Abstract
Polymer molecules respond to the application of stress by disentanglement, chain orientation and bond rupture. Being the last step in this series of events, the efficiency of flow-induced mechanochemical degradation depends markedly on the details of the pervading flow field. From the results of fluid mechanics, it is usual to distinguish degradation in simple shear flow from degradation in elongational flow. Polymer dynamics require a further subdivision between transient elongational flow, characterized by a short residence time (less than the chain relaxation time τ 1) in the high strain rate region, from quasi-steady-state elongational flow which possesses a stagnation point and a long residence time . This chapter reviews the main factors which influence the degradation kinetics in transient elongational flow, exemplified by flow through a narrow contraction and ultrasonic irradiation. The experimental results reveal a fundamental difference in the kinetics of chain scission in transient and stagnant conditions. Differences in the characteristic residence time prevalent in each type of flow permits one to probe the different stages of the chain unravelling process up to the point of bond rupture. It is suggested that the intricate degradation behavior observed in transient elongational flow stems from the compact nature of the weakly deformed molecular coil. This favors intramolecular interactions during the dynamics of deformation.
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8 References
Staudinger H (1930) Ber Dtsch Chem Ges 63: 3152
Kuhn W, Kuhn H (1944) Helv Chim Acta 27, 493
Frenkel YaI (1944) Acta Physicochim URSS 19: 51
Peterlin A (1966) Pure and Appl Chem 12: 563
Frank FC (1970) Proc Roy Soc London A 319: 127
Marucci G (1975) Polym Engin Sci 15: 229
de Gennes PG (1974) J Chem Phys 60: 5030
Pope DP, Keller A (1978) Coll and Polym Sci 256: 751
Farrell CJ, Keller A, Miles MJ, Pope DP (1980) Polymer 21: 1295
Fuller GG, Leal LG (1980) Rheol Acta 19: 580
Chaveteau G, Moan M (1981) J Phys (Paris) 42: L-201
Rabin Y (1987) J Chem Phys 86: 5215
Smith KA, Merrill EW, Peebles LH, Banijamali SH (1975) In: Wolf C (ed) Polymères et lubrication, Colloques Internationaux du CNRS, no. 233, Paris, p 341
Dennisson GL (1976) Master's thesis, Pennsylvania State University
Kausch HH (1987) Polymer fracture, 2nd (edn) Springer, Berlin Heidelberg New York, chap 5
Forsman WC (1986) Polymers in solution, Plenum Press, New York, p. 91
Kramers HA (1944) Physica 11: 1
Kuhn W (1936) Kolloid Z 76: 258
Flory PJ (1969) Statistical mechanics of chain molecules, Wiley Interscience, New York, chap VIII
Aharoni SM (1983) Macromolecules 16: 1722
Peiffer DG, Kim MW, Lundberg RD (1986) Polymer 27: 493
Tinland B, Rinaudo M (1989) Macromolecules 22: 1863
Ricka J, Meewes M, Nyffenegger R, Binkert Th (1990) Phys Rev Lett 65: 657
Flory PJ (1973) Principles of polymer chemistry, Cornell University Press, Ithaca, New York, chap XIV
Kuhn W (1934) Kolloid-Z 68: 2
Solc K, Stockmayer WH (1971) J Chem Phys 54: 2756
des Cloizeaux J, Jannink G (1987) Les polymères en solution: leur modélisation et leur structure, Les Editions de Physique, Les Ulis, France, p 269
de Gennes PG (1972) Phys Lett 38 A: 339
Ohta T, Oono Y, Freed KF (1982) Phys Rev A 25: 2801
de Gennes PG (1979) Scaling concepts in polymer physics, Cornell University Press, Ithaca, p 165
Park IH, Wang QW, Chu B (1987) Macromolecules 20: 1965
Treloar LRG (1975) The physics of rubber elasticity, 3rd (edn) Oxford University Press, London, chap VI
Warner HR Jr (1972) Ind Eng Chem Fundamentals 11: 379–387
Jhon MS, Sekhon G, Armstrong R (1987) The response of polymer molecules in a flow, Adv. Chem Phys 66: 153
Rabin Y, Creamer DB (1985) Macromolecules 18: 302
Kuhn W, Kuhn H (1945) Helv Chim Acta 28: 1533
Cerf R (1957) J Polym Sci 23: 125
de Gennes PG (1977) J Chem Phys 66: 5825
Rabin Y, Öttinger HC (1990) Europhys Lett 13: 423
Kuhn W (1934) Kolloid-Z 68: 2
Bird RB, Curtiss CF, Armstrong RC, Hassager O (1987) Dynamics of polymeric liquids, 2nd (edn) John Wiley, New York, vol 2, p 58
Booij HC (1988) J Rheol 32: 47
Tanner RI (1988) Engineering rheology, Clarendon Press, Oxford, rev (ed), p 185
Doi M, Edwards SF (1986) The theory of polymer dynamics, Clarendon Press, Oxford, chapters 4 & 5
Rouse PE (1953) J Chem Phys 21: 1272
Debye P, Bueche AM (1948) J Chem Phys 16: 573
Kirkwood JG, Riseman J (1948) J Chem Phys 16: 565
Zimm BH (1956) J Chem Phys 24: 269
Oono Y, Kohmoto M (1983) J Chem Phys 78: 520
Larson RG (1988) Constitutive equations for polymer melts and solutions, Butter-worths, Boston, p 256
Henyey FS, Rabin Y (1985) J Chem Phys 82: 4362
Larson RG, Magda JJ (1989) Macromolecules 22: 3004
Fuller GG, Leal LG (1980) Rheol Acta 19: 580
Ambari A, Deslouis C, Tribollet B (1984) Chem Engin Comm 29: 63
Wiest JM, Bird RB, Wedgewood LE (1988) On coil-stretch transitions in dilute polymer solutions, RRC Report no. 116, University of Wisconsin-Madison, May
Larson RG, Magda JJ (1989) Macromolecules 22: 3004
Müller AJ (1989) Extensional flow of macromolecules in solution, Ph D Thesis, University of Bristol, Physics Department
Phan-Thien N, Atkinson JD, Tanner RI (1978) J Non-Newt Fluid Mech 3: 309
James DF, Saringer JH (1980) J Fluid Mech 97: 655
King DH, James DF (1983) J Chem Phys 78: 4749
Broachard F, de Gennes PG (1977) Macromolecules 10: 1157
Batchelor GK (1971) J Fluid Mech 46: 813
Ryskin G (1987) J Fluid Mech 178: 423
Rabin Y (1988) J Chem Phys 88: 4014
Bleha T, Gajdos J (1988) Coll Polym Sci 266: 405
Rallison JM, Hinch EJ (1988) J Non-Newtonian Fluid Mech 29: 37
Boots S (1989) Anal Chem 61: 551 A
Schwartz DC, Koval M (1989) Nature 338: 520
Larson RG (1990) Rheol Acta 29: 371
Kausch HH, Nguyen TQ (Feb. 1991) Molecular coils and their deformation, IUPAC Symposium Polymer 91, Melbourne 10–15
Sacher E, Engel PA, Bayer RG (1979) J Appl Polym Sci 24: 1503
Tecante A, Choplin L, Lencki RW (1987) Polym Prep 28: 624
Viallat A, Pincus PA (1989) Polymer 30: 1997
Dikstra DJ, Pennings AJ (1988) Polym Bull 19: 73
Takahashi H, Matsuoka T, Ohta T, Fukumori K, Kurauchi T, Kamigaito O (1988) J Appl Polym Sci 36: 1821
Buerger DE, Engberg K, Jansson J-F, Gedde UW (1989) Polym Bull 22: 593
Ladik JJ (1988) Quantum theory of polymers as solids, Plenum Press, New York London
Michalske TA, Bunker BC (1984) J Appl Phys 56: 2686
Popov A, Rapoport N, Zaikov GE (1991) Oxidation of stressed polymers, Gordon and Breach Sci Publ New York London Tokyo, p 335
Smoilov GG, Tomashevskii EE (1969) Sov Phys — Solid State 10: 2395
Vershinina MP, Kvachadze NG, Tomashevskii EE (1977) Sov Phys — Solid State 19: 1382
Lloyd BA, Dvries KL, Williams ML (1972) J Polym Sci A 2 10: 1415
Gooden R, Davis DD, Hellman MY, Lovinger AJ, Winslow FH (1988) Macromolecules 21: 1212 (1988)
Adam RE, Zimm BH (1977) Nucleic Acis Res 4: 1513
Basedow AM, Ebert KH, Hunger H (1979) Makromol Chem 180: 411
Casale A, Porter RS (1978) Polymer stress reactions, Academic Press, New York, vol 1, p 9
Kelly A (1966) Strong solids, Clarendon Press, Oxford, p 6
Boudreaux DS (1973) J Polym Sci Polym Phys (ed) 11: 1285
Crist B, Ratner MA, Brower AL, Sabin JR (1979) J Appl Phys 50: 6047
Penning JP, van der Werff H, Roukema M, Pennings AJ (1990) Polym Bull 23: 347
Wool RP, Boyd RH (1980) J Appl Phys 51: 5116
de Boer JH (1936) Trans Far Soc 32: 10
Tomashevskii EE (1971) Sov Phys — Solid State 12: 2588
Krausz AR, Eyring H (1975) Deformation Kinetics, John Wiley New York, p 338
Tobolsky A, Eyring H (1943) J Chem Phys 11: 125
Zhurkov SN, Vettegren VI, Korsukov VE, Novak II (1969) Sov Phys — Solid State 11: 233
Bernstein HI (1962) Spectrochim Acta 18: 161
Zhurkov SN, Korsukov VE (1974) J Polym Sci Polym Phys (ed) 12: 385
Yew FFH, Davidson N (1968) Biopolymers 6: 659
Odell JA, Keller A, Rabin Y (1988) J Chem Phys 88: 4022
Crist B Jr, Oddershede J, Sabin JR, Perram JW, Ratner MA (1984) J Polym Sci Polym Phys (ed) 22: 881
Pope DP, Keller A (1977) Coll & Polym Sci 255: 633
Farrell CJ, Keller A, Miles MJ, Pope DP (1980) Polymer 21: 1292
Mikkelsen KJ, Macosko CW, Fuller GG (1988) Xth Internat Congr Rheol Sidney, vol 2, p 125
Tanner RI (1988) Engineering rheology, Clarendon Press, Oxford, rev (ed), p 185
Lodge TP, Miller JL, Schrag JL (1982) J Polym Sci 20: 1409
Cressely R, Hocquart R (1981) Polym Prepr 22: 120
Merrill EW, Leopairat P (1980) Polym Eng in Sci 20: 505
Nguyen TQ, Kausch HH (1986) Coll & Polym Sci 264: 764
Nguyen H, Boger DV (1979) J Non-Newtonian Fluid Mech 5: 353
Moreau V (1984) internal report T-84-2, Fluid mechanics laboratory, EPFL, Lausanne
Dennisson GL (1976) Master's thesis, Pennsylvania State University
Hill JW, Cuculo JA (1976) In: Elongational flow behavior of polymeric fluids, Rev in Macromol Chem 14 B, Marcel Dekker, New York, p 143
Besio GJ, Prud'homme RK, Benziger JB (1988) Macromolecules 21: 1070
Robinson IM, Yeung PHJ, Galiotis C, Young RJ (1986) J Mater Sci 21: 3440
Ambari A, Deslouis C, Tribollet B (1984) Chem Eng Comm 29: 63
Sheth PJ, Johnston JF (1978) in Polymer stress reactions, Academic Press, New York, vol 2, p 501
Mason TJ, Lorimer JP (1989) Sonochemistry: Theory, applications and uses of ultrasound in chemistry, Ellis Horwood Limited, Chichester, chap 2
Odell JA (December 1990) private communication
Ederer HJ, Basedow AM, Ebert KH (1981) In: Ebert KH, Deuf Chard P, Jager W (eds) Modelling of chemical reaction systems. Springer, Berlin Heidelberg New York, p 197
Van der Hoff BME, Glynn PAR (1974) J Macromol Sci-Chem A 8: 429
Ryskin G (1990) J Fluid Mech 218: 239
Culter JD, Zakin JL, Patterson GK (1975) J Appl Polym Sci 19: 3235
Polyflow, a finite element program for calculating viscous and viscoelastic flows, Polyflow SA, Place de l'Université 16, B-1348 Louvain-la-Neuve, Belgium (1988)
Nguyen TQ, Kausch HH (1989) Makromol Chem 190: 1389
Giesekus H (1962) Rheol Acta 2: 122
Gardner K, Pike ER, Miles MJ, Keller A, Tanaka K (1982) Polymer 23: 1442
Leal LG (1986) In: Rabin Y (ed) Studies of flow-induced conformation changes in dilute polymer solutions, Proceedings of the 1985 La Jolla Institute Workshop, Academic International Press, New York, p 5
Rabin Y, Henyey FS, Creamer DB (1986) J Chem Phys 85: 4696
Bird RB, Curtiss CF, Armstrong RC, Hassager O (1987) Dynamics of polymeric liquids, 2nd (ed), John Wiley & Sons, New York, vol 2, p 71
Gatski TB, Lumley JL (1978) J Fluid Mech 86: 623
Bueche F (1960) J Appl Polym Sci 4: 101
Ballauff M, Krämer H, Wolf BA (1983) J Polym Sci Polym Phys (ed) 21: 1205
Zakrevskii VA, Pakhotin VA (1981) Polym Sci USSR 23: 741
Fuhrmann J, Scherer GH, Nick L (1987) Makromol Chem 188: 2241
Dickinson JT, Crasto AS (1988) ACS Symposium Series no. 367, American chemical society, Washington DC, p 145–168
Kinpara H, Hori Y, Shimada S, Kashiwabara H (1985) Polym Comm 26: 142
Porter RS, Casale A (1985) Polym Engin Sci 25: 129
Ranby B, Rabek JF (1977) ESR Spectroscopy in polymer research, Springer, Berlin
Fijiwara H, Goto K (1990) Polym Bull 23: 27
Price GJ (1990) Adv Sonochemistry 1: 231
Berlin AA Chem Abstr 52: 11456b
Zhurkov SN, Zakrevskii VA, Korsukov VE, Kuksenko VS (1972) J Polymer Sci A 2 10: 1509
Grayson MA, Wolf CJ (1979) In: Stress mass spectrometry of polymeric materials: a review, ACS Adv Chem Series no. 174, Koenig JL (ed), p 53–80
Porter RS, Cantow MJR, Johnson JF (1967) J Polym Sci C 16: 1
Abdel-Alim AH, Hamielec AE (1973) J Appl Polym Sci 17: 3769
Nguyen TQ, Kausch HH (1988) J Non-Newtonian Fluid Mech 30: 125
Grubisic-Gallot Z, Marais L, Benoit H (1976) J Polym Sci A-2 Polym Phys 14: 959
Nguyen TQ, Kausch HH (1988) J Chromatogr 449: 63
Ishige T, Lee SI, Hamielec AE (1971) J Appl Polym Sci 15: 1607
Abbas KB (1980) Polym Engin Sci 20: 703
Ballauff M, Wolf BA (1981) Macromolecules 14: 654
Basedow AM, Ebert KH, Ederer H (1978) Macromolecules 11: 774
Ziff RM, McGrady ED (1986) Macromolecules 19: 2513
Nguyen TQ, Kausch HH (1989) Makromol Chem 190: 1389
ref 86, vol 1, p 125 and vol 2, p 2612
Brostow W, Ertepinar H, Singh RP (1990) Macromolecules 23: 5109
Malhotra SL (1986) J Macromol Sci Chem A 23: 729
Herold FK, Schulz GV, Wolf BA (1986) Polym Comm 27: 59
McCormick CL, Hester RD, Morgan SE, Safieddine AM (1990) Macromolecules 23: 2124
Deshmukh SR, Singh RP (1986) J Appl Polym Sci 32: 6163
Odell J, Keller A (1986) J Polym Sci Polym Phys (ed) 24: 1889
Nguyen TQ, Kausch HH (1987) Polym Prep 28: 409
Encina MV, Lissi E, Sarasua M, Gargallo L, Radic D (1980) J Polym Sci Polym Lett 18: 757
Odell JA, Muller AJ, Narh KA, Keller A (1990) Macromolecules 23: 3093
Nguyen TQ, Kausch HH (1990) Macromolecules 23: 5137
Fujita H (1990) Polymer solutions, Elsevier, Amsterdam Oxford, chap 6
Aharoni SM (1983) Macromolecules 16: 1722
Keller A, Odell JA, Miles MJ (1985) Polymer 26: 1219
Ballauff M, Wolf BA (1988) Adv Polym Sci 85: 1
Merrill EW, Horn AF (1984) Polym Comm 25: 144
Horn AF, Merrill EW (1987) Polym Comm 28: 172
Muller AJ, Odell JA, Carrington S (April 1991) In: Degradation of polymer solutions in extensional flow, Proceedings of the polymer physics: a Conference to mark the retirement of A Keller, Bristol UK 3–5
Keller A, Odell JA (1985) Coll Polym Sci 263: 181
Levinthal D, Davison PF (1961) J Mol Biol 3: 674
Harrington RE, Zimm BH (1965) J Phys Chem 69: 161
Nguyen TQ, Kausch HH (1991) Influence of nozzle geometry on polystyrene degradation in transient elongation flow, to be published in Coll Polym Sci
Ref 105, p 329
Basedow AM, Ebert KH (1977) Adv Polym Sci 22: 83
Basedow AM, Ebert KH (1978) Makromol Chem 179: 2565
El'tsefon BS, Berlin AA (1964) Polym Sci USSR 5: 668
Doullah MS (1978) J Appl Polym Sci 22: 1735
Hano AL, Williams MC, Grens EA (1986) II, J Appl Polym Sci 32: 3649
Hoyt JW (june 1972) J Basic Engin Trans ASME 258
Peterlin A (1970) Nature 227: 598
Lumley JL (1969) Ann Rev Fluid Mech 1: 367; (1973) J Polym Sci Macromol Rev 7:263
Nguyen TQ, Kausch HH (1986) Chimia 40: 129
Muller HG, Klein J, Rottlof A (1981) Makromol Chem 182: 529
Horn AF, Merrill EW (1984) Nature 5990: 140
Ting RY, Little RC (1973) J Appl Polym Sci 17: 3345
Gold PI, Amar PK, Swaidan BE (1973) J Appl Polym Sci 17
Brostow W (1983) Polymer 24: 631
Dupuis D, Wolff C (1985) Chem Eng Comm 32: 203
Lindner P, Oberthür RC (1985) Coll Polym Sci 263: 443; (1988) Coll Polym Sci 266: 886
Janeschitz-Kriegl H, Burchard W (1986) J Polym Sci A 2 6: 1953
Müller HG, Klein J (1981) Makromol Chem 182: 513
Basedow AM, Ebert KH, Hunger H (1979) Makromol Chem 180: 411
Ref 86, vol 1, p 104
Abbas KB, Porter RS (1976) J Polym Sci Polym Chem (ed) 14: 553
Zysman V, Nguyen TQ, Kausch HH unpublished results
Huber C, Lederer KH (1980) J Polym Sci Pol Lett (ed) 18: 535
Barth HG, Carlin FJ Jr (1984) J Liq Chromatogr 7: 1717
McIntyre D, Shih AL, Savoca J, Seeger R, MacArthur A (1984) ACS Symposium series, no. 245: 227
Kauzmann WJ, Eyring H (1940) J Amer Chem Soc 62: 3113
Morris WJ, Schnurmann R (1947) Nature 160: 674
Bestul AB (1956) J Chem Phys 24: 1196
Goodman P, Bestul AB (1955) J Polym Sci 18: 235
Wolf BA (1987) Makromol Chem Rapid Comm 8: 461
Menasveta MJ, Hoagland DA (1991) Macromolecules 24: 3427
Reese HR, Zimm BH (1990) J Chem Phys 92: 2650
Hunkeler D, Nguyen TQ, Kausch HH (Aug 1991) ACS meeting in New York City
Cathey CA, Fuller GG (1990) J Non-Newt Fluid Mech 34: 63
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Nguyen, T.Q., Kausch, HH. (1992). Mechanochemical degradation in transient elongational flow. In: Macromolecules: Synthesis, Order and Advanced Properties. Advances in Polymer Science, vol 100/1. Springer, Berlin, Heidelberg. https://doi.org/10.1007/BFb0051636
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