GATE TUTORIAL: DRAWING & HEAT SETTING DRAWING INTRODUCTION The as-spun fibres have poor elasticity (inability to recover) and they undergo plastic deformation on _ application of low levels of stress. This makes them unsuitable for any application including that of apparel ‘The polymer chains in the as-spun fibres are in partially folded conformation and can extend easily on application of stress. Figure -1 shows a stress-strain plot of an as-spun fibre. The elastic region is small and is » bound by the yield point that occurs at a low stress and extension level. Following the yield point, the fibre shows deformation without much resistance till all the chains are unfolded and a new improved (more elastic) network of polymer is formed. In this region, the polymer chains assume new extended conformation and do, Rot recover back to their original state when stresses are released. This is known as the region of ‘natural draw” and the extensibility is called “Natural draw ratio (NDR)” of the fibres. This region of easy extensibility must be removed to make the fibres stable and show the behaviour of increasing resistance with increasing extension. Maximum draw ration (MDR)__ Stress (gdener) ‘Elongation % Figure 4.1: Stress-strain curves for (A) as-spun and (B) spun-drawn fibre. Drawing is necessary to remove the region of natural draw of the fibres. When the fibre is drawn beyond the NDR, polymer chains form an elastic network with extended conformation in the direction of draw (i.e. along the fibre axis). This gives fibres higher yield point, strength, intial modulus, and recovery compared to its as- igure 1 also shows a typical stress-strain plot of a drawn fibre in comparison to that of an as-spun spun form. Fi t, is the maximum extensibility a fibre may be subjected to, fibre. Maximum draw ratio (MDR), in contrast ‘fbefore it breaks ‘TRUE STRESS VS TRUE STRAIN member that the stress-strain curves that are usually drawn while explaining the properties ees of drawing are based on load per unit original denier and strain is calculated based on “Frthe specimen. However, at any point during tensile drawing, the true stress is different because the diameter or the denier of the material is continuously reducing. Similarly, the true strain must be calculated based onthe actual length ofthe fbre at that moment ¥ calcul It is important to rel of fibres and the proct Therefore, as shown in equation [1] true stress is given by o=o'xDR.. y ! totus & acapemyGATE TUTORIAL: DRAWING & HEAT SETTING 0 final length, as showr Whereas the true strain (e) is given by the integral of dV/| in the limits of original length t in equation [2] = In{L/Lo}.... --Q) Ifa stress-strain curve is converted to true stress-true strain curve then their behaviout selected standard curves in Figure 2. Le Strain 1 changes as shown for ‘True stress Figure 2: The stress strain curve vs. true stress or true strain curve EFFECT OF SPINNING SPEED ON MAX. DRAW RATIO The natural draw ratio in the as-spun fibre is a function of its spinning speed. Figure 3 shows the residual extensibility (which includes region of natural draw) of the fibres with the spinning speed for PET as-spun fibres. The extensibility is about 400-500% when the fibres are spun at low spinning speeds of 1000-1500 m/min to form LOY filament (low-oriented yarn). The POY filament (partially oriented yarn), which are spun at around 3000-4500 m/min, have the extensibility of around 70-90%. The extensibility significantly reduces at higher speeds due to stress induced crystallization. A natural draw of about 10% may still be observed at very high spinning speeds of 6000 m/min or higher. Therefore, the fibres spun at very high speeds may also have to be drawn though to a much smaller extent. Residual extension Spinning speeds Lotus & acapemyGATE TUTORIAL: DRAWING & HEAT SETTING Figure 3: Residual extension versus spinning speed in PET as-spun filament The spinning of fibres at a high speed results in increasing the deformation of the polymer network, however, the spin-draw imparted to the spinning fibres at high temperature in the spinning line is not able to create a very elastic network of polymer chains. Fast relaxation of polymer chains at the spinning temperature results in {caving a small amount of natural draw and poor mechanical properties even when the spinning is carried out at high speeds. For better properties, it is always desirable to draw the fibre at a temperature just above its Ty. Similar to PET, even in nylon 6, drawability of the as-spun material reduces with the increasing spinning speed, Owing to increased deformation of polymer network. Figure 4 shows a series of true stress-strain curves for undrawn nylon 6 yarns obtained over a wide range of wind-up speeds (500-6500 m/min) that have been shifted horizontally to coincide with the 500 m/min LOY curve. For yams spun at wind-up speeds below 4000 m/min, good fit with the first curve is obtained indicating the presence of substantial NDR (characterized by a flatter region). For yarns spun at wind-up speeds above 4000 m/min, on the other hand, the shifted true stress-strain curves coincide with the first curve only in the final strain-hardening regime. This indicates that network topology changes with increasing wind-up speed. A transition in structure-formation mechanism occurs at wind-up speeds of about 3000 m/min, associated with the onset of spin line crystallization, —As-spun yarn 500 m/min —As-spun yarn 1500 m/min —As-spun yarn 4200 m/min True stress 1.0 2.0 3.0 4.0 5.0 6.0 7.0 ‘True strain Figure 4: True stress-strain curve of undrawn nylon-6 at various winding speeds DRAWING MACHINES Drawing is carried out by simply stretching the filament yam between two sets of rollers. A typical drawing machine is shown in Figure 5. The drawing occurs between feed rollers and take-up rollers (Draw rollers) at room temperature or at an elevated temperature by providing a heater plate. The drawn material is given a stall twist and is wound on a bobbin as shown in Figure. The path of the yarn undergoing drawing is regulated by proving guide pins or alternately placing the feed and take-up (drawing) rollers perpendicular to each other. An idler roller at an angle is provided with each roller set (ie. feed or draw) to allow the yarn to be wound in 3 Lotus & acapemyGATE TUTORIAL: DRAWING & HEAT SETTING multiple loops separately on each on these rollers. This gives a better grip to the yarn and the yarn does not slip easily under drawing tension. The ratio of the surface speed of the draw (V2) and feed roller (Vi) is called the 'machine draw ratio’. The fibre after drawing may relax and recover some part of the machine draw ratio applied to it. Eventually, the fibre may attain a draw ratio called ‘actual draw ratio’, given by final length to the initial length, which is equal to or less than the machine draw ratio depending upon the amount of relaxation the fibre undergoes. The speed at which the fibre travels between the two rollers determines the rate of drawing. An estimate of this draw rate can be worked out as follows: The average speed between the rollers is (V1 + V2)/2; if the distance between the draw rollers is L, then the time spent by the fibre during drawing is t= L/ (V+V2)/2. Feed rollers Heater-plate Draw rollers Ring frame > Figure 5: Schematic diagram of a typical drawing frame. If the DR is 2 (which is also equal to ‘extension in fraction’ + 1) then th ; e rate is shown in equation [3] of extension is measured § Rate of extension = (1~ I)/t.....++-«(3) LOTUS BBB acancan, iGATE TUTORIAL: DRAWING & HEAT SETTING It must be noted that here the drawing zone was taken as the entire length (L) between the two rollers. However, the drawing occurs by forming a neck, which is localized in fibre length of a few centimeters. Therefore, the actual draw rate is much higher than what can be estimated using the above equation. The drawing is normally carried out by a cold drawing process (explained later) where the fibre is drawn by forming a neck (also known as neck drawing). The location and stability of the neck is important in obtaining @ uniformly drawn filament yam. A snubbing pin may be used to help the formation of the neck or to stabilize it in a narrow zone. The drawing is carried out at just above the T, of the polymer. For apparel grade nylon-6, drawing is carried out at the room temperature, while for PET it is carried out at 80°C or above. Drawing may be carried out in a single step called single stage drawing as in apparel grade yarn or in two or more steps called two stage drawing or multistage drawing, as in high performance tire yams. There are certain advantages of drawing the material in more than one stage and these are described later in this section. Drawing is normally carried out as a separate process on a separate machine as described above, however, at times, drawing may be combined with spinning machine to provide in-line drawing as shown in Figure 6. In such machines heating to the yam is provided by using feed rollers or intermediate rollers as heated godets. ~3000 m/min Drawing Stage IT (OR=4.0) ~600 m/min Figure 6: Spin-draw process for a high performance nylon-6 tire cord manufacturing NECK DRAWING Cold drawing or neck drawing of polymers is a frequently used technique for obtaining polymers in an oriented state, The term cold drawing was initially applied to amorphous polymers stretched in a temperature range between the brittle point and glass transition. Cold drawing occurs when a fibre sample is forced to extend at a rate faster than the rate of molecular mobility or relaxation (ie. a little below T,). At the T,, the rates become ‘comparable and the neck disappears. Lotus & acaDEmyGATE TUTORIAL: DRAWING & HEAT SETTING By analogy to amorphous polymers, the term cold drawing has been expanded to semicrystalline polymers. This was promoted by the circumstance that exterior attributes of cold drawing, i.e. necking and the specific shape of stress-strain curves, are observed for semicrystalline polymers also. However, many semicrystalline polymers can deform with necking at temperatures that are considerably higher than their glass transition. Therefore, for semicrystalline polymers, the cold drawing is defined as any large strain of a sample (without dependence on neck formation) accompanied by large amount of plastic deformation, but with some portion of elastic deformation. During cold drawing, plastic deformation results in a substantial transformation of structure, associated with processes of crystallization or melting/recrystallization. If a semicrystalline fibre draws without undergoing such transformations, it would recover back to original dimensions after the drawing stresses are removed. This is called rubber flow deformation drawing. In hot drawing (flow deformation drawing), only plastic deformation or flow processes are observed. The mechanism of neck formation in cold drawing is believed to consist of three main stages (Figure 7) : (8) Initially, the fibres resist the deformation similar to an elastic material. In this region fibre tends to maintain its original shape and undergoes uniform stretching. (b) Thereafter, a critical point is reached, where some portion of the fibre, due a mechanical irregularity, is unable to bear the localized stress and fails (i.e. deforms). This initiates catastrophic break down of the remaining structure as well and the fibre undergoes rapid deformation by forming a neck. (c) Lastly, this deformation continues till it removes the natural draw of the material, The level of stresses is high in the neck, and therefore, the polymer chains are able to orient and undergo stress- induced crystallization during neck drawing, This stabilizes the structure of the fibre by forming a more stable elastic network. (4) As soon as this network is formed, the fibre is able to resist the applied drawing stresses and further deformation. This forms a drawn and stabilized fibre. Most of the drawing takes place through this mechanism. Strain Figure 7: Various stages in cold drawing leading to neck formation i id drawing is defined by the brittle The temperature-interval of col ng ness temperature, on the one hand, and th temperature ofthe supermolecular mobility from the othe, The temperature of supormetecnt mobility, To approximately equals 08-039 of te melting point ofa polymer ona Kelvin sale, abe oe movi, Te LOTUS & acapEemy ‘GATE TUTORIAL: DRAWING & HEAT SETTING melting point, hot drawing is realized. In this temperature interval, mobility of large supermolecular elements (such as fibrils and crystallites) are observed without their fracture during sample deformation, EFFECT OF DRAWING PARAMETERS Effect of parameters on drawing behavior As stated earlier, in drawing, polymer chains are unfolded and oriented by applying an external tensile stress in the direction of the fibre axis. The various parameters that can influence drawing are: (a) the morphology of as-spun fibre, (b) the draw ratio, (©) the draw rate, (d) the draw temperature and (©) the moisture content of the fibre. Depending upon the above factors, the drawing of a fibre may occur as per one of the curves given in Figure 8. Type'e’ Stress ‘Type ‘bt ‘Type'at Extension Figure 8: Family of stress-strain curves shown by a thermoplastic material. ‘At the bottom of the plot are curves (type a) depicting flow deformation (hot) drawing. In this, the fibres extend uniformly through out the length without the formation of any neck. The diameter of the fibre decreases gradually without any abrupt change and keeps on becoming thin on application of higher and higher stress till the fibre breaks. ‘The second type of curve (type b) is called neck drawing. As explained earlier, in neck drawing, the fibres draws uniformly (i.e. gradual decrease in diameter over the length of the fibre) at the initial stage, thereafter, it is followed by formation of a neck (characterized by a hump) and a nearly flat deformation zone, and finally a strain hardening region, which symbolizes formation of a stabilized or locked structure. The rapid deformation and the high levels of stress in the neck, orients the molecular chains and initiates stress-induced crystallization, This stabilizes the structure of the fibre by forming a more stable elastic network. Most of the drawing takes place through this mechanism, Lotus & acaDEmyGATE TUTORIAL: DRAWING & HEAT SETTING ; aes $ we move away from flow deformation curves (type a) t0 (type ¢) the natural draw region ieee defined. However, on moving more towards (type c), the material starts to lose its mobility haar ductile or brittle failure (type ¢ curves) Most of the thermoplastic materials show all the three kinds of drawing behaviour explained above. The type of drawing curve shown depends on the starting material or the drawing parameters. (a) Effect of drawing temperature: If the drawing temperature is very low, the fibre breaks before it can draw due to limited mobility, i.e. ‘(type c)’, however, as the temperature is increased, the drawing behaviour ee from (type c) to (type b) and finally to (type a). At very high temperature, polymer chains are highly mobil ir are able to deform easily with high relaxation rates. A moderate temperature where enough stresses could be built that can initiate a neck drawing with a well defined natural draw region is most preferred route. Therefore the drawing temperature of a filament is determined where good natural draw is obtained with neck formation. (b) Effect of rate of drawing: Rate of drawing at a constant temperature has an opposite effect. As the rate of drawing is low, polymer has enough time to relax from the drawing stresses and shows flow deformation behaviour (type a). As the rate of drawing is increased, the material is able to draw through the formation of a neck (type b). At very high rates, the material may not be able to relax at all and the built up of elastic stresses leads to a brittle failure (curve type c). Therefore, if we need to draw a material at a very fast rate, which is true for modern high production machines, the temperature of drawing would need to be raised substantially to get desirable neck drawing. (© Effect of starting material: Starting material may also have great influence on the kind of draw the fibre would undergo. In purely amorphous materials, itis often said that the cold drawing (neck drawing) occurs at temperatures that are a little below the glass transition temperature. However, in semicrystalline materials the necking phenomena can occur at temperatures above the glass transition temperature. If the fibre is highly crystalline or highly oriented, the fibre may show a brittle failure (type a). A highly amorphous material is able to undergo neck drawing if it can crystallize. A purely amorphous material without any tendency to crystallize will only show flow deformation behaviour and will break eventually by thinning down (@) Effect of moisture/plasticizers content: The presence of plasticizers or even moisture may change behaviour of the drawing material. Presence of plasticizer lowers the build up of elastic stresses and the material may show more of flow deformation behaviour. Nylon-6 is more sensitive to moisture content and therefore shows flow deformation drawing (type a) at higher moisture content. Solution spun fibres with traces of, solvent, which have already undergone crystallization (such as wet spun acrylic fibres) show only flow deformatio drawing (type a). Such structures lock, when the T, of the drawn fibre is pushed to a high tem, ‘ te solvent is removed from it on subsequent washing. See OPTIMIZATION OF PARAMETERS Formation of a stable neck is the most important criteria to di angle of neck is related to the level of internal stresses. necking. Necking can also be related to the birefringence of ' level of orientation of the polymer chains. However, i be difficult and unstable. Higher draw ratio, i of neck. At very high necking angle, i lecide that a good drawi igher the internal ence of the drawn fibre, wever, if the angle of neck is t higher extension rate, and low the fibre may develop defects such ing is being carried out. The Stresses, sharper is the angle of as Internal stress alone dictates the ‘0 sharp, the drawing may prove t0 temperature all lead to higher angle 4s internal cracks and fissures. This Lotus acapemy ’/ GATE TUTORIAL: DRAWING & HEAT SETTING fay give opaque appearance to the fibre. Therefore, fibre should be drawn just short of when such defects start ‘appear. This defines the maximum extent (Apex) to which a fibre may be safely and usefully drawn. This Are ~ ay be maximized for a given as-spun fibre by subjecting the fibre to the optimum drawing parameters. |: this point, the readers must also recall, that the state of polymer chains (i.e. entanglement density has ‘cofound effect on the drawability of the fibre. Both very high and very low entanglement density may lead to a ~90rer mux Value even at optimized drawing parameters. ADVANTAGES OF MULTIDSTAGE DRAWING As mentioned earlier, cold drawing is more effective in producing a well connected oriented structure than drawing during melt spinning. Therefore, for producing high performance fibres, the fibres are normally spun at low spinning speeds to produce LOY. This allows the as-spun fibres to be drawn to very high draw ratio of ~5-6 for achieving high orientation, Such drawings are effectively carried out by using multi stage drawing rather than single stage drawing. During drawing process, the stresses are not distributed equally on all chains because of randomly existing tie points (crystallites or entanglements) and certain high stress points are created. If such a system is stretched further to a large draw ratio, many of these high stress points may produce defects such as chain breakage or crack propagation. It is important that the fibre is allowed to relax and adjust after partial drawing so that stresses at high stress points are dissipated. Multi stage drawing allows fibres to be drawn or stretched in steps with relaxation built in to large draw ratios without fear of producing defects. The second advantage of multistage drawing is that fibre may be subjected to correct temperature of drawing as the draw ratios are increased, On drawing,fibre starts to get oriented and undergoes stress induced crystallization. This increases the glass transition temperature (T,) of the fibre and drawing at low temperature becomes difficult to achieve high draw ratios. In multi stage drawing enough mobility may be provided to fibre by increasing the temperature as the fibre structure changes with each step of drawing. This allows efficient and defect free drawing unlike in single stage where only one temperature can be kept. . STRUCTURE DEVELOPMENT DURING DRAWING Drawing is associated with significant changes in the structure of the fibre. Due to the high stresses developed during drawing, the orientation of fibres increases, crystallinity usually changes, and type of crystals may undergo transformation. The morphology of the structure may also change from micellar to fibrillar, with concurrent change in connectivity between amorphous and crystalline phases. Overall change is to lower Gibb’s free energy (G) by lowering enthalpy (H) of the system. a. Orientation development ‘The network draw ratio reflects the state of deformation of the molecular network present in the undrawn and drawn fibres. It is of interest to look at the development of molecular orientation with network draw ratio, since this provides insight into the mechanisms of deformation throughout fibre processing. There are two theoretical schemes for prediction of orientation from network deformation: the affine and pseudo-affine deformation mechanisms. In the affine scheme, network junctions are thought to be connected by flexible chains. Upon Stretching, the network points are displaced in direct proportion to the macroscopic deformation. As a result, the rotatable ‘random links’ comprising the network chains gradually adopt a more and more oriented Configuration. This is a rubber-like deformation, where the orientation parameter can be described as a ‘function of the network draw ratio 4 according to equation [4]. totus & acapemyGATE TUTORIAL: DRAWING & HEAT SETTING \ An 1 1 (P>) = — te [2 i= tee a (5) a : Where An is the sample birefringence, Annex is the intrinsic birefringence and N is the number of random links: between network points. In pseudo-affine deformation, the structural elements undergoing deformation are assumed to be rigid entities having no extensibility themselves. These simply rotate in proportion to the macroscopic deformation of the sample, Here orientation parameter is given by equation [5]: crystalline orientation Orientation factor 2 w amorphous orinetation, 0.0 1.0 2.0 3.0 40 Draw Ration 5.0 Figure 9: Crystalline and amorphous orientation factors f- and f, of drawn yams as a function of draw ratio The amorphous and crystalline orientation factors are plotted as a functi ie kav crystalline orientation factor f, initially increases sharply, leveling off at Wiaher fon rai xh mel ay tises very slowly becoming important only atthe highest draw ratios. The erystallnne ato teres nil ratio in w pseudovaffine fashion whereas the amorphous phase follows a rubber: teens Crystallites act as rigid entities in the fibre structure whereas the amorphous phase coniete nee acting as a rubber network. On drawing of a semicrystalline Ses Ce ees sampl =, ry . comparatively low even at the maximum draw ratios because drawing of an ePHOUS Orientation remasS crystalline phase. 'g of amorphous phase is hampered by th Lotus 3 acapemy iGATE TUTORIAL: DRAWING & HEAT SETTING The early work of Ward and co-workers has shown that orientation development in PET fibres spun at low spinning speeds follows the affine deformation theory of rubber elasticity. Whereas in nylon-6, pscudo-affine mechanism is dominant. The difference between nylon-6 and PET in this respect can be attributed to differences in crystallization behaviour of the two polymers. Nylon-6 has a lower T, than PET and the T, of nylon-6 shows @ pronounced dependence on moisture content. As a result, nylon-6 fibres tend to rapidly crystallize after winding and conditioning, even if crystallization does not occur in the spinning thread itself. This means that undrawn nylon-6 yarns are always partially crystalline, irrespective of wind-up speed. In contrast, undrawn PET yarns produced at low speed are nearly fully amorphous and develop moderate levels of erystallinity only at wind-up speeds sufficiently high to induce spin line crystallization. b. Change in crystallinity during drawing: ‘Whereas the degree of orientation always increases in the course of drawing, the crystallinity can change in both directions. Three types of behavior can be distinguished 1. Deformation is accompanied by additional crystallization and an increase of crystallization. 2. Deformation does not affect phase structure: an undrawn amorphous sample remains amorphous after drawing; a crystalline sample does not change its degree of crystallinity. 3. Deformation is accompanied by partial destruction of the original structure and reduction of crystallinity. Orientation of the polymer chains may be accompanied by change in crystalline region. However, it is not necessary that the crystallinity will always increase with drawing. In a semicrystalline thermoplastic polymer with low crystallinity, the orientation is normally accompanied with increase in crystallinity. Example is POY PET drawn at neck drawing conditions at high draw ratio, However, if the polymer is already at an equilibrium state as far as crystallinity is concerned such as wet spun fibres, where crystallinity has developed to the full extent in the coagulation bath itself due to high mobility of the chains, no further increase in crystallinity is observed on drawing. Altemately, if the material is drawn at a very slow rate (flow deformation) at a low temperature so that thermal crystallization does not take place, then also, change in crystallinity is negligible. Example is drawing of amorphous PET at a slow rate in a cold bath. In some other instances, crystallinity may decrease as the fibre is drawn. This may occur ifthe starting fibre has igh crystallinity and due to applied stresses of drawing, small imperfect crystallites may get deformed or broken. For example, a fully crystallized PET sample drawn forcibly at a high temperature may result lowering of crystallinity with drawing. (©) Change in crystal type during drawing In many fibres, initial crystal type may get transformed as the fibre is subjected to drawing stress. In this, crystal type of high energy may get transformed to more stable crystals (crystal type of low energy). For example smectic phase of PP transforms to a (alpha) crystalline phase on drawing. Similarly, y (gamma) crystals in nylon-6 are transformed to a on drawing. The ‘alpha type’ structure in nylon-6 possesses hydrogen bonding between antiparallel! chains while ‘gamma type’ structure possesses hydrogen bonding between parallel chains, The ‘gamma type’ structures generally have a shortened crystallographic repeat distance in the direction of chain axis. nu Lotus &} acapEemyGATE TUTORIAL: DRAWING & HEAT SETTING i ing spinni In materials, where there is only one type of crystal, imperfect crystallites formed during spinning stress m, Set transformed into more stable and perfect crystals during drawing. (4) Changes in long-range morphology of the fibres i i i hange j The morphology of the structure may also change from micellar to fibrillar, with concurrent change connectivity between amorphous and crystalline phases. Overall change is to lower Gibb’s free energy (G) lowering enthalpy (H) of the system. Long range order is important in fibre morphology. This decides the formation of fibrillar structure, which more load bearing. Also, it decides the manner in which crystalline and amorphous Tegions are connected each other for load transfer. It is observed that length of long range order reduces with shear of drawin, stresses. However, if the drawing temperature is sufficient, the long range order may improve as the fibre drawn. DRAWING OF NYLON-6 Drawing of nylon-6 is usually carried out at room temperature as its T, at standard conditions of humidity (ie RH = 65%) is close to the room temperature. However, high molecular weight nylon-6, used for tyre cori application, needs to be drawn at high draw ratio of 4-5, and therefore, is required to be drawn at significant) higher temperature using two zone drawing system as shown in Figure 6 (as referred earlier in drawing machines). Because of low Ty, nylon-6 has a tendency to undergo crystallization as soon as the spinning is accomplished. Therefore, nylon-6 is stored in a room with standard temperature and humidity conditions (ie. 25°C and 63% RH) for 24-48 bh. This allows the polymer to attain equilibrium crystalline state, which is stable enough i further processing. This step is known as ‘conditioning’. If the spun yarns are not conditioned belie th drawing operation, the spun yar would continue to change its morphology on the feed bobbin ac drawing continues. This would result in yarn with nonuniform drawing behaviour. As the spun yam is conditioned, the partially oriented molecules undergo both relaxation and erystallization Relaxation disorients the chains and brings about shrinkage, whereas crystallization throws oi bends and curves in partially oriented chains in the axial direction resulting in extension of fibres. The relative evr ns shrinkage and extension is greatly influenced by the spinning speed of the yarn, At low spinning speeds, the shrinkage is much smaller compared to the extension and the net result is increase in length of the spun yarn as it undergoes substantial crystallization. Due to crystallization of oriented chains, the birefringence values also increase substantially. At a speed of 2000 m/min, the extension is maximum at about 10% as shown in Figure 10 . As the spinning speed is increased, the shrinkage component increases and extension tendency decreases as the chains get more oriented and partly crystallized at higher speeds. At a spinning speed of 4000 m/min, there is no net extension or shrinkage during conditioning of spun fibres, At spinning speeds higher than 4000 m/min, the yarns show net shrinkage though it is not high. With higher and higher spinning speed, i.e. around 5000 m/min, a significant amount of y crystallinity develops during spinning, which remains stable during the conditioning phase and the yarn does not undergo further crystallization into. phase on conditioning.GATE TUTORIAL: DRAWING & HEAT SETTING Spinning speed (km/min) Shrinkage (%) ° Figure 10: Shrinkage behaviour on conditioning of as-spun nylon-6 spun at various spinning speed ‘Once the as-spun yarns are conditioned, they are subjected to drawing. During drawing, unoriented amorphous phase undergoes orientation, and the oriented amorphous phase undergoes crystallization into « phase. Those spun yarns, which have y phase crystals due to high speed spinning, undergo crystal phase transformation. The y crystals disappear at high draw ratios (> 3) and a crystals are found to get formed. Eventually, most of the unoriented phase converts to oriented amorphous phase, and subsequently, both the oriented amorphous phase and y crystalline phase convert into a crystalline phase. It is also possible; that rather than converting, y phase gets destroyed on drawing and a phase is formed from the oriented amorphous phase. It has been found that y phase undergoes transformation only on drawing and is otherwise quite stable to annealing even at very high temperatures because the integrity of the H-bonded sheets is maintained during heating up to the melt state. Transformation of morphology of nylon 6 on drawing: As spun nylon fibres exhibit shish-kebob type morphology. The shish is composed of both the y-phase of nylon 6, which forms in the spinning process due to its less organized parallel chain stacking arrangement, and of amorphous polymer. These structures are composed of a lamellar stacking of crystalline and amorphous zones. Regularly spaced along the shish are pockets of a-phase crystals in groupings known as kebobs, which crystallize in an anti-parallel chain-stacking pattem. The kebobs are in a lamellar stacking pattem with additional amorphous phase intervening between the crystalline lamellae as shown in Figure 11. Kebob made up of « crystals \orphous region @ lamellar crystalline region Amorphous region 2B Lotus & ACADEMYGATE TUTORIAL: DRAWING & HEAT SETTING Figure 11: Schematic representation of transformation of morphology of nylon-6 on drawing As the fibres are drawn, the shish structures which comprise extended chain y-phase crystals begin to be torn apart. They either become amorphous polymers or transform directly into a-phase crystals. Amorphous Polymers surrounding the shish-kebob structure may also transform into d-phase crystals. As the draw increases a-phase crystals begin to be destroyed in addition to the y-phase shish. This increases the distance between two kebobs, and thus, increasing the long period. Finally, as most of the extend chain y-phase shishes get destroyed or transformed to a-phase crystals, the morphology becomes lamellar with alternating stacks of amorphous and a-phase crystalline polymers. With increased stress, these lamellar stacks then transform to a microfibrillar type structure. Drawing of PET The polymer chains are highly entangled with each other. Therefore, they undergo three types of relaxations after deformation. Relaxation time Ta: It is the fastest kind of relaxation between the two entanglements. This happens in mili seconds. At the time scale of this relaxation, the polymer chains remain fixed at the entanglements, and the ‘segment moves to the minimum energy state. This is given by equation [6]: Retraction time Tx: This is slower than the above and involves adjustment of chain at one or both of the entanglements. This process results in a change in the length of polymer strands between entanglements. This is given by equation [7]. Reptation time Tc: This is the third stage of relaxation and involves. removal of chain from one of the entanglements to form a different coiled path and attain isotropic configurations as given in equation [8]. The slower relaxations [Ts and Tc are related to T, and the molecular weight M of the polymer through: M\ = 27,| — aaan(zr) Ms eao(Z) . NM (7) and (8) Estimated values of Ta is 0.001 s, To is 2.2 s and Tc is 220 s for M of 40000, Me of 1200 at 90 °C. These value reduce drastically as the temperature is increased. For example, Tp is 0.003 s and Tc is 0.32 s at 120°C. In regime I, where the draw rate is high and temperature is low, such that the draw rate is faster than the retraction rate (1/ Ta), the chain entanglements act as temporary crosslinks in the time scale of the deformatior process. In this region, temperatures are above but sufficiently close to the T,, In this region chains underg¢ high orientation as relaxation is highly restricted. The highly oriented chains result in increase of the rate 1 Lotus & acapemyGATE TUTORIAL: DRAWING & HEAT SETTING crystallization by several orders of magnitude. This leads to formation of highly oriented crystals along the enue chains. The formation of crystals, however, takes place once the drawing is complete. Formation of mesophase due to high drawing stresses is the precursor to the development of crystals after drawing has ended. At draw rates slower than 1/[: (Regime I1}), no oriented crystallisation occurs. This is because significant segment orientation was not achieved during the deformation stage in this regime and oriented crystallization is not observed. This region corresponds to flow deformation region and does not allow attainment of high orientation of chains due to high relaxation rates. At intermediate draw rates (Regime Il), oriented crystallisation can occur but is able to commence during the draw process. = pormins ae ig) iteptation: Rewnction Temperature of drawing COD Figure 12: Schematic representation of different regions of drawing as a function of temperature and rate of drawing INSTABILITIES IN DRAWING Instability in drawing may arise due to three reasons; the starting material, the drawing parameters, and the drawing machine. (a) Starting material: If the starting material is non uniform along its length, for example, having thick and thin places or having different levels of crystallinity, etc, the fibre may show unstable drawing. The non uniformity in the samples lead to nonuniformity in drawn fibres with initial defects amplified to a great extent. (b) Drawing Parameters: If the drawing tension is too high, because of drawing parameters, the drawing may not stable. This is because any small difference in material morphology would result in magnified changes in the tension of the drawing filaments. Also, very high or very low DR may induce instabilities. Too low draw ratio may give a dancing neck and Portions of drawn and undrawn material along the length of the drawn fibre. At high draw ratio, the fibre may tend to break or develop defects 15 Lotus & acapemyy Lotus & acapemy ee GATE TUTORIAL: DRAWING & HEAT SETTING in machine parts su ations in drawing rollers, improper (©) Machine: The eccentricity (non circular form) i Se al ge periodic instability or control of speed or drawing temperature may all lead to fluctu: jrawing ‘non uniformity in drawn material HEATSETTING ; jon, It is carried out to bri Heat setting or annealing of the drain fibres isan important post spinning operation. It is Fat ease the material to its thermal equilibrium at a particular temperature of use. At thermal equilibrium, ‘would not change its morphology even if kept at that temperature for a long time. ing is the measure of how close the The di ibe the extent of heat settit a 1e. degree of set, a term often used to describe the ex i tp be at its thermal equilibrium ‘material has moved to a thermal equilibrium. A 100% set material is consid ata given temperature, Types of heat-setting There are three types of heat-setting: (a) temporary heat setting ‘This type of setting is destroyed with regular use of the materials. For example, a steam pressed cotton textile. (b) semi permanent heat setting; In this type of heat setting, material is raised above its T, and then set into a new form: This type of set is ined with normal use of the material, however, the setting is lost when the material is subjected to severe conditions of use.For example, hot washing or steaming of material above Ty. (©) Permanent heat setting. This type of heat setting involves change of internal morphology of the material in such a way that it would not reverse till the material is destroyed by taking it above its melting point. For example: Heat setting to develop new crystallites. In this form the crystals can only be destroyed by heating the material above its melting point. This would destroy the fibre itself, and therefore, such conditions of high temperature can not be given under normal use. PARAMETERS OF HEAT SETTING ‘The permanent heat setting is the most important of the three types described above as this can be used to stabilize the material in its final form. As the spun yam is drawn during a drawing operation, it undergoes chain orientation and crystallization under stress. This leaves the material with a lot of internal stresses and incomplete crystallization process If left like this, the drawn yams would tend to shrink slowly depending upon the temperature of use and start to lose their orientation. Also, they may continue to crystallize with fuse and assume an undesirable form. These materials ean be brought to thermal equilibrium by heat treating them (ie annealing them o heat setting them) at the temperature of crystallization for a short time. This reiewes tel internal stresses and helps in development of more crystals that can lock the structure in the oriented state There are several parameters that can affect heat-setting. These are as follows: 16GATE TUTORIAL: DRAWING & HEAT SETTING (a) Temperature of heat setting Heat-setting involves formation of new crystallites in the amorphous part of the fibre. The formation of crystals is a thermal process and maximizes at a certain temperature. Crystallization involves nucleation followed by growth of the nucleated crystallite. Nucleation is facilitated at a low temperature, while growth is facilitated at a higher temperature. Since rate of crystallization involves both nucleation and growth. There exists an optimum temperature for a given fibre, where the rates of nucleation and growth together result in the highest rate of crystallization. The rate of crystallization is also dependent on the orientation of the fibre being crystallizec. At higher orientation, the rates of crystallization may be significantly higher than the lesser oriented material. Therefore a drawn yam may undergo heat-setting through crystallization in a fraction of time than otherwise needed for an unoriented yam. ‘Temperature of heat-setting also has another effect. At a high temperature, oriented chains tend to relax fast and fibre can lose its orientation if left at that temperature for a sufficiently long time. Therefore there is a competition between the relaxation of polymer chains resulting in shrinkage of the fibre and locking of structure due to formation of crystallites. Therefore, selection of an appropriate temperature for heat-setting is very important so that thermal equilibrium may be reached without significantly losing the orientation. (b) Time of heat setting As explained above, the rate of crystallization is dependent on the temperature of heat setting and the orientation of the drawn yarn. Also, the disorientation is a function of time. Keeping in view the two, the time is decided so that thermal equilibrium is reached in a minimum time with minimum loss of the orientation. (©) Tension given to the material during heat-setting: The drawn yarn may be subjected to heat either in loose (free) or taut (stretched under tension) form. In free form, the chains can disorient at a faster rate and fold to form lamellar crystals at the heat setting temperature. This results in high shrinkage of the fibres and lowers connectivity among the polymeric chains ( Figure 4.13 ) Though the yam reaches thermal equilibrium easily (i.e. 100% set), it loses all its mechanical properties. Because the connectivity (network formation) is poor among the chains, the fibres are unable to elongate (low extensibility) and bear load (low strength). @) Drawn fiber Taut anneal ©) 7 Lotus &¥ acaDEMYGATE TUTORIAL: DRAWING & HEAT SETTING Fi ; , “Sure 13: Heat setting of drawn yam in free and taut form. Applying ‘ension at the time of heat-setting restricts the rate of folding of polymeric chains, which gives enough sent, Small crystallites to grow along the length of oriented chains. This improves connectivity among the haw 24 chains as many chains are involves in a single crystallite ( Figure 13 ). However, the polymer chains have difficulty in teaching thermal equilibrium and heat-setting may remain at levels lower than 100%. Heat. tensig tins under tension is able to retain mechanical properties of the starting material. When high values of ns ©" are applied, even marginal improvement of tensile strength may be achieved. (@) Moisture in the starting material and its sensi ty to it Certain polymers such as nylons are sensitive to moisture. Their T, becomes lower as their moisture at increases. Since moisture acts as a plasticizer for such materials, their chains may relax and fold easily when in Wet state compared to the dry state. For example, in drawn nylon 6, the dye uptake and the diffusion coefficient are generally increased when heat- Setting is carried out by steam. This tendency increases with the temperature of the steam setting, However, dry heat setting up to about 160°C gives the reverse tendency. With steam, chains fold to grow into large erystals and the molecular packing of amorphous regions loosens as a result of inclusion of water. On the other hand, in dry heat setting, the increase in crystallinity and also closeness of packing in the amorphous regions results in poor dyeability and diffusion coefficient of the heat-set material. Interestingly, in both types of setting treatments, the diffusion coefficient decreases with increasing tension of the sample during heat-setting. (©) Morphology of starting material The morphology of the starting material has significant effect on the effectiveness of the heat-setting process. If a material is already crystalline, it may not undergo setting to retain a deformed state. Therefore, materials which have tendency to crystallize during spinning or during storage such as nylon and poly(propylene) are difficult to heat-set. In such materials, imperfect crystallites such as pseudo-hexagonal « higher energy crystalline) phases in nylon-6 or smectic crystallites in poly(propylene) may undergo transformation into perfect monoclinic a phase on set-setting. However, y phase of nylon-6 induced during high speed spinning of nylon-6 has been found to be extremely stable to heat and does not convert to a phase even with high temperature annealing. EFFECT OF HEAT-SETTING ON MORPHOLOGY OF FIBRE As explained earlier, heat-setting involves bringing the material to its thermal equilibrium. This is achieved when a material, which has a tendency to crystallize can crystallize to the maximum extent possible with the given structure. A polymeric material owning to its entanglements and defects can never achieve 100% crystallinity or even close to it. As the crystals develop, entanglements and defects are thrown out to the remaining amorphous regions. With this it becomes inereasing difficult forthe remaining amorphous resions to convert to ordered crystalline regions. As crystallization proceeds, a time comes when further conversion of amorphous region to crystalline region results in increasing the overall energy of the system, the conversion stops and a thermal equilibrium is reached. Lotus &} AcaDEMy 18GATE TUTORIAL: DRAWING & HEAT SETTING a of 2<*ling can increase crystallinity of the material, transform imperfect crystals into perfect low energy form fibseeS**'S, grow smaller erystals into larger crystals. Also, long range order, such as fibrillar structure of the in the MY also change with annealing. All such changes are dependent on the parameters of heat setting used Process, For example, long range order of nylon-6 undergoes marked increase with steam-setting in comparison to dry-heat-setting (Figure 14 ) — free annealing —taut annealing ‘Long Period (A) Heat Setting Temp. (°C) Figure 14: Effect of heat setting conditions on long range order of heat set fibres\ Morphology ofa fibre can also be explained by a modified Tagayanaki Model proposed by V. B. Gupta. In this raodel, shown in Figure 15 , the crystalline regions of a fibre are connected (coupled) in series as well as in parallel with the amorphous region. These values are shown by 2 and © fractions, respectively. Figure 15: Representation of modified Tagayanaki model 19 Lotus & acapemyGATE TUTORIAL: DRAWING & HEAT SETTING IE}. increases to 1, then the entire crystalline region gets coupled with amorphous region in series and if factor becomes 1, then the erystalline region gets coupled in parallel with the amorphous region. With heat- Setting, these parameters tend to change as shown in Figure 16. As shown in the figure, with free annealing, the fraction of series coupling increases, while that of parallel coupling reduces significantly. Whereas, on taut ~ annealing, though series coupling still increases, the drop in parallel coupling is significantly less. A increases Free annealing @ decreases A increases Arbitrary values Taut annealing Is retained Increasing degree of heat-setting Figure 16: Effect of degree of heat setting on parallel () and series (4) coupling for free and taut annealing .), Lotus © acapemy y|