative” types depending on the possibility of controlling the yarn feeding speed and uniformity. A yarn feeder is the negative type when the needle takes the yarn directly from the ackage during the stitch formation step, and the feeding tension of the yarn cannot be controlled.

Picture – A negative yarn feeding device

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This feeding technique can generate differences in the yarn length used for stitch formation. This is due to the variable tension of the yarn since a new spool has a certain diameter which gradually reduces as more yarn is unwound and fed into the machine. In addition, the spool can be too hard or too soft. Circular knitting machine manufacturers have eliminated this problem by implementing two distinct solutions: 1. The motorised yarn accumulator levels off the yarn tension since when rotating, it accumulates a certain quantity of yarn on a constant-diameter pulley and then stops. The yarn wound on the accumulator is then conveyed to the thread guide always maintaining the same tension. The machine takes up the yarn, gradually emptying the accumulator, which is then restarted automatically to replenish its yarn reserve. This solution is particularly indicated when the same type of feeding technique cannot to be applied to all the feed systems due to the structure of the knit stitches. Therefore, yarn accumulators are mainly used on machines for the manufacturing of fabrics of pre-set length, or also of continuous cloths with Jacquard patterns. 2. Positive feed systems control the tensions of the yarn fed by means of a drive wheel or a drive belt system. The drive wheel systems, which in the past were much more widespread than today, consist of two conical toothed wheels. The thread passes between the two wheels and the quantity of yarn can be adjusted by approaching or withdrawing the wheels. This positive system grants a smooth feeding of the yarn on all the feed systems. Today, the belt system has by far become the most common positive feeding system. The belt makes the spool rotate, and the number of rotating spools corresponds to the number of feed systems. By adjusting the belt RPM, the quantity of thread can be increased or reduced. This system grants an accurate control of the yarn tension (picture 80).

Stitch Formation Motions
Circular knitting machines, both the single or double-bed types according to our initial classification, can incorporate various stitch formation motions depending on the machine’s technical features.

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Take-down and Winding Motions
The fabric take-down and winding motions have been designed to facilitate stitch knock-over and fabric take-down procedures. The take-down and winding functions are kept separated in order to allow a smooth running of the machine and avoid possible fabric distortions.

Take-down Motion
The take-down motion consists of 2 or 3 rollers placed beneath the cylinder. In the simplest system configuration (i.e. the two-roller) the fabric passes between two rollers that stretch it by rotating in opposite directions. Anyway, the best system is the three-roller take-down motion which pulls the fabric without slipping and without exerting too much pressure that could damage the fabric. From a mechanical point of view, a take-down system can be either equipped with a swivelling arm or with a lever and spring mechanism. Modern take-down systems are motorised and the latest models also incorporate an electronic control.

Picture 97 – A 2-roller take-down motion

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Circular knitting machines pose some problems as regards the winding of the fabric, as the fabric itself is delivered in tubular form and must be spread flat prior to winding. The spreading of the tubular fabric generates some distortions because of the different distances between the various zones of the tubular fabric emerging from the take-down system and the same zones wound on the fabric roll. These differences reflect into uneven winding tensions (the tension is lower in the fabric centre and higher at its edges). To avoid these problems, a metal frame called “spreader” has been incorporated before the fabric winding system. The spreader increases the width of the tubular fabric by giving it an almost circular shape, equalising the distances between the various zones of the fabric and the nip line of the winding system.

Picture – Take-up and winding motion with fabric spreader A special take-down system has been designed for variable needle-bed machines since these machines do not use the whole needle-bed. This special take-down motion features independent rollers to adjust the tension during the knitting process and differentiate the tension between the central part of the cloth and the edges. On the most recent machines, it is possible to set up to 99 different tension values.

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Winding Motion
The fabric winding motion is provided with a clutch. In this way, to grant a steady peripheral speed, the angular speed of the winding roller can be gradually reduced as the diameter of the fabric roll increases.

Picture 99 – Clutch connection between the winding roller and the take-down motion rollers At the ITMA ‘99 fair in Paris, an Italian manufacturer of circular knitting machines exhibited an innovative winding system mounted on a 30-inch circular knitting machine. In practice, this machine features an “open” base that allows the fabric cutting and opening on only one side prior to winding. Obviously, in order

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to allow the take-up of the open fabric, the width of the winding roller must be twice the width of a standard one. The take-up step is carried out on the already opened fabric, and the edges of the fabric are kept tensioned by means of two rollers with worm-screw profiles. Thanks to this innovative solution, no further rollers squeeze the knit fabric. This avoids the problem of central marks which is particularly serious on elastane fibres.

Control and Monitoring System
Modern circular knitting machines feature on-board computers (CPU) complete with a display and a keyboard to control and monitor the most important functions: - speed - number of machine revolutions - working hours - causes of machine stops - detector of the yarn length fed into the machine On modern microprocessor-controlled machines, the LCD display is equipped with an alphanumeric keyboard for entering the operator’s settings. The whole system is controlled by an electronic circuit which signals the status of the machine and the possible causes of machine stops by means of flashing lights. All the electronic control components are accommodated in a cubicle linked with the machine by special connectors. Sometimes, together with these functions, the machine can also carry out needle selection procedures by retrieving the information saved on floppy disks or by means of a direct connection to a dedicated CAD system.

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Picture – Control unit

Stitch Formation on Dial-cylinder Knitting Machines
The stitch formation cycle on double-bed dial-cylinder machines is similar to that of flat knitting machines. The needles start rising from their lowest position; the previous stitch slips along the needle stem and opens the latch; when the needle reaches its highest position the previous course is on the stem, beyond the open latch. The needle starts lowering and the thread guide feeds the thread for the new stitch which is seized by the hook; at the same time the previous one slips forward on the stem and closes the latch. Once the previous course has been knocked over on the new course, the cycle is completed. The same movements are carried out by the needles in the dial. Here, however, the dial needles move on a horizontal plane, so instead of raising and lowering movements, we will have forward and backward needle movements.

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Picture – The various steps of stitch formation on dial-cylinder knitting machines Several machine models allow the variation of the stitch knocking over in order to have either a simultaneous or a differentiated knocking-over operation. In the former case, the needles of the cylinder and the needles of the dial form the stitch simultaneously; in the latter case, by varying some controls or by racking the dial by five of six needles with respect to the cylinder, it is possible to knock over first the needles of the cylinder and then the needles of the dial. With the simultaneous knocking-over technique, the resulting fabric will be more consistent, soft and stretchable since the two series of needles can take up the quantity of thread necessary to form the stitch. On the contrary, with the differentiated knocking-over technique, in order to take up the quantity of thread necessary for the stitch formation, the needles in the dial have to make the thread slip with respect to the needles of the cylinder that have already been lowered. In fact, it is easier to take up part of the thread from the stitches already formed on the cylinder.

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In this way, the fabric formation will require less thread, resulting in a denser and less stretchable construction. On dial-cylinder circular knitting machines it is also possible to transfer the stitches from a needle-bed to the opposite one to create complicated design patterns. The stitch transfer is carried out usually from the cylinder to the dial to exploit the wider possibilities for selection offered by the cylinder needle bed. Obviously, the stitch transfer in the opposite direction is also possible. To carry out the stitch transfer on mechanically controlled machines, it is necessary to replace some of the knitting feed systems with special feed systems equipped with transfer cams on the cylinder and receiving cams on the dial. In general, there is one transfer system for every two knitting feed systems. Obviously, the replacement of these knitting feed systems with transfer systems causes a reduction of output rates. Besides the transfer cams, it is also necessary to provide the machine with special needles with opening spring, like that of flat-bed knitting machines.

Rib-stitch Machines
Rib-stitch machines constitute the most typical category of double-bed machines. The dial needles of rib-stitch machines are arranged in staggered position with respect to the cylinder needles. These machines are mainly used for manufacturing continuous tubular fabric with rib-stitch or derived patterns. Manufacturers offer rib-stitch machines in a wide range of models with diameters up to 40 inches; the most common models are however the 30, 34 and 36 inches, with gauge from E 10 to 28. The models with multi-track selection feature up to 5 tracks on the cylinder and up to 2 tracks on the dial.

Interlock Machines
Interlock machines are dial-cylinder machines of special design. In fact, the cylinder needles and the dial needles are arranged in front of each other. Obviously, in order to achieve different needle motions, the needles themselves must be of different types: on interlock machines, needles are generally arranged in such a way that a short needle is alternated with a long one in the cylinder, and a long needle is alternated with a short one in the dial. To drive short and long needles, two cam tracks are necessary on both the cylinder and the dial. On one feed system, the short needles of a needle-bed and the long needles of the opposite one operate alternately and form a half-course of rib stitches; in the next feed system, the needles operate inversely and form a second half-course of rib stitches

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interknitted with the previous one. In interlock fabrics, a knit stitch course is therefore made up by two interknitted halfcourses of rib stitches. Interlock machines, built mainly in the 30-inch diameter version, and E 18 to E 32 gauges, feature a huge number of feed systems (up to 108) and are designed mainly for the production of cloths with interlock patterns.

Picture – Arrangement of needles and tracks on interlock machines

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Fabric Production With Projectile weaving machine
weaving Pretreatments: WINDING
Unevenness in traditionally spun staple yarns is a natural phenomenon usually induced by the process of manufacturing (spinning). Although with modern process controls and machines many imperfections in the spun yarns can be controlled, some still remain in the final yarns. Most common of all imperfections are thin or weak places, thick places, slubs, neps, and wild fibers, as shown schematically in. During the subsequent processes of winding, warping, and slashing, not all but some of these imperfections create obstacles to steady and smooth working. Therefore, it is important to classify, quantify, and remove those imperfections which may cause the interruption of the operation In other words, only ‘‘objectionable’’ faults need to be removed for trouble-free processing of the yarns. The ring-spinning operation produces a ring bobbin containing just a few grams of yarn which is unsuitable for the efficiency of further processing, such as warping, twisting, and quilling. This necessitates the preparation of a dense and uniform yarn package of sufficiently large size which can unwind in the subsequent operations without interruptions. The packages prepared for warping are normally cross-wound, containing several kilograms of yarns. This implies that a number of knots or splices are introduced within each final package. Bear in mind, each knot or splice itself is an artificially introduced imperfection; therefore, the size of this knot or splice must be precisely controlled to avoid an unacceptable fault in the final fabric. In modern winding machines, knots and splices are tested photoelectrically for size, and only acceptable knots and splices are allowed to pass on to the winding package. In modern spinning processes, such as open end, friction and air jet, the spinning process itself produces a large cross-wound package, thus eliminating the winding operation. Nowadays splices are used on all the spinning systems including ring, open end, and air jet for repairing ends down during spinning. In the absence of winding, it is pertinent to note that the yarn spun on such modern spinning systems must have no or only a small number of

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objectionble imperfections. In most modern spinning machines, the manufacturers have incorporated devices that continuously monitor the quality of the yarn being spun, thus assuring fault-free spun yarns.

Functions of the Winding Operation
Important functions of the winding operation are 1. Clearing of yarn faults 2. Making larger wound packages 3. Preparing soft packages for dyeing

Knotting/Splicing
The process of piecing (joining) two yarn ends—resulting from yarn breaks, removal of a yarn defect, or due to the end of the supply package—has received considerable attention in the past two decades. An ideal yarn piecing would be one which can withstand the subsequent processes without interruption and which does not lead to any deterioration in the quality of the finished product . The yarn joining or piecing technique should be suitable for all fiber types irrespective of yarn structure and linear density. Earlier attempts in this area were directed to tying two ends by a weaver’s knot or fisherman’s knot such that the ends do not slip apart. However, the size of the knot, which depends on the type of knotter and the linear density of the yarns, would normally be two to three times the diameter of the single yarn, leading to a characteristic objectionable fault in the finished product. Knots have a detrimental effect on quality; they are obstructive because of their prominence and so frequently cause breaks due to catching in thread guides or even being sheared off. This leads to time-wasting stoppages of the machinery during warping, sizing, and weaving. Due to the above-mentioned drawbacks of knotted yarns, knotless yarn joining methods have received considerable attention by researchers

WARPING
Warping is a process of transferring yarn from a predetermined number of single-end packages, such as cones or cheeses, into a sheet of parallel yarns of a specified length and width. The individual warp yarns are uniformly spaced across the whole width of the beam. In warping, the sheet of parallel yarns is wound onto a flanged beam called a warper’s beam . The function of warping is primarily to transfer large lengths of yarns from a number of large wound packages to a warper’s beam containing a predetermined number of yarn ends (threads), so that it

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runs without interruption at a high speed. Removing faults from yarns during warping is not recommended because it affects the efficiency of the process. A single break makes several hundred other good warp yarns inoperative, thus affecting productivity

Warping Systems
There are two basic systems of warping, namely, the direct system and the indirect system, as shown in. In the direct system the warp yarns from a creel are wound directly onto a flanged warper’s beam. This system is most widely used for mass production of warper’s beams containing only one type of warp yarns. Because of the difficulties involved in setting up a pattern of different types and colors of warp yarns, the direct system is not normally used for the preparation of a patterned warper’s beam [1]. Any pattern that is required to be produced is adjusted by combining beams of different colors during the slashing operation. The cumbersome work of setting the pattern at the slashing stage is time intensive and inefficient. In the indirect

Fig. 4.12 Direct warping system. (Courtesy of West Point Foundry and Machine Company.)

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number of these beams is placed at the back of the sizing machine. The type of creel, tensioner, warp stop motion, head stock, and control devices on warping machines may vary depending on the manufacturer; however, their basic functions remain the same. Indirect System Unlike the direct system, warping and the preparation of a weaver’s beam takes place on the same machine but in two consecutive steps. In the first step, the warp is prepared in sections on a large drum with one conical end, as shown in Then the rewinding of the entire warp sheet from this drum to a weaver’s beam is done in the second step. The operations in the first and the second step are commonly known as warping and beaming, respectively. For preparing the sections on a drum, the warp yarn is withdrawn from the creel through a tension device and stop motion (similar to the one described in the previous section) and is in turn passed through a leasing reed.

Fig. 4.15 Sectional warping and beaming machine. (Courtesy of Sucker-MullerHacoba GmbH & Co., Germany.) Then all Jthe sectional warps are condensed into a section of the desired width by passing them through a V-shaped reed guide and over a measuring roller to the rum. The density of the warp in a given section is the same as the number of ends

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per unit width required in the weaver’s beam for producing a fabric with a given color pattern and specification. The length of each section is generally equal to the length of the warp required in a weaver’s beam plus due allowance for the waste in the process. One end of the warping drum is conical shaped, as shown in Fig. 4.15. This is necessary for providing support to the outside ends of the first section to prevent the yarns from sloughing off at the end of the drum.

SIZING
The primary purpose of sizing is to produce warp yarns that will weave satisfactorily without suffering any consequential damage due to abrasion with the moving parts of the loom. The other objective, though not very common in modern practice, is to impart special properties to the fabric, such as weight, feel, softness, and handle. However, the aforementioned primary objective is of paramount technical significance and is discussed in detail herein. During the process of weaving, warp yarns are subjected to considerable tension together with an abrasive action. A warp yarn, during its passage from the weaver’s beam to the fell of the cloth, is subjected to intensive abrasion against the whip roll, drop wires, heddle eyes, adjacent heddles, reed wires, and the picking element [12], as shown in. The intensity of the abrasive action is especially high for heavy sett fabrics. The warp yarns may break during the process of weaving due to the complex mechanical actions consisting of cyclic extension, abrasion, and bending. To prevent warp yarns from excessive breakage under such weaving conditions, the threads are sized to impart better abrasion resistance and to improve yarn strength. The purpose of sizing is to increase the strength and abrasion resistance of the yarn byencapsulating the yarn with a smooth but tough size film. The coating of the size film around the yarn improves the abrasion resistance and protects the weak places in the yarns from the rigorous actions of the moving loom parts. The functions of the sizing operation are 1. To lay in the protruding fibers in the body of the yarn and to cover weak places by encapsulating the yarn by a protective coating of the size film. The thickness of the size film coating should be optimized. Too thick a coating will be susceptible to easy size shed-off on the loom.

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Fig. 4.17 Parts of the loom and major abrasion points.

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2. To increase the strength of the spun warp yarn without affecting its extensibility. This is achieved by allowing the penetration of the size into the yarn. The size in the yarn matrix will tend to bind all the fibers together, as shown in. The increase in strength due to sizing is normally expected to be about 10 to 15with respect to the strength of the unsized yarn. Excessive penetration of the size liquid into the core of the yarn is not desirable because it affects the flexibility of the yarn. 3. To make a weaver’s beam with the exact number of warp threads ready for weaving. illustrates various possible conditions that may occur in practice depending upon the properties of the size employed. This emphasizes the importance of an optimal balance between the penetration of the size into the yarn and providing a protective coating around the yarn, as shown in Fig. 4.19d. The flow properties of the size liquid and the application temperature have important effects on the distribution of the size within the yarn structure. More size at the periphery of the yarn will tend to shed off on the loom under the applied forces because the size is not well anchored on the fibers. Too much penetration, as shown in Fig. 4.19a, may leave too little size around the yarn surface to protect it against the abrasive action. To rectify such a condition, a higher size add-on is required to provide the required protective surface coating [13].

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Fig. Head end of a sizing machine. (Courtesy of West Point Foundry and Machine Company.)

Preparation of weaving machines
To obtain satisfactory weaving performance, it is essential to have not only a correct yarn preparation, but also an efficient organization which permits to have warps available at the right moment, thus avoiding any dead time with style or beam change. All these prerequisites aim at ensuring to the weaving mills a sufficient flexibility and at permitting them to cope promptly with a variable market demand. Currently several weaving mills have installed weaving machines which enable to perform the quick style change (QSC), leading to a considerable reduction of the waiting time of the machine. The following chart presents the possible alternatives for the preparation of the weaving machine: Changing style means producing a new fabric style, weaver’s beam changing means going on weaving the same fabric style just replacing the empty beam with a full beam of same type. Drawing-in consists of threading the warp yarns through the drop

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wires, the healds and the reed (fig. 28). Depending on the styles of the produced fabrics and on the company’s size, this operation can be carried out manually, by drawing-in female workers

Fig. 28 −Drawing-in operating in pairs (a time consuming activity which requires also skill and care), or by using automatic drawing-in machines.

piecing-up
The piecing-up of the warp yarns (Fig. 32) permits to the weaving mills which are in a position to use it (not many mills at the moment) to simplify and speed up considerably the loom starting operations in case of warps which were drawn-in or tied-up outside the weaving machine. The warp threads are laid into a uniform layer by the brush roller of the piecing-up machine and successively pieced-up between two plastic sheets respectively about 5 cm and 140 cm wide, both covering the whole warp width. The plastic sheet can be inserted into the weaving machine simply and quickly, avoiding to group the threads together into bundles; the threads are then pieced-up on the tying cloth of the take-up roller. If a new drawing-in operation is not necessary (this expensive operation is avoided whenever possible) because no style change is needed, the warp is taken from the beam store and brought directly to the weaving room, where it is knotted on board the loom to the warp prepared with the knotting machine.

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Fig. -Piecing-up

Projectile weaving machines
The projectile weaving machine made its appearance in the market at the beginning of the 50’s and is today still used in the whole world. Thanks to its steady renovation and to the use of advanced electronic systems as well as of microprocessors for the supervision and the control of the various devices, this machine is characterized by a good productivity level (450 rpm and 1050 m/min of inserted weft) and by high operational reliability. It is established especially in the field of machines with high reed width.

General operation
In this weaving machine the weft insertion is carried out by small clamp projectiles which number depends on the weaving width and which with their grippers take out the weft yarn from big cross-wound bobbins and insert it into the shed always in the same direction. The projectiles work in sequence, that is they are launched in succession. They run therefore one after the other, describing in the space a continuous, endless route, as if they would be stuck on a conveyor belt. The first projectile takes and holds in its back the weft in form of a tail; then, pushed by the release of the projectile thrower, it passes through the shed and deposits the weft inside the warp; subsequently the projectile falls and is collected by a device which, by passing under the array of the warp threads, takes it at reduced speed

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back to the starting point. Here the projectile goes up to take up a new weft; meanwhile the other projectiles have run after each other making the same operation. shows the projectile conveyor chain (shuttle return chain), the projectile (shuttle) with its back clamp to seize the yarn (thread grippers), the cutting tool (scissors) to separate the inserted weft from the bobbin and the strap which, through twisting, launches the projectiles (torsion rod).

Projectile guide
The limited weight and the reduced volume of the projectile make a projectile guide necessary. The projectiles therefore do not come into contact with the threads, but run inside a sort of channel composed of the thin prongs of a rake, which form reminds a semiclosed hand. This rake goes up from under the threads at the moment of the projectile launch and has of course to fall back lowering itself at the slay stroke. To enable this movement, the rake is secured on the slay and is positioned very close to the reed; the rake’s laminas are not in contact with the warp, or touch it very lightly because the reed opens them the way. The latest models of the projectile machine have been equipped with new types of guide dents, which are divided and placed in alternate position, in order to reduce the stress on weft and warp threads. This permits to use in warp even very delicate yarns as for instance untwisted or entangled yarns and at the same time to cope with high quality requirements.

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Fig: Projectile guide

Projectile launching mechanism
The operational principle of the launching mechanism is the following (fig. 48 and 49): a torsion bar 2 is anchored, at one side, to the fixed point 1, whereas the free end is connected by a toothed groove to the percussion shaft 3. The percussion lever 9, which is fixed to the percussion shaft 3, follows per force the movements of this last and consequently of the free end of the torsion bar 2. During its rotation, the cam 8 shifts the knee-joint lever 4+5, so that the torsion bar 2 is put under tension by the percussion shaft 3 and the percussion lever 9 is put in launching position (the scheme shows the launching mechanism with the torsion bar in the phase of maximum tension). The torsion bar 2 remains under tension until the roller 7 slides along the bend of lever 5. The particular shape of this lever makes so that the roller, when leaving it, presses its end, thus giving the starting point to the torsion bar for the articulation of the knee-joint lever 4+5. Subsequently the torsion bar 2 returns suddenly to its rest position imparting a strong acceleration to the projectile 11 through the percussion shaft 3 , the percussion lever 9 and the percussion element 10.

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Fig. 48 - Projectile launching mechanism

Fig. 49 − Loading of the torsion bar: a) torsion bar 2 in rest, knee-joint lever 4+5 in articulate position; b) loading phase; c) torsion bar in tension and kniejoint lever in stable position, before the launching control by roller 7.

The oil brake 6 serves to damp the stroke. The projectile’s stroke time, that is the insertion time, is adjusted by modifying the torsion angle of the bar through an angular shift of the anchorage point, which has proper adjustment windows.

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Insertion cycle of the projectile machine
The schemes in Fig. 50 show the insertion cycle of the projectile machine: a) The projectile 1 is put in launching position; the weft is hold at its end by the weft carrier 2 and is controlled by the weft tensioner 3, by the weft brake 4 and by the eyelet 7 situated in proximity of the feeding bobbin 8; b) The weft carrier 2 gets open after the projectile clamp has got hold of the end of the weft thread; c) The projectile 1 is launched and crosses the shed dragging with itself the weft, while the weft tensioner 3 and the weft brake 4 operate in a way as to minimize the stress on the yarn (the critical phases are particularly the initial acceleration phase and the final stop phase in the collector box); d) The projectile 1 on the one hand and the weft carrier 2 on the other take up the right position to build up the selvedge, while the tensioner arm opens to adjust the weft tension; e) The weft carrier 2 closes while the selvedge clamps 5 get hold of the weft thread on both sides and the projectile clamp is opened to release the weft end; f) The thread is cut by the scissors 6 on the launching side, while the projectile 1 is placed in the transport chain;

Fig. 50 − Insertion cycle of the projectile machine

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g) The weft is beaten by the reed, while the weft carrier 2 moves back to its initial position and the weft tensioner 3 opens further to recover the thread piece and to keep it under tension. The projectile is brought back to the launching zone; h) The selvedge needles 9 insert the weft ends into the subsequent shed (tuck-in selvedge), while a new projectile is placed in launching position.

Electronically controlled projectile brake
The present machines have the projectile brake adjusted by a microprocessor, and this permitted to increase the efficiency rate and to reduce the maintenance costs. The electronically controlled brake has the function of stopping the projectiles in the correct position, without any need of manual intervention (contrarily to previous mechanism). This result is obtained by means of a controlled double upper brake lining and of a lower fixed brake lining (Fig. 51 and 52). The mechanism works as follows: the sensor 1 and 3 detect the position of projectile 4 inside the collector mechanism and communicates it to a microprocessor which, on the basis of the received information, transmits a corresponding order to the stepping magnet 14. This last operates on a wedge-shaped guide element 13 which, by shifting the upper bracket lining 8, modifies the braking intensity. The sensor 2 controls instead the timely arrival of the projectiles in the collector mechanism. Three cases are possible: A) Position I (normal projectile position): the control co-ordinates S of sensors 1 and 3 are covered by the projectile; B) Position II (projectile too far penetrated / insufficient braking): the control coordinate S of sensor III is not covered; C) Position III (projectile insufficiently penetrated / excessive braking): the control coordinate S of sensor 3 is not covered. In the first case the microprocessor does not answer; in the second and third case, it causes respectively the closing and opening of the brake, thus controlling the number of steps necessary to bring the projectile again to normal position.

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Fig. − Projectile brake

Fig. − Brake adjustment

Colour selector
In the multi-colour weaving machine, the weft carrier is controlled by a turret loader (fig. 53); as it is a 4-colour system, 4 weft carriers will be mounted on the loader. The weft carrier loader is driven by a conical gear controlled by a toothed quadrant; when the quadrant moves upwards or downwards, the loader is pushed in the opposite direction and the extension of the oscillation defines which carrier to take position opposite the clamp of the projectile to be launched. A block ensures that the turret loader remains in the selected position until further order. In the case of cam-controlled heald frames, the colour is selected by a punched card special unit. If the heald frames are driven by a dobby or by a Jacquard machine, the gear which drives the toothed quadrant is integrated in the dobby or in the Jacquard machine. The modern selectors are controlled by servomotors and the weft sequence is programmable.

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Fig. − Colour selector

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How to Dye Nylon?
Dyes for Polyamide Fibers
With the exception of the aramid fibers, the polyamides dye readily with a wide variety of dyes. Since the polyamides contain both acid carboxylic and basic amino end groups and have a reasonably high moisture regain, the fibers tend to dye like protein fibers such as wool and silk. Since the molecular structure is somewhat more hydrophobic, more regular, and more densely packed in the polyamides than in protein fibers, they also exhibit to some degree the dyeing characteristics of other synthetic fibers such as polyesters and acrylics. Due to their highly regular molecular structure and dense chain packing, the aramid fibers resemble polyester and are dyed only by small dye molecules such as disperse dyes. Polyamides such as nylon 6, 6,6, and Qiana can be readily dyed with dyes containing anionic groups, such as acid, metallized acid, mordant dyes, and reactive dyes and with dyes containing cationic groups such as basic dyes. Acid dyes on nylon can be mordanted effectively for additional fastness; however, the colorfastness of basic dyes is poorer and more difficult to stabilize by mordanting. Vat and azoic dyes can be applied to nylons by modified techniques, and polyamides can be readily dyed by disperse dyes at temperatures above 80°C. Aramids can only be dyed effectively with disperse dyes under rigorous dyeing conditions. The biconstituent fiber of nylon and polyester can be effectively dyed by several dye types due to the nylon component, but for deep dyeings disperse dyes are preferred. Nylon 6 and 6,6 are produced in modifications that are light, medium, or deep dyeableby acid dyes or specially dyeable by cationic dyes.

PRE-DYEING TREATMENTS
The pre-dyeing stage includes a series of operations that prepare the textile product for subsequent finishing treatments such as dyeing, printing and finishing. These operations vary according to the type of fibre on which they have to be carried out, to the structure of the textile product (staple, top, sliver, yarn, fabric) and also depend on the subsequent treatments to be carried out, which may change according to various factors such as market demands, customer requirements, staff experience, and availability of machines. The pre-dyeing stage includes for example desizing, singeing, mercerising, scouring, and bleaching. Each process varies according to the processing conditions and the above-mentioned specific situations. Some of these processes (for example bleaching and mercerising) can

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be considered either preliminary operations or finishing treatments; this depends on the type of the downstream processes to be carried out on yarns or fabrics. Singeing With this treatment fuzz and fibre ends are burnt off in order highlight the fabric weave. It is generally carried out on gray pieces and the residues are removed by a further washing process. An oxidising flame, which does not leave any trace of sooty residue on fibres, is used to carry out this operation. The flame can be perpendicular to the fabric, and only rarely tangential; the fabric is positioned at a distance of 1.5 - 4 mm from the end of the flame and the machine is equipped with a suction device under the fabric, which attracts the flame and concentrates the heat on the fabric. The fabric speed can range from 60 to 120 metres per minute. The singeing process with perpendicular flame is the most common one, while the process with tangential flame is used for fine fabrics (light singeing).

Picture 1 - Fabric singeing with perpendicular flame

Picture 2 - Fabric singeing with tangential flame

Singeing is carried out rarely on knitted fabrics and frequently on yarns and woven fabrics. Instead of the traditional singeing process, it is possible to apply an enzymatic treatment (for cotton and lyocell fabrics), for example with cellulase,

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which uses chemical agents to corrode the fibre surface and remove the fuzz from the fabric.

Desizing
This treatment is carried out on woven fabrics to remove the sizing substance from the warp. The size must be totally eliminated since the fabric must absorb the liquor of subsequent processes homogeneously. Since amylaceous sizes are generally used for cotton yarns, it is possible to apply amylolytic enzymes (enzymatic desizing), which carry out a biological degradation process of the starch, transforming it into soluble by-products which can be then eliminated by washing. The enzymatic process depends on the quantity of enzyme molecules per gram of fabric, while the thermal stability of the enzyme depends on the bacteria strain from which it originates. The amylases only react with starch molecules and do not affect the other glucose polymer (cellulose), since they attack the 1.4 alphaglucoside bond of starch and not the 1.4 betaglucoside bond of cellulose. This reaction makes the use of amylases profitable (when applying starchy sizes) compared to other desizing agents such as alkali and oxidising agents (oxidising desizing), which attack both starch and cellulose. The oxidising desizing process is used to remove non-starchy sizes that do not dissolve in water or to eliminate starchy sizes combined with polyvinyl alcohol (this treatment is carried out before the singeing process). This last treatment requires accurately controlled operating conditions to solubilise only sizes and avoid any possible fibre degradation. Enzymatic desizing can be carried out in discontinuous systems (jigger) but semicontinuous or continuous techniques are more frequent after the pad-batch wetting of the fabric. The most frequently used processes are pad-roll and pad-steam. If the size is water-soluble, it can be eliminated by hot washing.

Scouring
On cotton fibres, this treatment removes fatty and pectic substances, softening motes and preparing the material to absorb the subsequent treatment agents. Scouring is usually carried out in soft water additivated with textile auxiliaries such as absorbing agents, detergents, emulsifying agents, caustic soda and/or Solvay lye and sequestering agents. Alkali make the fibre swell and enhance the action of surfactants. This treatment can be carried out on filaments, yarns and fabrics. Instead of the traditional scouring process, it is also possible to carry out an enzymatic scouring process (bioscouring) to remove non-cellulosic material from cotton fibres, to make them more easily wettable and enhance the subsequent absorption of

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finishing liquors. The scouring of pure silk is a degumming process used to remove sericin (silk gum) from fibroin floss. Sericin is the gummy element which keeps together the fibroin floss and gives the silk a hard hand and dull appearance. It is carried out on yarn, on dyed yarn, piece-dyed fabric or on products ready for printing. The treatment, which causes a loss of weight ranging between 24 and 28%, gives the degummed silk a lustrous appearance and a soft hand; the treatment is carried out with soapy solutions or with buffer dissolving agents. It is also possible to use enzymes (protease), which hydrolyses sericin. Recently, a treatment with H2O at 120°C has also been successfully applied especially on yarns. On wool, the scouring process removes oils and contaminants accumulated during upstream processing steps and can be carried out on slivers, yarns and fabrics with solutions containing sodium carbonate with soap or ammonia, or anionic and nonionic surfactants, which carry out a softer washing to avoid any damage to the fibres. The scouring process applied to synthetic fibres removes oils, lubricants and anti-static substances, dust, contaminants and can be carried out on yarns and fabrics (when warp yarns have been bonded, the treatment is called debonding). It is carried out by means of surfactants, detergents and emulsifying agents. Scouring is usually carried out by means of continuous or discontinuous systems, with the same machines used for downstream treatments; temperature, processing time, pH, concentration of reagents, depend on the fibre and on the machine used. Incomplete scouring processes usually originate dyeing and printing defects due to different degrees of wettability and to inconsistent affinity for dyes of the material.

Bleaching
Bleaching treatments are applied to eliminate any impurity and obtain a pure white tone, to prepare substrates for low-density dyes or prints and to level off undesired tone variations. Bleaching agents mainly used for cellulosic fibres are sodium hypochlorite and hydrogen peroxide. They both require the addition of sodium hydroxide in the bleaching liquor to make it alkaline it by favouring the formation of the bleaching ion, which in the first case is the hypochlorite ion and in the second one is the perhydroxyl ion. When using hypochlorite the pH must range between 9 and 11 and the temperature must not exceed 30° C. In fact, as far as the pH is concerned, pH values below 4 give rise to the formation of chlorine while pH values ranging between 4 and 9 give rise to the formation of hypochlorous acid: these chemical substances affect the fibre negatively and do not perform a bleaching action. After the bleaching with hypochlorite it is necessary to carry out an antichlor treatment. Fibres must be treated with hydrogen peroxide, which completely removes the chlorine and avoids the formation of chloramines, which,

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in drying machines, could generate HCl dangerous for cellulose. With hydrogen peroxide, in the presence of alkali, little motes can be eliminated and the autoclave scouring can therefore be avoided.The optimum temperature ranges between 80° and 90° C and the pH between 10.7 and 10.9. Hydrogen peroxide at a concentration of 1-2 vol can be used also for silk after degumming, with a pH of 8 . 9, at 70-80° C for 1-2 hours. On wool, it is possible to improve whiteness with a bleaching process using hydrogen peroxide, with a vol. range of 1 to 3, stabilised with pyrophosphate with a pH value between 8 and 9, at a temperature of 45-50° C for a time which can vary from 30 minutes to 3-4 hours. In alternative, it is possible to carry out a treatment with a pH value of 3-4, in acid environment for HCOOH at ambient temperature; in this case, the formic acid reacts with peroxide, generating performic acid, which carries out the bleaching action. This method slightly damages the wool but gives good results. From an environmental point of view, hydrogen peroxide is more suitable than hypochlorite since it has a lower impact on the environment and effluents can be decontaminated with simpler operations. It is recommended to add sequestering agents to the bleaching liquors. Another bleaching agent used in textile processing is sodium chloride (suitable for synthetic fibres) that takes advantage of the oxidising action of chlorine dioxide generated as a result of the hot acidification of the solution of this salt. Unfortunately, chlorine dioxide is a toxic substance and attacks stainless steels; therefore it is necessary to work in hermetically closed units equipped with suction systems with resistant materials such as stoneware. Bleaching operations can be carried out on yarns, fabrics and knitting with continuous and discontinuous process in circulating liquor machines (autoclaves, jigger, paddle wheel, jet, overflow), semi-continuous (pad-batch, pad-roll).

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Continuous bleaching can be carried out on knitted fabrics using a J-box . The products to be used on the fabric are applied by means of suitably positioned angles; the fabric is introduced in the machine where it remains for the time necessary to complete the bleaching process. Temperature, speed, pressure and pH are controlled automatically. It is also possible to carry out optical bleaching using substances that do not perform a chemical action on the fibre but obtain a whitening effect by means of an optical compensation process of physical nature. These substances release a blue light compensating white and grey, and giving a dazzling white effect. For example an optical bleaching on wool can be carried out after chemical bleaching, using 0,2-0,6 g/l optical bleaching agent at pH 4-5 for acetic acid, at a temperature of 50-60 ° C for 30 minutes.

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Acid Dyes
What are acid dyes?
Acid dye class is a water soluble class of dyes with anionic properties. The textile acid dyes are effective for protein fibers such as silk, wool, nylon and modified acrylics. Acid dyes fix to the fibers by hydrogen bonding, vander waals forces and ionic linkages. An acid dye is a dye, in chemical regard a sodium (less often–ammonium) salt of a sulfonic, carboxylic or phenol organic acid. Acid dye possesses affinity for amphoteric fibers while lacking direct dyes' affinity for cellulose fibers. When dyeing, ionic bonding with fiber cationic sites accounts for fixation of colored anions in the dyed material. Acids are added to dyeing baths to increase the number of protonated amino-groups in fibers.

Chemical structure of acid dyes
The chemistry of acid dyes is quite complex. Dyes are normally very large aromatic molecules consisting of many linked rings. Acid dyes usually have a sulfo or carboxy group on the molecule making them soluble in water. Water is the medium in which dyeing takes place. Most acid dyes are related in basic structure to the following: Anthraquinone type:

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Anthraquinone Many acid dyes are synthesised from chemical intermediates which form anthraquinone-like structures as their final state. Many blue dyes have this structure as their basic shape. The structure predominates in the levelling class of acid dye. Azo dyes: The structure of azo dyes is based on azobenzene, Ph-N=N-Ph (see right showing cis/ trans isomers) Although Azo dyes are a separate class of dyestuff mainly used in the dyeing of cotton (cellulose) fibers, many acid dyes have a similar structure, and most are red in color.

Triphenylmethane related:

Triphenylmethane

Acid dyes having structures related to triphenylmethane predominate in the milling class of dye. There are many yellow and green dyes commercially applied to fibers that are related to triphenylmethane. These dyes are normally very complex in structure but have large aromatic molecules, having a sulphonyl or amino group which makes them soluble in water. Most of the acid dyes belongs to following three main structural molecules, 1.Anthraquinon type 2.Azo dye type

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3.Triphenylmethane type.

Different types of acid dyes
The basic dyes are classified into several groups , based on the leveling properties, economy of the dyeing and fastness properties, however generally these are classified into these three classes,

1.Neutral acid dyes
These are supra milling or fast acid dyes, having medium to good wet fastness properties , some of the dyes have poor light fastness in pale shades . many of the dyes are used as self shades only. These are applied to the fiber in a weakly acid or neutral pH.

2.Weak acid dyes
These dyes belongs to the milling class of dyes. These dyes have good fastness properties but light fastness is moderate to poor.

3.Strong acid dyes
These dyes are applied in a strongly acidic medium and also called leveling dyes, however there wet fastness properties is a limitation. These dyes are very good to produce the combination shades.

Classification according to dyeing characteristics
Acid dyes are commonly classified according to their dyeing behaviour, especially in relation to the dyeing pH, their migration ability during dyeing and their washing fastness. The molecular weight and the degree of sulphonation of the dye molecule determine these dyeing characteristics. The original classification of this type, based on their behaviour in wool dyeing, is as follows: (1) Level dyeing or equalising acid dyes; (2) Fast acid dyes; (3) Milling acid dyes; (4) Super-milling acid dyes. Milling is the process in which a woollen material is treated, in weakly alkaline solution, with considerable mechanical action to promote felting. Dyes of good fastness to milling are essential to avoid colour bleeding during the process.

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Properties of acid dyes
The main properties of acid dyes are , Since these are sold as a sodium salt, there fore these form a large anion in the aqueous medium. 1.These dyes are anionic in nature. 2.These dyes are suitable for wool, silk, polyamide and modified acrylics. 3.These are applied from a strongly acidic to neutral pH bath. 4.These dyes have no affinity for cotton cellulose’s , hence not suitable for cellulosics. 5.These dyes combine with the fiber by hydrogen bonds , vander waals forces or through ionic linkages.

Mechanism of dyeing with acid dyes
Dissolution of dyes in aqueous solvent, produces a colored anion,

The protein and polyamide fibers produce cationic sites in water under acidic conditions, as the acidity of the solution is increased more cationic sites are produced under these strongly acidic conditions. These cationic sites are thus available for the acid dye anions to combine with through hydrogen bonding, vander waals forces or ionic bonding. These linkages are strong enough to break , and thus dyeing produced are fast. Electrolyte in the acid dye bath acts as a retarding agent because of chlorides ions attracted by the positive sites at the fiber and in the competition between. Addition of acid acts as a n exhausting agent , because strongly acidic conditions makes

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more cationic sites available and thus available dye anions got combined with these.

Dye Processes
We can divide dye processes into two categories: immersion dyeing and direct application. In immersion dyeing, the dye is dissolved in a dye bath. The fabric is immersed in the dye bath and processed. A typical immersion process uses a lot of water, has a means of agitating the goods or circulating the bath, requires heating or temperature control, and is processed for an hour or more. The heat and time provide energy for the dye-fiber bonds to form. The term exhaust dyes is used to describe dyes that can bond all the dye molecules onto the fiber. The term exhaust is also used to describe the percentage of dye in the dye bath that is fixed to the substrate at the end of the dyeing process. Well-exhausted dye baths are nearly colorless. Pale colors can exhaust well; blacks never exhaust completely. Direct application refers to any process where the dyes are put directly on the cloth in a concentrated concoction without a bath. Typically, the dye is dissolved in a small amount of water with other auxilliaries such as thickeners, acids, alkalis, or salts. This dye mixture is then applied by printing, painting, stamping, flinging, or other imaginative methods. Subsequent steps, batching or steaming, are required to form the dye-fiber bonds; this is called fixing the dye. The colored goods must now be washed to remove the auxilliaries that were in the dye mixture. When done properly, nearly all the dye fixes to the cloth, even dyes that do not exhaust well in a dye bath. This method does not require heating of large volumes of water nor disposal of dye baths, making it more economical and reducing environmental impact. Small-scale dyers rarely use direct application to lay down a large field of level color. In most direct-application techniques, level dyeing is not a goal. Immersion dyeing usually gives the best penetration, meaning that the entire cross-section of the fiber is uniformly colored. Direct applications may reach only the surface of the fiber. Dyeing temperature

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The dyeing is generally carried out at boiling temperature for 30- 60 minutes depending upon the depth of the shade and dyestuffs used.

Dyeing leveling agents In the case dyeing with acid dyes , mainly cationic agents such as ethoxylated fatty amines are used as leveling agents. Heating rates Heating rate is generally kept 1-30C/Min Washing off proces A typical dyeing cycle of nylon filament dyeing with acid dyes is shown in the above chart, Wool dyeing method with acid dyes

Method 1

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At A set bath at 50° with: 4% Sulphuric Acid (96%) 5% Glaubers Salt anhydrous, pH 2.5 to 3.5 At B add required amount to dyestuff. Method 2 At A set bath at 50° with: 2% Formic Acid (85%) 5% Glaubers Salt anhydrous, pH 3.5 to 4.5 At B add required amount of dye. At C add 2% Sulphuric Acid (96%) or 2% Formic Acid (85%). Thoroughly rinse after dyeing to remove loose colour.

A dyeing cycle for nylon filament dyeing

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Fastness properties of acid dyes?
The wet and light fastness properties of the acid dyes varies from poor to excellent , depending upon the molecular structure of the dyes.

The fastness properties as per the category are as follows
Neutral acid dyes:-since these dyes have very good leveling and migration properties ,and have a low affinity for the fiber, therefore the wet fastness properties of this class are generally poor. Weak acid dyes or half milling dyes :- These dyes have a medium to good affinity for the fiber and are generally applied in a weakly acidic bath, shows medium to good wet fastness properties. Strong acid dyes or super milling dyes :These dyes have poor exhaustion properties, therefore applied under very strong acidic condition , exhibit good fastness properties.

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CLASSIFICATION OF ACID DYES
Strong acid dye-bath Weak acid dye-bath pH acid required solubility level dyeing dyeing time wetfastness color range 3.5 2-4%sulfuric acid high Very good Relatively short fair wide range bright colors examples Lanaset Kiton Pro WashFast Nylomine Miyako Ricoamide 3.5-5.5 2-4% acetic acid intermediate intermediate intermediate better intermediate Neutral dye-bath 5.5-7 ammonium sulfate low fair longer time very good moderate brightness

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Safety Considerations
The two major hazards I encounter in my work are inhaling the very finely powdered dyestuffs and fumes from discharge procedures. Make sure you have good ventilation. Dust and fumes can circulate in a home and affect people in other rooms. Any tiny particle that gets deep into your lungs can cause damage. Wear a particle or dust mask, available at any hardware store, when working with dye powders. Make sure it fits well. When doing discharge procedures, wear a respirator with acid gas cartridges. A clean studio is a healthy studio. Spilled dye will dry into powder and find its way into your lungs. Wipe up any spills with water. Some people develop allergies to certain dyes after exposure to them. The best way to deal with these allergies is to prevent them. Do not let any dye enter your body. Don’t eat it, don’t breathe it, don’t absorb it through your skin. In addition to the mask and respirator already mentioned, wear gloves when working with dye baths or wet dye on fabric. Consider wearing a plastic apron (especially if you are sloppy, like me!). Never use the same equipment for both dyeing and food preparation. The best way to dispose of dye baths is the sewer system--it is designed for waste disposal. The amount of waste from home dyeing is insignificant in the total waste treated, even in a small village. If you work outside, you may have to carry the spent dye bath to the toilet for disposal. Sulfuric acid, H2SO4. A strong acid. Used for pH<3.5. A clear, colorless, odorless liquid. Acetic acid, CH3COOH. A weak acid. Used for pH 3.5-5.5. Acetic acid is a liquid that has a recognizable pungent odor. Vinegar is about 5% acetic acid with a pH 2.4-3.4. It can be purchased as 26% solution from shops that sell chemicals for developing photographs (sometimes it also contains a yellow colorant that renders it unsuitable for dyeing), or as a 56% solution from some dye suppliers (this must be shipped as a hazardous material and the shipping is thus expensive)

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and as glacial acetic acid (99.5%) from chemical suppliers (the name glacial comes from the fact that at slightly below room temperature it solidifies or freezes). . Acetic acid and sodium acetate form a buffer system that maintains the pH constant around pH 4.7.

Citric Acid, HOC(CH2COOH)2COOH. A weak acid but stronger than acetic acid. It is a white crystalline solid at room temperature. Widely occuring in plant and animal tissues, responsible for the pleasant sour taste of citric fruits. Easy to buy (used in the kitchen) and ship. Can fom a buffer with sodium citrate but this buffers works best around pH 3.1.

Disperse dye for Nylon dyeing
Disperse dye is originally developed for the dyeing of cellulose acetate. They are substantially water insoluble. The dyes are finely ground in the presence of a dispersing agent then sold as a paste or spray dried and sold as a powder. They can also be used to dye nylon, triacetate, polyester and acrylic fibres. In some cases a dyeing temperature of 130 deg C is required and a pressurised dyebath is used. The very fine particle size gives a large surface area that aids dissolution to allow uptake by the fibre. The dyeing rate can be significantly influenced by the choice of dispersing agent used during the grinding. Disperse dyes have low solubility in water, but they can interact with the polyester chains by forming dispersed particles. Their main use is the dyeing of polyesters, and they find minor use dyeing cellulose acetates and polyamides. The general structure of disperse dyes is small, planar and non-ionic, with attached polar functional groups like -NO2 and -CN. The shape makes it easier for the dye to slide between the tightly-packed polymer chains, and the polar groups improve the water solubility, improve the dipolar bonding between dye and polymer and affect the colour of the dye. However, their small size means that disperse dyes are quite volatile, and tend to sublime out of the polymer at sufficiently high temperatures.

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The dye is generally applied under pressure, at temperatures of about 130oC. At this temperature, thermal agitation causes the polymer's structure to become looser and less crystalline, opening gaps for the dye molecules to enter. The interactions between dye and polymer are thought to be Van-der-Waals and dipole forces. The volatility of the dye can cause loss of colour density, and staining of other materials at high temperatures. This can be counteracted by using larger molecules, or making the dye more polar (or both). This has a drawback, however, in that this new larger, more polar molecule will need more extreme forcing conditions to dye the polymer2. The most important class is the azo class. This class of azo disperse dyes may be further sub-divided into four groups, the most numerous of which is the aminoazobenzene class. This class of dye can be altered as mentioned before, to produce bathochromic shifts. A range of heterocyclic aminoazobenzene dyes are also available. These give bright dyes, and are bathochromically shifted to give blues. The third class of disperse dye is based on heterocyclic coupling components, which produce bright yellow dyes. The fourth class are disazo dyes. These tend to be quite simple in structure.

1. High temperature high pressure dyeing
Pretreatment:
The pretreatment is essential to remove the lubricant oils and other auxilairies used during spinning and weaving or knitting operations. The following simple treatment is enough to remove those impurities.

Recipe:
Lissopal D paste Soda Ash Temparature Time = 2 grams/liter = 2 grams/liter = 90~95°C =20 minutes.

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pH

= 5.5 to 6.

2. Drain - Hot Wash @ 70°C for 10 minutes - Cold wash - Neutralize with 1 cc/liter Acetic Acid.

Dyeing Process:
Nylon textiles require a Heat Setting operation before dyeing. Heat setting eliminates the internal tensions within the fiber generated during manufacture and the new state can be fixed by rapid cooling. This heat setting fixes the fabrics in the relaxed state and thus avoids subsequent shrinkage or creasing of fabric. Read Heat Setting Process ...

Dyebath Setting & dyeing:
Set up the dyebath with the following auxilaries and chemicals:
• • • •

Lyogen DFT = 0.5 gpl Sandozen PES = 1.0 gpl Acetic Acid = 1 gpl Check pH to 5.5 to 6.0

- Set the dyebath with the above materials. Raise the temperature to 50°C and run for 10 minutes. - Dissolve the dyestuff with soft water at 50°C and filter it. - Add the dyestuff slowly in to the bath. Check the pH to 5.5. to 6. - Raise the temperature to 115°C at 2°C per minute and run 10 minutes. - Raise the temperature further from 115°C t0 135°C at 0.5°C per minute. - Hold for 45 to 60 minutes according to the depth of the shade. - Lower the temperature to 80°C and drain the bath.

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- Do Hot Wash (70°C) for 10 minutes followed by cold wash.

Reduction Clearing:
This is the process to improve the fastness of the dyed material by removing all the dyestuff that is superficially adhearing to the fabric and staining the cotton portion of the blend. The following method is found to be most suitable for any depth of dyeing. Recipe: Cyclonon ECO = 2 gpl Acetic Acid = 2 gpl Treat the fabric at 70°C for 20 minutes. Do hot wash and cold wash. Drain and unload the batch.

Dyeing process for nylon

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At A set bath at 50° A - Add Auxiliaries & Acetic Acid At B add Disperse Dyes (pre-dispersed)

2. Carrier dyeing
Carrier dyeing is carried out under atmosphere pressure by an addition of carrier to the dyeing liquor. Methylnaphthalene or chlorobenzene type carrier is used generally, which is added in concentration of 2-7 g/L to the dyeing liquor. Other conditions of the dyeing liquor are the same as those for high temperature dyeing. The temperature is raised gradually from 40-60°C and continued for 90120 min at 100°C. In carrier dyeing, in some case the troubles such as tarring of dye or carrier spot are taken from the no stability of emulsifier in the carrier under high temperature or some other conditions. Therefore, it is necessary to select the carrier so as to prevent the troubles. Reduction cleaning as stated in high temperature high pressure dyeing.

3. Thermosol dyeing
Thermosol dyeing is a continuous dyeing method which is applied mainly for the Nylon,polyester/cotton blended materials. General dyeing condition is as follows. Dye and 0.5-2g/L of migration inhibiter (for example, sodium alginate) and also wetting agent if necessary are added to the padding liquor.

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Squeezing is carried out 1dip 1 nip at room temperature, pick up 65-70%. Drying at 70-90_C. After padding and intermediate drying, thermosol fixation is carried out by dry heating for 60-120 sec. at 180- 210°C depending on the form of the material and type of disperse dyes. - E type: 180-190°C x 60-120 sec - SE type: 180-200°C x 60-120 sec - S type: 200-210°C x 60-120 sec Reduction cleaning as stated in high temperature high pressure dyeing.

Reactive Dyes:
Reactive dye s are dye s which usually have the basic structure of acid, direct , or mordant dyes but which in addition have a reactive group capable of covalent bond formation with the fiber. Since the fiber must have reasonable reactivity toward the dye reactive group, application of these dyes has been limited to cellulosic , protein, and nylon fibers for the mos t pa rt.

REACTIVE RED The fastness of reactive dyes covalently bound to the fiber is excellent . Reactive functional groups have been selected for incorporation into reactive dyes which will react readily with the fiber after diffusion into the structure but which will not hydrolyze (decompose) in the water solvent used in dye application. Acidic or basic conditions are necessary for successful and rapid reaction of the reactive dye

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with the fiber, so dye appl ication is carried out at either sl ightly acid or basic pH (hydrogen ion concentration). Procion dyes are the best known of the reactive dyes.

Used Dyeing Machine Jiggers
These machines have been used for a long time to treat medium-size lots of woven with an open-width exhaust dyeing process. The fabric moves while the liquor stands still, except for the very latest machines, which are also equipped with a circulation pump. The fabric pieces are sewn together tail-to-head, forming a sort of .ribbon.. At the head and at the tail of the ribbon two cloths are added (4.5 m long) to allow the regular dyeing of the whole pieces, also leaving the machine drawn-in once the dyeing process has come to an end. Theassembled pieces are taken down from a roll, pass through the liquor (they are kept in thecorrect position by means of transport cylinders and a tension equaliser, which avoids the formation of wrinkles). The fabric is then wound on a takeup roll until the dyeing process has ended. The piece through speed and tensions are adjusted by special devices to avoid any change in dimensional stability, above all when treating lightweight fabrics and/or delicate fibres. The maximum diameter of the roller can be 1,450 mm with a width of the piece of cloth ranging between 1,400 and 3,600 mm. The piece through speed is adjusted between 30 and 150 m/min. and kept constant during the whole operation. Also the tension must be constant and it can be adjusted between 0 and 60 kg. Since the passage time is very short, dyeing occurs above all on the fabric wound on the rolls. The composition of the liquor absorbed must be as uniform as possible on the whole width and length of the fabric piece; for big lots, many additions may be necessary to avoid the so-called head-tail defects. Lightweight fabrics (viscose, nylon) that are stretched excessively during the takeup step can show .shading. defects. Jiggers work with a quite low liquor ratio (from 1:1 to 1:6). Together with standard atmospheric systems, builders also offer HT jiggers inside autoclaves working at high pressure. Jiggers are suitable for dyeing all type of fibres.

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Pigment Dyeing on Fabric:
Pigments implied general insolubility and complete insolubility in water.

Required Properties of pigments:
1. They should have covering power which is influenced by particle size 2. Should be inert, stable and have long life 3. Should have capability of mixing 4. Good wet fastness, light fastness and abrasion resistance 5. Good resistance to acid, base, perspiration, chlorine, peroxide and gas fading 6. Good solvent resistance (insoluble in water, CCl4, Cl2C=CHCl) 7. Suitable brilliance, hardness and stability 8. Suitable characteristics for good dispersion including particle size and distribution, electrical charge (most are negatively charged particle), specific gravity, purity and crystalline structure, conditions of precipitation of the pigments 9. Should be applicable to all fibers.

Classification of pigments: o According to origin
1. Natural/Mineral: Iron ores, clays, chalk etc 2. Synthetic/chemical: white lead, ZnO, TiO2 and large number of inorganic and organic color

o According to Reactivity
1. Reactive pigment: some pigments on account of the chemical character react with oil, fatty acids and soaps. These are called reactive pigments e.g. ZnO, red lead 2. Inert pigment: TiO2

o According to Chemical Nature
1. Organic pigment: appx 25% (by wt.) of the world production of organic colorant is accounted for organic pigments. They account for only 4% of total pigment production. Of the total organic pigments production yellow, red and blue

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tones accounted for 89%. Most organic pigments exhibit a small solubility, typically in polar solvent. All the organic pigments are soluble in one or more of the four chemical: Chloroform (CHCl3), Methyl alcohol (CH3OH), Dimethyl formamide (DMF) and concentrated H2SO4. Organic pigment consists of:

1. Azo pigment:
o Strong tinctorial strength o Good alkali resistance o Excellent brightness o Cover a wide range with regard to other application properties o Poor alkali resistance of certain organometallic pigments make them unsuitable for printing

2. Diarylide orange and yellows:
o Extremely bright color o Inferior light fastness

3. Phthalocyanine
o Blue, greens are dominant shade especially in plastic coloration o Offer low migration o Good temperature stability o Excellent light fastness o Good heat resistance o Excellent alkali resistance o Good solvent resistance o Used extremely in printing, pad dyeing and dope dyeing

4. Hasna yellow
o Good light fastness o Have migration tendency

2. Inorganic pigment:
o They account for 96% (by wt.) of total production. More than half of their production volume is accounted for a single production, TiO2, the most important white pigment

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o H2SO4 is a good solvent for many inorganic pigments o They are opaque o Less expensive o More weather resistant o More chemical resistant o Insoluble in most organic solvents o Highest degree of light fastness o Excellent heat resistance

They consist of
1. Salts: Sulfates, carbonates, silicates and chromates of many metal elements like, Ti, Zn, Ba, Pb, Sb, Zr, Ca, Al, Mg, Cd, Fe, Mo, Cr etc. 2. Oxides of Ti, Zn, Ba, Pb, Sb, Zr, Ca, Al, Mg, Cd, Fe, Mo, Cr etc. 3. Metal Complexes: Naturally occurring oxides and silicates

Uses of Pigment:
1. Pigments are used for coloration of a very broad and diverse number of materials 2. Surface coating for interior, exterior, automotive and other application 3. Paints based on olegoresinous liquid and water emulsion 4. Printing ink for papers (lithographic, rotogravure and flexographic systems (and for other materials such as metal plates, foils, artists and writing material) 5. Coloration of plastics and rubber 6. Textile printing 7. Coloration of manmade fibers by mass pigmentation before fiber formation (dope dyeing) etc.

Typical Recipe;
Pigment: 10-20gm/L Binder: 40-50 gm/L Thickener: 35-50 gm/L Catalyst: 5 gm/L Thickener: 2 gm/L Dispersing agent: 2 gm/L

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Procedure:

 Binder is weighted and diluted with cold water  Pigment and thickener is added with cold water  Catalyst solution is added  Dispersing agent is added  The dyeing liquor is well filtered and stirred; material is padded  The material is dried at 70 -100°C in hot flue steam but no use of cylinder dryer.  Curing is done at 150°C, 2-3 min

Precautions:

 No alkalinity: The fiber to be dyed should not be alkaline  OBA: OBA may produce faulty shade No  No formation of skein: Binder should not be allowed to form skein which ultimately give specky shade

Typical procedure for Garment dyeing:

 First bleach the material then treat with a synthetic mordant cationising agent at pH 7  Rinse at 60°C at a rate of 2°C/ min for 20 min  Cold rinse  Apply pigment at 7O°C (pH 5) for 20 min  Add salt, acid and raise temperature when necessary  Now use binder 4% for 10 min at 70°C  Cold rinse with 1 gm/L soap wash for 10 min at 65°C  Cold rinse and dried

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Textile printing
Textile printing is used to signify the production, by various means of colored patterns on designs upon all sorts of textile fiber. Textile printing is the most important and versatile of the techniques used to add design, color, and specialty to textile fabrics. In other words, dyes and pigments are applied locally or discontinuously to produce the various designs. In fact, printing is described as ‘localized dyeing.’ The forces which operate between the dye and the fiber (on mechanical retention, hydrogen bonding, chemical reaction, electrostatic attraction etc.) are the same in dyeing and printing. The term 'colorant' is used here because it covers both dyes and Pigments.

STEPS OF PRINTING
• Preparation of the fabric • Preparation of the print paste. • Printing the fabric. • Drying the printed fabric. • Fixation of the printed dye or pigment. • Afterwashing.

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STYLES OF PRINTING
Percentage of rejection is lower than the discharge method • Direct style • Discharge: white and colored • Resist style • Raised style • Flock style • crimp/ crepon style • Burn out style

Direct printing
This method involves the following steps: printing, drying, steaming and washing. This type of printing is generally used for white or dyed cloths (usually dyed in pastel shades), by applying the sequence of all the colours, until the original pattern has been reproduced. This is the most common printing method and can be used with all the main colour classes of dyes and on fabrics produced with any kind of fibre (some problems may only arise with blends). The technical limits of this printing method appear with endless design patterns (particularly those obtained with screen printing methods, while no problems occur for roller printing). Some problems may also arise when printing on backgrounds dyed with pastel shades: in fact, this could create problems on several areas of the design to be printed in light shades, thus limiting the number of reproducible pattern variants. Pigment printing represents an alternative to direct printing With pigment printing there is no need to carry out a steaming process, as steaming is replaced by polymerisation (generally carried out simultaneously with drying). This type of printing process is very simple, low-cost and can be carried out easily on all types of fabrics, particularly on blends, since pigments can adhere to all fibres; there is no need to use dyes of different colour classes. On the other hand, the adhesives, which bind the pigments to the fabric, can give serious problems when the fabric hand varies. For prints with a low coverage ratio, the hand variation can be acceptable but it is not acceptable when the coverage ratio is high, or at least for all uses. Furthermore, the pigment lies on the surface and has low fastness to friction (this depends mainly upon the type and quantity of binding agent and upon the polymerisation degree). Some valid alternatives to this type of printing can give special effects such as printing with swelling agents (generally synthetic

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polyurethane-base pastes are used), with covering pigments and glitter (metal powders or particles of plastic materials) etc.

Four-colour printing
In the four-colour printing process, primary colours (magenta, yellow and cyan, plus black) are used. The different shades are obtained by applying dots of the primary colours in variable densities: this technique also takes advantage of the ability of the eye to combine colours when observing them from a certain distance. Design patterns with different hues and tones can be obtained by using only four printing plates. This method however limits significantly the possibility of pattern varying. This technique is used only for fixed patterns and pure saturated colours cannot be reproduced.

Discharge printing
Basic steps are printing, drying, steaming and washing. This technique is used on dyed fabrics (usually in dark shades). The fabric is dyed in the piece and then printed with a chemical that destroys the colour in designed areas. Sometimes the base colour is removed and another colour is printed in its place; but usually a white area is desirable to brighten the overall design. This printing method is generally used to obtain designs with tiny details, sharp and welldefined edges on coloured backgrounds, patterns with low coverage ratio on coloured backgrounds, and to avoid pattern matching problems on endless design patterns with coloured backgrounds. The results obtained with this printing method could be hardly eproducible with direct printing since it would be very difficult to obtain wide backgrounds, smooth and well penetrated, with sharp edges without seam defects. A problem for this printing method is represented by the need to choose perfectly destroyable dyes for backgrounds, which cannot be affected by the discharging agent used as brightener. The selection restricts the number of applicable dyes and above all, for some colour classes, very few dyes grant a good fastness to light and moisture, but excellent colour effects. With this type of printing carried out on black or navy blue backgrounds it is also impossible to check if the various colours are correctly positioned; any mistake will be visible only after the steaming process and at that point it would be impossible to correct it. This problem could be limited by testing the printing result on a white cloth before beginning the printing process.

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Resist printing
With the old method of physical resist printing, (hydrophobic) products or printing pastes were applied to the fabric to avoid contact and penetration when the fabric was subsequently immersed in the dyeing liquor (Batik). Now the most diffused printing system is the chemical resist printing carried out with different printing methods, using pastes containing chemicals, which avoid fixation of background dyes (particularly for .reactives on reactives. applied on fabrics made of cellulose fibres). Some of the printing methods are detailed in the following: a) Resist printing on covered background: a pad dye is applied and dried; the printing is carried out with printing pastes containing products avoiding the fixing of background colour (but they do not avoid the fixing of any brightener used). The fabric is then dried, steamed and washed (this is the most diffused resist printing method). b) Resist printing by overdyeing: the operations of the resist printing method previously detailed are carried out in inverse sequence; therefore the fabric is first printed and then covered. c) Resist printing by overdyeing: this method is similar to the previous one, but the covering operation is replaced with the roller printing of the background. d) Printing on polyester: polyester printing must be carried out applying the resistdischarge printing method. Printing pastes containing both the discharge and resist products applied on covered background must be used.

Transfer printing
This printing method is used for printing on synthetic fibres, particularly P.L. With this efficient method disperse dyes, previously printed on special continuous paper on the fabric, are transferred on the fabric by means of rollers with engraved frames. The design is transferred by contact between the paper and the fabric, which is then passed through heated rollers at a temperature of 190-210°C. With this method, disperse dyes sublime (i.e. change directly from the solid to the gaseous state without passing through the liquid phase) melt, penetrate the fibres and bind by heat and pressure onto the fabric surface in a few hundredths of a second.Recently many manufacturers have used this printing method also with acid dyes on PA and reactives on cellulose fibres.

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METHODS OF PRINTING
• Block printing • Stencil printing • Roller printing • Screen Printing o Hand screen o Semi automatic flat screen o Rotary screen • Transfer printing o Flat bed o Continuous transfer o Vaccum transfer • Digital Inkjet Printing

Colour kitchens
The colour kitchen can be a manual system where all the operations for preparing the thickener, weighing the dyes and the auxiliaries, dissolving and preparing of master batches and cutting pastes is manually carried out by the operators working on the colour kitchen. This approach to work entails some problems both for health protection and results; small inaccuracies, momentary distraction of the operator as well as different ways of working of various operators can compromise the reproducibility of results. Now many manufacturers use automatic colour kitchens both for sampling and production purposes. In these colour kitchens the various master batches and the cutting thickeners are stored in big containers from which they are automatically taken by means of pumps to be then used or to prepare the cuts. Special automatic distribution systems can reproduce the stored recipes (by recalling them by means of the keyboard) and accurately weigh, blend and mix the components. In several colour kitchens the balance incorporating the container for preparing the pastes is placed on a trolley, which is moved automatically under the dispenser ozzle of the containers (for cutting and blending the various master batches). In other colour kitchens distribution nozzles are assembled all together above the balance. The products must be perfectly blended before use.

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Picture 78 - Scheme of a colour kitchen

Pigment Printing
In pigment printing, insoluble pigments, which have no affinity for the fiber, are fixed on to the textile with binding agents in the pattern required. This description is perhaps oversimplified, but it does obviously set pigments apart from dyes that are absorbed into the fiber and fixed there as a result of reactions specific to the dye.

Historical Development of Pigment Printing:

 Until 1937 natural polymers as binders and thickeners (starch, glue)  Around 1937 emulsion thickening  Around 1960 use of aqueous self-crosslinking dispersions as binders  Around 1970 development of synthetic thickening agents based on acrylic acid  After 1980 ecological improvements (e.g., emission)

Why Pigment Printing is Important:

 The pigment can be applied to all fibers potentially and it is the only coloration to glass fiber, fabric and polyester  No wet treatment is required, so drying and curing is applicable to all fiber.  Extensive color range of highly light fast colors  Possible to produce good combination shades on blended fiber in one padding operation  Application procedure is simple  No change of hue of colorant throughout processing

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 Less expensive

A good quality pigment print is characterized by:

 Brilliance and high color value relative to the pigment concentration in material  Minimum stiffening in the handle of the textile  Generally acceptable fastness properties.

Components of a pigment printing system:
A pigment printing system consists of three essential components:  Pigment dispersion: Specific pigments are treated in a grinding mill in the presence of suitable non-ionic surfactants. A particle size of 0.1-3 μm is typical. Generally, the pigment pastes are aqueous based and contain the dispersing agent, humectants (to prevent evaporation and drying out).  Binders and cross-linking agents (polymers): The binders used in pigment printing systems are film-forming substances made up of long-chain macro molecules which, when heated with a suitable acid-donating catalyst, form a threedimensional structure in the pigment.  Thickeners and auxiliary agents: These give the required print thickening power (rheology). Binder: The binder is a film forming substance made up of long-chain macromolecules which, when applied to textile together with the pigment, produce a three dimensionally linked network. Binder- CH2-OR + HO-Textile Binder –O- textile + HOR Where R is H or CH3. The links are formed during some suitable 'fixing' process, which usually consist of dry heat and a change in pH value, bringing about either self-crosslinking or reaction with suitable crosslinking agents. The degree of cross linking should be limited, to prevent the macromolecules becoming too rigidly bonded, thus preserving some extensibility. The important criteria, which ensure that the pigment within the crosslinked binder film is fast to wear and cleaning, are elasticity, cohesion and adhesion to the substrate, resistance to hydrolysis, as little thermoplasticity as possible and absence of swelling in the presence of dry cleaning solvents.

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Required properties for Binders:

 Should be film forming  Should be water swell  Should not be too thermoplastic  Should have atmospheric stability  Should be colorless and clear  Should be of even thickness and smooth; neither too hard nor too stiff.  Should have good adhesion to substrate without being tacky.  Should possess good resistance to chemical and mechanical stress  Should be readily removable from equipments  Should provide good color yield  Should be non toxic

Types of Binders:

 According to the origin
• Natural: glue, gelatine etc • Synthetic: acramin binders

 According to chemical groups
• Acrylic binders: These are normally an aqueous dispersed co-polymer of butyl acrylate and styrene, having N-methylol acrylamide groups for cross-linking purposes. Other Auxiliaries:

 Catalysts:
§ Diammonium phosphate: - most widely used acid catalyst  used in conc. of 0.5% and 0.8% in screen and roller printing respectively  when used in correct proportion produces a pH of 3 in fabric and brings a cross linking reaction § Ammonium salts: sulphocyanide, sulfate and chloride are suitable. Ammonium nitrate: not recommended and it turns polyamide fiber yellow  Urea These are agents that are added to improve “runnability” on printing machines. Owing to their low

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volatility these auxiliaries are used sparingly, maximum amounts of 20 parts/1000 being common; otherwise the fastness properties may be adversely affected.  Softening agents After curing fixation the resultant “handle” of the printed fabric depends on a number of factors: - monomer composition of the binder - presence of water-soluble protective colloids (e.g. alginates, etc.) - extent and type of cross-linking. By the addition of certain compounds (usually termed “plasticisers”) improves the handle of printed goods.  Cross-linking agents These agents are universally based on either urea-formaldehyde types (e.g. dimethylolurea) or melamineformaldehyde types. They are incorporated into printing compositions in an attempt to increase various aspects of fastness, particularly rub and scrub fastness with synthetic fibers. A maximum addition of 10-20 pts/1000 is normally encountered: larger amounts can have a quite marked effect on the “handle” of the fabric

Pigment Printing Recipe and Procedure:
Typical Recipe:
Pigment: 10-20gm Binder: 40-50 gm Thickener: 35-50 gm Catalyst: 5 gm Dispersing agent 2 gm Water x ml

Procedure:

 Preparation of printing paste using dispersing agents and thickener and catalyst.  Application of pigment paste and binding resin together  Drying at 140 – 150°C  Curing to fix the resin pigment

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Affect of curing on Nylon:
Temperature Time Strength loss 205°C 1 min 0% 220°C 1 min 0% 235°C 1 min 2% 245°C 1 min 5% 260°C 1 min 13%

Problems of Pigment Printing:

 Adverse effect due to binder as it changes texture of fabrics.  The quality of printing or dyeing depends on the characteristics of binder used to affix the pigment even more than the properties of pigment.  Some solvents used in emulsion like kerosene, white spirit cause problem like flammability.  The chemical and physical influences on the binder and print paste can interfere during production and processing resulting in sticking especially in roller printing.  The gumming up of equipments, odor, air and water pollution  Difficulty in obtaining the necessary wet treatment fastness and abrasion resistance with certain products, may not be obtained pigment printing or dyeing.

Screen Printing
Screen printing is arguably the most versatile of all printing processes. It can be used to print on a wide variety of substrates, including paper, paperboard, plastics, glass, metals, fabrics, and many other materials including paper, plastics, glass, metals, nylon and cotton. Some common products from the screen printing industry include posters, labels, decals, signage, and all types of textiles and electronic circuit boards.

Screen Printing Process:
• Hand screen • Semi automatic flat screen • Rotary Screen

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Screens:
• Made of cotton, silk, nylon cloth, polyester or metal gauze • Screen mesh refers to the number of threads per inch of fabric. The more numerous the threads per inch the finer the screen. • The usual mesh of screen employed for cotton and silk printing is 80 threads per inch. • The finer the screen the sharper are the outlines but more effort is needed to force the printing paste through the screen.

Screen Frames:
• There are two types of screen frames, metal and wood. • Screen frames for commercial use are usually made of steel, or a lighter metal, with a hollow cross section to provide rigidity with minimum weight. • Screen frames are usually 26" x 55" (measured externally) and 23" x 52" (measured internally) for printing 45" wide cloth

Screen Fabric:
There are two types of threads for screen fabric: • Monofilament - single strands weaved into fabric • Primarily used in commercial printing and other applications • Advantage: Monofilament is easier to clean than multifilament • Multifilament - multiple strands wound together like a rope, then weaved into fabric. • Primarily used in textile printing. • Disadvantage: ink tends to build up on screen, more difficult to clean. Monofilament mesh has become the industry standard.

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What Can Be Finish Of Nylon?
Textile Finishing :
Finishing has been defined by Textile Institute as ‘Descriptive of processes, physical or chemical, applied to a substrate to produce a desired effect.’ Finishing encompasses chemical or mechanical treatments performed on fiber, yam, or fabric to improve appearance, texture, or performance.

Mechanical Finishing
• Heatsetting • Brushing and napping • Softening, Calendering, or ironing • Optical finishing • Shearing • Compacting

Chemical Finishing

• Softener • Anionic, cationic, nonionic, silicone • Durable press / resin finish • Water repellency • Stain Resistance • Soil Release • Fire Retardancy • Antimicrobial finishes • Slow release of fragrance and odor absorption

FABRIC SOFTENERS
A Softener is a chemical that alters the fabric hand making it more pleasing to the touch. The more pleasing feel is a combination of a smooth sensation, haracteristic of silk, and of the material being less stiff. The softened fabric is fluffier and has better drape.

Functions of softeners:

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• Increase aesthetics (drape and silkiness), • Improve abrasion resistance, • Increase tearing strength, • Reduce sewing thread breakage and • Reduce needle cutting when the garment is sewn. Because of these functional reasons, softener chemicals are included in nearly every finish formulation applied to fabrics.

How softeners alters the handle of textile materials
• Softeners act as fiber lubricants and reduce the coefficient of friction between fibers, yarns, and between a fabric and an object (an abrasive object or a person's hand). Whenever yarns slide past each other more easily, the fabric will be more pliable and have better drape. • Tearing resistance, reduced abrasion and improved sewing characteristics are also related to lower coefficients of friction. • Fabric tearing is a function of breaking yarns, one at a time, when tearing forces are applied to the fabric. Softeners allow yarns to slide past each other more easily therefore several yarns can bunch up at the point of tear. More fiber mass is brought to bear and the force required to break the bunch is greater than the force required to break a single yarn. • Sewing problems are caused by the friction of a needle rapidly moving through the fabric. Friction will cause the needle to become hot and soften thermoplastic finishes on the fibers.

Desirable properties of softener:
• Good compatibility with chemicals • Stable to high temperature, no volatile by water and water vapor • No effect on fastness • No change of shade of color and no yellowing • Low forming, stable to shearing, no deposit on rollers • Regular and complete bath exhaust • Non‐toxic, non‐caustic, non‐corrosive • Easily biodegradable • Dermatologically harmless • Easy handling (liquid and stable) and no restriction of transport and storage

Raw Materials for Softeners:

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Hydrocarbon radicals having a total of 8 to 20 carbons are the most effective molecular group used in textile softeners. Commercially, there are two main sources of raw material supply that are inexpensive and available in large quantities:

1. Fat derived Raw Materials: obtained from animal and vegetable fats and
oils i. Fatty acids ii. Fatty acids monoesters iii. Fatty acids ethoxylates iv. Fatty amines v. Fatty alcohols

2. Petrochemical derived Raw Materials: based on crude oil and natural
gas i. Long chain hydrocarbons ii. Short chain hydrocarbons iii. Long chain alcohols iv. Alkyl aromatics v. Ethylene, propylene oxides vi. amines

Anti-static Treatments
Being characteristically hydrophobic, synthetic fibres present a low electrical conductivity, so low that, after rubbing against other bodies, they can retain an electrical charge for a long time. Indeed, when two bodies, characterised by a neutral electrical charge and each having a different chemical composition, are rubbed together, the electrons of each of them will attract those of the other in such a way that both bodies acquire an electrical charge. Generally speaking, the body with the higher dielectric constant takes a positive charge, while the substance with the lower dielectric constant takes a negative one. A potential difference, of as much as several hundred millivolts, is created between the two contact surfaces. If these two bodies, both charged with electrical energy, are separated, the potential is

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increased, even as high as many tens of thousands of volts. As far as fabrics are concerned, this discharge of energy occurs mainly between the innumerable fibrils. It is responsible for creating the familiar crackling sound and for the formation of the tiny sparks and the genuine electrical discharges that can cause perceptible discomfort. To reduce this phenomenon, one can operate in a controlled environment that has high relative humidity, use conductors that can discharge the material, ionise the atmosphere, or apply hydrophilic chemical substances. Chemical products that confer an anti-static effect on synthetic fibres form, on the fibre surface, a thin film whose electrical conductivity is higher than that of the fibre. These substances are anionic, cationic, amphoteric, or even non ionogenic. The conductivity of a synthetic fibre is thus increased when it is covered with a surface-active substance in which the hydrophobic groups are oriented towards the fibre and the hydrophilic groups are oriented away from it. The presence of mobile electrical ions is, however, important. Depending on the substantivity of the chemical products used, it is possible to choose between different application processes: immersion, exhaust or padding. Anti-static finishing treatments are rarely applied through spraying. Chemical products that have the capacity to confer a permanent anti-static effect condense at high temperatures; they can even condense when stored at ambient temperature in hermetically sealed rooms or containers (as can epoxy resin-based products). All the anti-static products available on the market can be applied by padding, while only a few can be applied using the exhaust process. The material is immersed in liquor containing the anti-static chemical product, squeezed (to 40-60% absorption) and finally dried in a stenter at 80-100°C. If the stenter is equipped with additional chambers that can be used to carry out heat setting processes, then it is also possible to condense, at the same time, anti-static products able to confer permanent effects

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Care Of Your Nylon Garment:
1) Machine wash in cold water. 2) Wash it separately from other types of fabric. 3) If needed, use only non-chlorine bleach to bleach your nylon garment. 4) Turn the setting to low before tumbling dry. 5) Remove your nylon garment promptly from the tumbler.

Other Tips:
• • •

Extensive washing and drying in an automatic dryer can lead to piling. White nylon should be washed separately to avoid it turning grey. To avoid yellowing of your white nylon, you should bleach it frequently with Sodium Perborate bleach.

Uses:

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Nylon is popular for hosiery and is used to make track pants, shorts, swimwear, active wear, windbreakers, bedspread and draperies. It can also be made into parachutes, flak vests, combat uniforms, tires and life vests, or used as the netting of bridal veils, umbrellas and luggage.

Md.Abul Hasan University of South Asia Bangladesh.

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