Nylon 66 yarn was exposed to near-ultraviolet radiation in a dry oxygen atmosphere for exposure periods up to 240 hr. Dye take-up, viscosity, and density measurements, DSC thermograms, and wideline nmr spectroscopy were employed to assess the effects of the irradiation. Measureable changes were observed with each analytical technique. It was concluded that exposure of nylon 66 to the above conditions caused considerable chain scission in the defect regions, there was no detectable crosslinking, and the newly freed chain ends relaxed resulting in a more highly ordered fiber structure.
Achhamer, B.G. , Reinhart, F.W., and Kline, G.M., Mechanism of the Degradation of Polyamides , J. Res. Nat. Bur. Stds.46, 391-420 (1951).
2.
American Association of Textile Chemists and Colorists, Rhode Island Section. Doyle, M., chairman. Degradation of Polyamide Fibers Exposed to Various Sources of Radiation, Textile Chem. Colorist1, 99-104 (1969).
3.
American Society for Testing Materials.D 1505-68, Standard Method of Test for Density of Plastics by the Density Gradient Technique. ASTM Book of Standards, Part 27. Philadelphia , ASTM, 1971, pp. 469-474.
4.
American Society for Testing Materials.D 2857-70, Standard Method of Test for Dilute-Solution Viscosity of Polymers. ASTM Book of Standards, Part 27. Philadelphia, ASTM, 1971, pp. 713-717.
Atherton, E. and Peters, R.H., Studies of the Dyeing of Nylon with Acid Dyes. Part II: Kinetics of the Process, Textile Res. J.26, 497-511 (1956).
7.
Bell, J.P., Relation Between Nylon Fiber Mechanical Properties and Dye Diffusion Behavior , J. Appl. Polymer Sci.12, 627-638 (1968).
8.
Bell, J.P., Effect of Fiber and Dyehath Variables on the Rate of Acid Dyeing of Nylon 66, Textile Res. J.38, 984-985 (1968).
9.
Bell, J.P., Carter, W.C., and Felty, D.C., Dye Concentration Profiles within Single Nylon Filaments, Textile Res. J.37, 512-516 (1967).
10.
British Patent 772, 724, E. I. du Pont de Nemours and Co.; (C. A. 9937 (1957)).
11.
Burnett, G.M. , and Riches, K.M., Oxidation of Nylon Model Systems, J. Chem. Soc. B 12, 1229-1234 (1966).
12.
Carlsson, D.J. and Wiles, D.M., Photooxidation of Polypropylene Films IV: Surface Changes Studied by Attenuated Total Reflection Spectroscopy, Macromolecules4, 174-179 (1971).
13.
Carrington, A. and McLachtan, A.D., "Introduction to Magnetic Resonance with Applications to Chemistry and Chemical Physics," New York, Harper and Row, 1967.
14.
Charlesby, A. , Effect of High Energy Radiation of Long Chain Polymers, Nature171, 167 (1953).
15.
Charlesby, A., "Atomic Radiation and Polymers," Vol. 1 (Inter. Series Monographs Radiation Effects in Materials), London, Pergamon Press, 1960, pp. 556 ff.
16.
Coblentz, W.W. , Correlation of Bioclimatic Ultraviolet and Total Solar Radiation in Washington, D. C., 1941 1948 ; Bull. Amer. Met. Soc.30, 204207 ( 1949).
17.
Davis, G.T. and Taylor, J.S., Diffusion Kinetics of Orange II in Nylon 66, Textile Res. J. 35, 405--411 (1965).
18.
Deeley, C.W. , Woodward, A.E. and Sauer, J.A., Effect of Irradiation on Dynamic Mechanical Properties of 6-6 Nylon, J. Appl. Phys.28, 1124-1130 (1957).
19.
Dumbleton, J.H., Bell, J.P., and Murayama , T., TheEffect of Structural Changes on Dye Diffusion in Poly-(ethylene terephthalate), J. Appl. Polymer Sci.12, 2491- 2508 (1968).
20.
Egerton, G.S. and Shah, K.M., TheEffect of Temperature on the Photochemical Degradation of Textile Materials, Part I: Degradation Sensitized by Titanium Dioxide, Textile Res. J.38, 130-135 (1968).
21.
Fujiwara, S. , Amaniya, A., and Shinohara, K., Nuclear Magnetic Resonance in Irradiated Polyethylene, J. Chem. Phys.26, 1343 (1957 ).
22.
Fuschillo, N. and Sauer, J.A., Nuclear Magnetic Resonance and Crystallinity in Polyethylene and Nylon, BullAmer. Phys. Soc.2, 125 (1957).
23.
Fuschillo, N., and Sauer, J.A., Nuclear Magnetic Resonance, Radiation Damage and Rigidity in Branched Polyethylene as a Function of Temperature, J. Appl. Phys.28, 10731081 (1957).
24.
Fuschillo, N. and Sauer, J.A., Proton Resonance in Neutron and Gamma-irradiated Polyethylene, J. Chem. Phys.26, 1348 -1349 (1957).
25.
Glick, R.E. , Gupta, R.P., Sauer, J.A., and Woodward , A.E., Proton Magnetic Resonance of Poly (hexamethylene adipamide), J. Polymer Sci.42, 271-273 (1960).
26.
Gupta, R.P. , Nuclear Magnetic Resonance Investigation on Isotactic, Atactic, and Deuterated Isotactic Polypropytene, Kolloid-Zeit.174, 73-74 (1961).
27.
Gupta, R.P. , Proton Magnetic Resonance of Neutron Irradiated Polypropylene, Kolloid-Zeit.174, 74-75 (1961).
28.
Heuvel, H.M. and Lind, K.C.J.R., Electron Spin Resonance Study of the Initial Reaction of the Photodegradation of Nylon 6, J. Polymer Sci. A-28, 401-410 (1970).
29.
Hirt, R.C. and Searle, N.Z.Energy Characteristics of Outdoor and Indoor Exposure Sources and their Relation to the Weatherability of Plastics, Weatherability of Plastic Materials (Appl. Polymer Symp. No. 4), Edited by M. R. Kamal.New York, Interscience, 1967, pp. 61-83.
30.
Hopper, M.E. , McGregor, R. and Peters, R.H., SomeObservations on the Concentration Dependence of Diffusion Coefficients of Acid Dyes on Nylon, J. Soc. Dyers Colorists, 86, 117-122 (1970).
31.
Jellinek, H.H.G. and Chaudhuri, A.K., Inhibited Degradation of Nylon 66 in Presence of Nitrogen Dioxide, Ozone, Air and Near Ultraviolet Radiation, J. Polymer Sci.A-1 10. 1773-1788 (1972).
32.
Karpov, V.L. , Yurkevich, V.G., Kavalerova, L.M., Petrova, N.L., Glazkovskii, Y.V., and Egovrova , E.L., The Radiation Stability of Some Synthetic Fibers, Khim. Volokna1, 3032 (1969); Fiber Chem.1, 40--43 (1969).
33.
Kusy, R.P. and Turner, D.T., Influence of Gamma Irradiation on the Transition Temperatures of Crystalline Poly-(tetra fluoroethylene), J. Polymer Sci.A-110, 1745-1762 (1972 ).
34.
Lawton, E.J. , Bueche, A.M. and Balwit, J.S., Irradiation of Polymers by High Energy Electrons, Nature172, 76-77 (1953).
35.
Little, A.H. and Parsons, H.L., The Weathering of Cotton, Nylon, and Terylene Fabrics in the United Kingdom, Textile Inst. J. 58, 449462 (1967).
36.
Majury, T.G. and Pinner, S.H., TheIrradiation of Polycaprolactam with Gamma-rays and Electrons, J. Appl. Chem. (London)8, 168170 (1958).
37.
Marek, B. and Lerch, E., Photodegradation and Yellowing of Polyamides, J. Soc. Dyers Colorists81, 481-487 (1965).
38.
McGregor, R. and Peters, R.H., TheEffect of Rate of Flow on Rate of Dyeing I-The Diffusional Boundary Layer in Dyeing, J. Soc. Dyers Colorists81, 393-400 (1965).
39.
McGregor, R. and Peters, R.H., SomeObservations on the Relation between Dyeing Properties and Fiber Structure , J. Soc. Dyers Colorists84, 267-276 (1968).
40.
McGregor, R. , Peters, R.H. and Petropolous , J.H., Diffusion of Dyes in Polymer Films. Part 3: Naphthalene Scarlet 4R in Nylon 66, Trans. Faraday Soc.58, 1054-1063 (1962 ).
41.
Moore, R.F. , The Photochemical Degradation of Polyamides and Related Model N-Alkylamides, Polymer4, 493513 (1963).
42.
Munden, A.R. and Palmer, H.J., Measurement of Dyeing Properties and Correlation with Orientation in Nylon Yarn, J. Textile Inst.41, 609-631 (1950).
43.
Olf, H.G. and Peterlin, A., Nuclear Magnetic Resonance Observations of Drawn Polymers VII Nylon 66, J. Polymer Sci. A -29, '14491469 (1971).
44.
Peterlin, A. and Meinel, G.Calorimetry of Drawn and Rolled Linear Polyethylene of High and Low Crystallinity ; "Analytical Calorimetry," Vol. 2, Edited by R. S. Porter and J. F. Johnson.New York, Plenum Press, 1970.
45.
Peters, H.W. and White, T.R., TheEffect of Heat-Setting Treatments on the Dyeing Behaviour of Nylon Yarns and Fabrics, J. Soc. Dyers Colorists77, 601-602 (1961).
46.
Pomeroy, E.R. and Stevens, H.T., TheEffects of Weather on Drapery Lining Fabrics in Two Geographic Regions, J. Home Econ.56, 607-614 (1964).
47.
Rafikov, S.R. and Tsi-pin, S., Chemical Transformations of Polymers - V. Photochemical Transformations of Polycaproamide under Ultraviolet Irradiation in Vacuo, Vysokomol, soed. 3, 56-65 (1961); Polym. Sci. USSR3, 6-18 (1961).
48.
Rayonet Photochemical Reactor Operating Instructions, The Southern New England Ultraviolet Co., Middletown, Connecticut.
49.
Rosenbaum, S., Dyeing of Polyacrylonitrile Fibers: I. Rates of Diffusion with Malachite Green and Diffusion Model, J. Appl. Polymer Sci.7, 1225-1242 (1963 ).
50.
Rosenbaum, S., Role of Sites in Dyeing, Part II: Diffusion , Textile Res. J.34, 291-302 (1964).
51.
Rutherford, H.A. , "Textiles, Radiation Effects on Organic Materials ," Edited by R. O. Bolt and J. G.Carroll. New York, Academic Press, 1963, pp. 425445.
52.
Sharkey, W.H. and Mochel, W.E., Mechanism of the Photooxidation of Amides , J. Amer. Chem. Soc.81, 3000-3003 (1959 ).
53.
Singleton, R.W. and Cook, P.A.C., FactorsInfluencing the Evaluation of Actinic Degradation of Fibers, Part II: Refinement of Techniques for Measuring Degradation in Weathering, Textile Res. J.39, 43-54 (1969).
54.
Singleton, R.W., Kunkel, R.K. and Sprague, B.S., FactorsInfluencing the Evaluation of Actinic Degradation of Fibers, Textile Res. J.35, 228327 ( 1965).
55.
Slichter, W.P. and Davis, D.D., Nuclear Magnetic Resonance Studies of Molecular Motion in Natural Rubber, J. A ppl. Phys.34, 98-101 (1963).
56.
Slichter, W.P. and Mandell, E.R., Molecular Structure and Motion in Irradiated Polyethylene, J. Phys. Chem.62, 334340 (1958).
57.
Slonim, I.Y. and Lyubimov, A.N., "The NMR of Polymers," New YorkPlenum Press, 1970, pp. 365 ff.
58.
Starkweather, Jr., H.W. and Moynihan, R.E., Density, Infrared Absorption, and Crystallinity of 66 and 610 Nylon, J. Polymer Sci.22, 363368 (1956).
59.
Stephenson, C.V. , Moses, B.C., Burks, R.E. Jr., Coburn, W.C., Jr., and Wilcox , W.S., Ultraviolet Irradiation of Plastics. II. Crosslinking and Scission, J. Polymer Sci.55, 465475 (1961).
60.
Stephenson, C.V., Lacey, Jr., J.C. and Wilcox, W.S., Ultraviolet Irradiation of Plastics III. Decomposition Products and Mechanisms, J. Polymer Sci.55, 477-488 (1961).
61.
Sweet, G.E. and Bell, J.P., Multiple Endotherm Melting Behavior in Relation to Polymer Morphology, Y. Polymer Sci.A-210, 1273-1283 (1972 ).
62.
Szöcs, F., Becht, J., and Fischer, H., On Free Radical Recombination in Irradiated and in Strained Fibers of Polyamides , Eur. Polym. J.7, 173-179 (1971).
63.
Taytor, G.B. , TheRelation of the Viscosity of Nylon Solutions in Formic Acid to Molecular Weight as Determined by End-Group Measurements, J. Amer. Chem. Soc.69, 634-638 (1947).
64.
Taylor, H.A. , Tincher, W.C. and Hamner, W.F., Photodegradation of Nylon 66. I. Phototendering by TiO2, J. Appl. Polymer Sci.14, 141-146 (1970).
65.
Trommer, K.H. , RecentTechnology in the Dyeing of duPont Nylon Styling Yarns, Can. Textile J.85, 31-34 (1968).
66.
Verma, G.S.P. and Peterlin, A., Electron Spin Resonance Study of Mechanically Stretched Nylon 6 Fibers, Kolloid-Zeit.236, 111-115 (1970).
67.
Vickerstaff, T., "The Physical Chemistry of Dyeing," London, Oliver and Boyd, 1954, pp. 514 ff.
68.
Wall, M.J. and Frank, G.C., A Study of the Spectral Distribution of Sun-Sky and Xenon-Arc Radiation in Relation to the Degradation of Some Textile Yarns. Part I: Yarn Degradation , Textile Res. J.41, 38-50 (1971).
69.
Warwicker, J.O., TheStructural Causes of the Dyeing Variations of Nylon Subjected to Dry Heat , J. Soc. Dyers Colorists86, 303-310 (1970).
70.
Zimm, B.H., and Kilh, R.W., Dynamics of Branched Polymer Molecules in Dilute Solution, J. Polymer Sci.37, 19-42 (1959).
71.
Zimmerman, J., Degradation and Crosslinking inIrradiated Polyamides and the Effect of Oxygen Diffusion, J. Polymer Sci.46, 151-162 (1960).