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CONTENT
Abstract...3 1. Introduction...3 2. History...5 3. The Nylon Fiber Design Advantage....7 4. Advantages of Nylon-66...7 5. Use of Nylon-66 in Fiber Manufacturing....9 6. Preparing Nylon-66 Chip.9 7. Remelting Nylon 66 Chip9
11. Polycondensation...14 12. Spinning.14 13. Properties15 14. Types of Nylon-66 products Manufactured16 15. Advantages of DuPont Nylon 66 in Specific Fiber Applications17 16. Product Specification Parameters.20 17. Conclusion...23 References...24
ABSTRACT
Here in this term paper description is given about a type of polyamide fibre i.e. Nylon-66. Here in this paper the methods of preparation of monomers, polymerisation, manufacturing methods of nylon-66, spinning process to obtain fibres, different properties and wide range of applications and uses of nylon-66 are discussed. In this paper data are represented in the form of flow charts, histogram and pie charts for easy understandings. This paper covers all the processes related to nylon-66.
1. Introduction
There are several polyamides, which have been developed as fibres. The generic word for these products is 'Nylon'. Nylon is defined as a generic term for any long chain synthetic polymeric amide which has recurring amide groups as an integral part of the main polymer chain and which is capable of being formed into a filament in which the structural elements are oriented in the direction of the axis. DuPont researchers led by Dr. Wallace Carothers, invented nylon-66 polymer in the 1930s. Nylon, the generic name for a group of synthetic fibers, was the first of the miracle yarns made entirely from chemical ingredients through the process of polymerization. Nylon 66 polymer chip can be extruded through spinnerets into fiber filaments or molded and formed into a variety of finished engineered structures.Nylon-66 fibre is a member of the large group of polycondensation products of dicarboxylic acids and diamines with fibre forming properties. The individual member refers to the number of carbon atoms respectively in the diamine and dicarboxylic acid chains. Nylon-66 (polyhexamethylene diamine adipamide) is a polyamide made from adipic acid and hexamethylenediamine by polycondensation. The resulting polymer is extruded into a wide range of fiber types. The fibers are drawn, or stretched, in a process that increases their length and reorients the materials molecules parallel to one another to produce a strong, elastic filament. The thermo-plasticity of nylon permits permanent crimping or texturing of the fibers and provides bulk and stretch properties.
The nylon developed by Carothers at Du Pont was nylon 66. Because of the importance of starting out with equal amounts of the two reactants, salts of the diamine and of the diacid are made and then used in the commercial synthesis of nylon 66.
NYLON-66 YARN
MONOMERS OF NYLON-66
2. HISTORY
The development of nylon was started from 1927 by means of many researchers, notably among them W.H.Carothers and P.Schlack. The research activities preceding the manufacture of nylon yarn can be divided into the following categories: (a) Fundamental research activities which provided the foundation for the development. (b) Different types of polyamides, their synthesis, manufacture and their suitability for use as a new fibre. This includes all types of polyamides like aliphatic, aliphatic-aromatic and fully aromatic polyamides. (c) Commercial production of the fibres. (d) Development of the properties and serviceability of the fibres. Polyamides are characterized according to the number of carbon atoms present in the structural unit of the molecule. These are: (a) Nylon made from condensation of a diamine and a dicarboxylic acid is classified according to the number of carbon atoms present in the amine and acid respectively. Thus nylon formed by hexamethylene diamine (NH 2 (CH 2 )6 -NH2 ) having 6 carbon atoms and sebacic acid (COOH-(CH2)8-COOH) having 10 carbon atoms is generally referred to as nylon 6,10 (b) Nylon, made from amino acid, is classified according to the number of carbon atoms present in the acid. It will have only one number. For example, Nylon 6 can be made from amino acid having 6 carbon atoms i.e., amino caproic acid or its condense product caprolactum.
So the numbers indicate the number of carbon atoms in the monomer taking part in the polymerisation. In general,
Table 12.1 Raw materials of different Nylons Nylon Nylon 4,6 Nylon 6,6 Nylon 6, 1 0 Nylon 6,12 Nylon 3 Nylon 4 Nylon 6 Nylon 7 Nylon 11 Nylon 12 Raw materials 1 ,4 diamino butane, Adipic acid Hexamethylene diamine, Adipic acid Hexamethylene diamine, Sebacic acid Hexamethylenediamine, Dodecanedioic acid Acrylamide 2-pyrolidane Caprolactum Lactum of heptonoic acid W-amino-cendecanoic acid Dodelactum
4. Advantages of Nylon-66
Nylon 66 is superior in many applications to nylon 6the other large volume nylondue to its outstanding dimensional stability, higher melting point, and more compact molecular structure (see Figure 1). Nylon 66 exhibits only about half the shrinkage of nylon 6 in steam, for instance. And, with a less open structure, the 66 fiber has good dye wash fastness and UV light-fastness, and excellent performance in high-speed spinning processes. Typical advantages of nylon 66 over nylon 6 are its Higher tensile strength in use, Excellent abrasion resistance, and Higher melting point.
Nylon 66 provides high tensile strength for Tough fibers at fine deniers, Excellent performance for tyre applications, and High-speed mill processing. Excellent abrasion resistance makes nylon-66 polymer ideal for use in Carpets, Upholstery, and Conveyor belts. The rubber industry takes advantage of the higher melting point of nylon 66 in hightemperature tire curing. A high melting point also results in a fiber with High stretch and recovery in false-twist textured Yarns (e.g., hosiery and socks) and Thermal stability in high-temperature coating operations.
extruder, and spun into filament form. The filamentsare then packaged in a process that may include drawing, bulking, or cutting into lengths of staple.
Polymer Nylon 66 may produce undesirable crosslinked material (gel) if processing temperatures and holdup times are not properly maintained. Care must be taken to eliminate areas of stagnation in the screw and in the polymer piping. Good engineering practices require the application of optimum shear rates and frequent mixing of the melt. ConversionMolten Polymer to Final Product Form Due to the wide variety of nylon 66 products that can be produced and the range of processing equipment available, it is beyond the scope of this bulletin to specify ideal processing conditions. In general, most modern filament-producing equipment will process nylon 66 polymer adequately.
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2 CH2 CHCN + 2 H+ + 2e
NC (CH2)4CN
9. POLYMERISATION
Nylon-66 production from adipic acid and hexamethylene diamine comprises four steps: (1) Salt preparation (2) Polycondensation (3) Melting. (4) Extrusion. A schematic diagram of Nylon 66 polymer formation process is shown in Figure.
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60% solution in distilled water. It is a snow white crystal (mp - 190C). Owing to all these constraints, batch processing is used.
11. POLYCONDENSATION
The concentrated salt solution is then fed to the polymerisation reactor, where the second-stage of the reaction begins (Fig 12.5 c). 60% Aq. Solution of the salt in distilled water, 0.5% acetic acid (stabilizer) is pumped into an autoclave. Increased temperature and pressure are used to initiate the polymerisation reaction. So the autoclave is heated to 275C. The pressure is generally kept constant (1.8 MPa). Before the reaction, the autoclave is purged with very pure nitrogen (less than 0.005% oxygen) to avoid degradation and discoloration of the polymer. When the temperature of the batch reaches 275C, the pressure is allowed to fall to atmospheric pressure. The batch is held at 270C and atmospheric pressure for half an hour to allow removal of the water vapor. The heating is continued until all water has been distilled off. Towards the end of the distillation, the autoclave is evacuated. The polymer is obtained as a clear, low-viscous melt which is removed from the autoclave by pressure with pure nitrogen. The melt is extruded through the bottom of the reactor to form a ribbon. It is solidified and cooled in cold water cut into chips and dried. The dried chips are stored in a storage hopper in a similar manner like that of Nylon 6.
12. SPINNING
Nylon has sufficient stability of the melt and adequate viscosity. So it can be spun in the molten state with usual velocity (upto 2000 m/min). The polymer chips are fed to the hopper and then it is melted and homogenized in an extruder. The molten polymer after filtration is passed to the spinnerets. The melt is pumped through this system and solidifies immediately on contact with air. Cross air flow is used for solidification. The melting temperature for spinning is around 300C. After spinning like nylon 6, the flows are stretched to get the desired elongation. Details of spinning and stretching processes are discussed in Chapter - 2 (Fig 2.1 and 2.6). The different parameters which can be varied to influence fibre properties are: (a) Mass output, (b) Winding speed, (c) Spin draw ratio, (d) Draw ratio and (e) Draw temperature. The properties which will be considered are: tensile strength, elongation, modulus, crystallinity and orientation.
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13. PROPERTIES
13.1. PHYSICAL PROPERTIES
Like Nylon 6, different types of Nylon 66 fibre exhibit different physical properties.
Physical Properties Density (gm/cc) Moisture (%) at 65% rh 100% rh 4.0-4.5 6.0-8.0 4.0-4.5 6.0-8.0 4.0-4.5 6.0-8.0 Staple Fibre 1.13 Normal Filament 1.14 High Tenacity Filament 1.15
Tenacity (g/d) Dry Wet Elongation (%) Stiffness (g/d) 3.0-6.8 2.5-6.1 16-75 10-45 2.3-6.0 2.0-5.5 25-65 5-24 6.0-10.0 5.1-8.0 15-28 21-58
solutions of hydrochloric acid, sulphuric acid and nitric acid. The fibre is soluble in formic acid. In a similar way, the fibre is attacked by strong alkalies under extreme conditions otherwise it is inert to alkalis. The fibre can be bleached by most of the bleaching agents. The fibre is mostly insoluble in all organic solvents except some phenolic compounds. The fibre has excellent resistance to biological attacks. Prolonged exposure to sunlight causes fibre degradation and loss in strength. The fibre can be dyed by almost all type of dyestuffs like direct, acid, metal-complex, chrome, reactive, disperse and pigments. However only acid and metal complex dyes are preferred because of higher fastness properties.
5. Nylon 66/6, 40% Glass Fiber Reinforced 6. Nylon 66/6, Mineral Reinforced 7. Nylon 66/6, 60% Glass Fiber Reinforced 8. Nylon 66/Nylon 6 Blend, Glass Fiber Filled 9. Nylon 66, Unreinforced 10. Nylon 66, Impact Grade 11. Nylon 66, Unreinforced, Flame Retardant 12. Nylon 66, Heat Stabilized 13. Nylon 66, Extruded 14. Nylon 66, Film 15. Nylon 66, Nucleated 16. Nylon 66, PTFE Filled 17. Nylon 66, MoS2 Filled 18. Nylon 66, Glass Bead Filled 19. Nylon 66, 30% glass filled, extruded 20. Nylon 66, Mineral Filled, NCG Fiber Filled
High fiber modulus minimizes yarn distortion possible during winding, warping, knitting, and weaving processes minimizes barr and streaks during dyeing Wide operating window for heat setting, dyeing, and processing, this is especially important for fabric combinations with spandex Very good resistance to photo degradation Good dye light-fastness Good dye wet-fastness Tires and Conveyor Belts Heavy-duty tires and belts reinforced with nylon 66 polymer are capable of withstanding high temperatures and fast curing cycles. The superior performance is due to the high strength and modulus of nylon 66. Woven and modified nylon 66 tire cord provides aircraft and off-road vehicle tires with long life and high fatigue resistance. Nylon 66 has particular advantages in industrial products as a result of the polyamides High melting point, Superior dimensional stability, and reduced moisture sensitivity. Coated Fabrics Nylon 66 fabrics withstand coating temperatures with PU, PVC, and rubber up to 200C (392F) and display good dimensional stability for coating integrity. Carpeting During the late 1950s, two new developments opened up a new era for the carpet industry. First, equipment was developed to tuft carpet yarn into a backing material to produce pile carpeting. At the same time, DuPont invented a technique to impart bulk or loft to nylon by
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a fluid-texturing process called Bulk Continuous Filament (BCF). The combination of nylon 66 yarns, textured by the BCF process, yields carpets with High abrasion resistance, High resistance to pile crushing and Matting, ease of level dyeing, High dye light-fastness, and High dye wet/wash-fastness. Carpets of nylon now account for nearly 70% in a market that was once the exclusive domain of wool yarns. Furnishings/Floor Coverings Nylon 66 offers the furnishings/floor coverings industry A complete line of luster (from 0.0 to 1.0% TiO2), Products for direct use and post-polymerization Feed, Products intended for color addition during remelt, and A full line of dye variant polymers for yarn styling formulations.
Nylon is a material that runs from combs to ship propellers to ladies stockings. The applications can be summarized as follows: Textiles Automotive Furniture Packaging Mech. Engg. Apparel, tooth brushes, Tyre cord Bearings, slides, door handles, door & window stops. Locks, hangers, chairs etc., Film sheet Drive gears, bearings, fish plates for railways lines tubing.
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RV is determined by comparing the time required for a specific volume of polymer solution to flow through a capillary tube with the corresponding flow time of the same volume of pure solvent. Results are corrected for moisture content of the sample; alternatively, the sample is dried to a low moisture level. Values quoted in specifications are those measured in 90% formic acid. Figure 6shows the typical relationship between RV in 90% formic acid versus 98% sulfuric acid. Amine End Groups (AEG) A major nylon asset is its ability to accept a wide range of dyestuffs. These include both acid and premetallized dyestuffs that associate with the terminal amine groups of the polymer. The concentration of these end groups is an important factor in controlling dye ability (see Figure7).
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Analysis Method The technique commonly used for measuring AEG involves dissolution of polymer in 68/32 wt% phenol/methanol solvent and potentiometric titration with 0.05 m hydrochloric acid using commercially available equipment. Results are corrected for moisture and titanium dioxide content. For typical textile grade products, amine end Group concentration is usually within the range of 3550 and is expressed as gram equivalents/106 g of polymer.
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Moisture Content Nylon is a relatively hygroscopic polymer. Nylon 66 leaves our production plant with low moisture content (typically <0.3 wt %). However, the product can absorb more moisture (up to8 wt %) depending on the relative humidity (see Figure 8) and length of exposure time (see Figure 9). Customers must take precautions to keep the product free of moisture.
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17. CONCLUSION
After all the research works and information in this term paper we conclude that Nylon 6,6 is a semi-crystalline, off-white engineering thermoplastic that is the strongest and most abrasion resistant unreinforced aliphatic nylon with better low temperature toughness than Nylon 6 or acetal. Its very low melt viscosity can give industrial processing difficulties and weathering can cause embrittlement and color change unless it is stabilized or protected. Available with a wide range of fillers notably glass fibre, which gives a marked increase in stiffness, and solid and liquid (oil) lubricants. Super-tough grades are also available whose impact properties and low notch sensitivity are amongst the best of all engineering thermoplastics. Applications include mainly engineering components eg gears, bearings, nuts, bolts, rivets and wheels and power tool casings and rocker box covers. Widely used as monofilament for brushes etc and fibre - notable for its resilience and high abrasion resistance - for apparel, carpet and industrial end-uses.
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REFERENCES
1. Nylon 66, polyamide fibres, A Text Book of Fibre Science and Technology S.P. Mishra, New Age Publishers. 2. Advances in nylon 6, 6 Fibre Science and Technology, By Premamoy Ghosh. 3. Nylon manufacturing, Modern Fibres edited by J.W.S HEARLE. 4. http://en.wikipedia.org/wiki/nylon 6,6 . 5. http://www.encyclopedia.com/topic/nylon.aspx . 6. http://www.polymerprocessing.com/polymers/PA66.html . 7. http://www.goodfellow.com/E/Polyamide-Nylon-6%2C-6.html. 8. http://www.slideshare.net/nashton/nylon-66-presentation-5487525. 9. DuPont Nylon, DuPont Singapore (PTE) Ltd, and 07-01 World Trade Center1 Maritime Square Singapore 0409, Telephone: 65-279-3497, Fax: 65-272-7494. 10. Properties of nylon 66, Textile research journal, http://trj.sagepub.com/. 11. Technical details of nylon 6, 6 fibres, http://www.btraindia.com/articles_indian.asp. 12. http://www.sciencedirect.com/nylon-66. 13. Chemistry of textile fibres, W.S. Murphy 14. Testing of textile fibres, by J.E. Booth.
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