Rheologica Acta

, Volume 42, Issue 1–2, pp 132–141 | Cite as

Viscoelastic behaviour of partly hydrolysed polyacrylamide/chromium(III) gels

  • Klaas te Nijenhuis
  • Annemiek Mensert
  • Pacelli L. J. Zitha
Original Contribution

Abstract.

This paper reports an experimental investigation of the crosslinking process of high molecular weight partly hydrolysed polyacrylamides (HPAAm) in aqueous brine solution by trivalent chromium ions (Cr(III)). Crosslinking took place in the presence of a retardant agent (sodium citrate). First, sol-gel phase diagrams (in the polymer and concentration space) were established using the tilting tube method. Then, for a fixed composition, the gelation process was monitored systematically using dynamic viscoelastic measurements, varying the main parameters (pH, time, temperature and retardant concentration). Network formation proceeds rather slowly and an equilibrium state was not reached within 12 h. The gel was formed only at pHs between 5 and 9 and thus two gel points (i.e. at two pHs) were determined with the Winter-Chambon method. This is in agreement with the chemistry of aqueous chromium and of acrylic acid groups along the polymer backbone. Kinetics of network formation depends strongly on retardant concentration. Temperature plays an important role: network formation proceeds much faster at high temperature, in agreement with chemical kinetics.

Keywords.

Viscoelasticity Polyacrylamide/Cr(III) gel Phase diagram Gel point 

References

  1. Albonico P, Burrafato G, Di Lullu A, Lockhart TP (1993) Effective gelation-delaying additives for Cr+3/polymer gels. SPE Journal, paper SPE 25221, presented at the SPE International Symposium on Oilfield Chemistry, New Orleans, March 2–5Google Scholar
  2. Allain C, Salomé L (1987) Hydrolysed polyacrylamide/Cr3+ gelation: critical behaviour of the rheological properties at the sol-gel transition. Polym Commun 28:109–112Google Scholar
  3. Allain C, Salomé L (1988) Physico-chemistry of the hydrolysed polyacrylamide-chromium III interaction in relation to rheological properties. In: Kramer O (ed) Biological and synthetic polymer networks. Elsevier, London, chap 19Google Scholar
  4. Allain C, Salomé L (1990) Gelation of semidilute polymer solutions by ion complexation: critical behaviour of the rheological properties versus cross-link concentration. Macromolecules 23:981–987Google Scholar
  5. Bagassi M (1989) Comportement hydrodynamique des macromolécules dans les milieux poreux fins en régime de déformation faible. PhD Thesis, Paris, FranceGoogle Scholar
  6. Beltman H (1975) Verdikken en geleren. Doctoral Thesis, Wageningen, The NetherlandsGoogle Scholar
  7. Beltman H, Lyklema J (1974) Rheological monitoring of the formation of polyvinyl alcohol-congo red gels. Discuss Faraday Chem Soc 57:92–100Google Scholar
  8. Borchard W, Pyrlik M, Rehage G (1971) Association phenomena of PMMA in solutions and gels. Makromol Chem 145:169–188Google Scholar
  9. Burrafato G, Carminati S, Bonaccorsi F, Lockhart TP (1990) Evidence for molecular Cr3+ cross-links in Cr3+/polyacrylamide gels. Macromolecules 23:2402–2406Google Scholar
  10. Chambon F, Winter HH (1985) Stopping of crosslinking reaction in a PDMS polymer at the gel point. Polym Bull 13:499–503Google Scholar
  11. Chambon F, Winter HH (1987) Linear viscoelasticity at the gel point of a crosslinking PDMS with imbalanced stoichiometry. J Rheol 30:683–697Google Scholar
  12. Clark AH, Ross-Murphy SB (1987) Structural and mechanical properties of biopolymer gels. Adv Polym Sci 83:57–192Google Scholar
  13. Cotton FA, Wilkinson G (1988) Advanced inorganic chemistry, 5th edn. Wiley, New YorkGoogle Scholar
  14. de Gennes PG (1979) Scaling concepts in polymer physics. Cornell University Press, Ithaca NYGoogle Scholar
  15. Dorrestijn A, te Nijenhuis K (1990) Viscoelastic behaviour during gelation of solutions of polyvinyl chlorides of various molar masses and polymerisation temperatures. Colloid Polym Sci 268:895–900Google Scholar
  16. Dorrestijn A, Keijzers AEM, te Nijenhuis K (1981) Correlation between viscoelastic behaviour and small angle X-ray scattering of thermoreversible polyvinyl chloride gels. Polymer 22:305–312Google Scholar
  17. Flory PJ (1941) Molecular size distribution in three-dimensional polymers. III. Tetrafunctional branching units. J Am Chem Soc 63:3096–3100Google Scholar
  18. Flory PJ (1947) Molecular size distribution in three-dimensional polymers. V. Post gelation relationships. J Am Chem Soc 69:30–35Google Scholar
  19. Flory PJ (1953) Principles of polymer chemistry. Cornell University Press, Ithaca NY, chap 9Google Scholar
  20. Franse MWCP, te Nijenhuis K (2000) Crosslinking index, molecular weight distribution, and rubber equilibrium shear modulus during polyfunctional crosslinking of existing polymer. Part 5. Primary polymer with a discrete distribution of the molecular weights. J Mol Struct 554:1–10Google Scholar
  21. Franse MWCP, te Nijenhuis K (2001) Crosslinking index, molecular weight distribution, and rubber equilibrium shear modulus during polyfunctional crosslinking of existing polymer. Part 6. Primary polymer with a Schulz-Zimm distribution of the molecular weights. Macromol Theory Simul 11:342–351Google Scholar
  22. Gallino G, Molinari M, Lockhart TP (1991) Rheological studies of the gelation kinetics of Cr3+-polyacrylamide solutions. Makromol Chem Macromol Symp 45:137–144Google Scholar
  23. Guenet J-M (1992) Thermoreversible gelation of polymers and biopolymers. Academic Press, LondonGoogle Scholar
  24. Hunt JA, Young TS, Green DW, Willhite GP (1989) A study of Cr(III)-polyacrylamide reaction kinetics by equilibrium dialysis. AIChE J 35:250–258Google Scholar
  25. Ilavský M, Hrouz J, Stejskal J, Bouchal K (1984) Phase transition in swollen gels. 6. Effect of aging on the extent of hydrolysis of aqueous polyacrylamide solutions and on the collapse of gels. Macromolecules 17:2868–2874Google Scholar
  26. Lockhart TP (1991) Chemical and structural studies on Cr+3/polyacrylamide gels. SPE Journal, paper SPE 20998, presented at the SPE International Symposium on Oilfield Chemistry, Anaheim, Feb 20–22Google Scholar
  27. Lockhart TP, Albonico P, Burrafato G (1991) Slow-gelling Cr+3/polyacrylamide solutions for reservoir profile modification: dependence of the gelation time on pH. J Appl Polym Sci 43:1527–1532Google Scholar
  28. Mabire F, Audebert R, Quivoron C (1984) Synthesis and solution properties of water soluble copolymers based on acrylamide and quaternary ammonium acrylic comonomer. Polymer 25:1317–1322Google Scholar
  29. Morton SD, Ferry JD (1962) Dynamic mechanical properties of polyvinyl chloride gels. J Phys Chem 66:1639–1645Google Scholar
  30. Prud'homme RK, Uhl JT, Poinsatte JP, Halverson F (1983) Rheological monitoring of the formation of polyacrylamide/Cr+3 gels. SPE J (Oct 1983) 804–808Google Scholar
  31. Pyrlik M, Rehage G (1975) Viskoelastische Eigenschaften von nebenvalenzmässig vernetzen Gelen. I. Gelen aus stereospezifischen Polymethylmethacrylaten. Rheol Acta 14:303–311Google Scholar
  32. Pyrlik M, Rehage G (1976) Rheologische Untersuchungen an nebenvalenzmässig vernetzen Gelen aus iso- und syndiotaktischem PMMA. Colloid Polym Sci 254:329–341Google Scholar
  33. Pyrlik M, Borchard W, Rehage G, Uerpmann EP (1974) Untersuchungen über den Gelierungsvorgang in Lösungen von stereoregulären Polymethylmethacrylaten. Angew Makromol Chem 36:133–144Google Scholar
  34. Stockmayer WH (1943) Theory of molecular size distribution and gel formation in branched-chain polymers. J Chem Phys 11:45–55Google Scholar
  35. Stockmayer WH (1944) Theory of molecular size distribution and gel formation in branched-chain polymers. II. General cross-linking. J Chem Phys 12:125–131Google Scholar
  36. te Nijenhuis K (1979) Dynamic mechanical studies on thermoreversible ageing processes in gels of polyvinyl chloride and of gelatin. Doctoral Thesis, Delft, The NetherlandsGoogle Scholar
  37. te Nijenhuis K (1981a) Investigation into the ageing process in gels of gelatin/water systems by the measurement of their dynamic moduli. Part I. Phenomenology. Colloid Polym Sci 259:522–535Google Scholar
  38. te Nijenhuis K (1981b) Investigation into the ageing process in gels of gelatin/water systems by the measurement of their dynamic moduli. Part II. Mechanism of the ageing process. Colloid Polym Sci 259:1017–1026Google Scholar
  39. te Nijenhuis K (1991a) Calculation of network parameters during cross-linking of uniform and non-uniform polymer with cross-links of various functionalities. In: Patsis AV (ed), Proceedings of 5th International Conference on Crosslinked Polymers, Luzern, chap 6Google Scholar
  40. te Nijenhuis K (1991b) Crosslinking index, molecular weight distribution, and rubber equilibrium shear modulus during polyfunctional crosslinking of existing polymer. Part 1. Theory. Makromol Chem 192:603–616Google Scholar
  41. te Nijenhuis K (1991c) Crosslinking index, molecular weight distribution, and rubber equilibrium shear modulus during polyfunctional crosslinking of existing polymer. Part 2. Application to real systems. Makromol Chem Macromol Symp 45:117–126Google Scholar
  42. te Nijenhuis K (1993a) Crosslinking index, molecular weight distribution, and rubber equilibrium shear modulus during polyfunctional crosslinking of existing polymer. Part 3. Primary polymer with a cumulative Flory distribution or a cumulative Schulz-Flory distribution of the molecular weights. Polym Gels Networks 1:185–198Google Scholar
  43. te Nijenhuis K (1993b) Crosslinking index, molecular weight distribution, and rubber equilibrium shear modulus during polyfunctional crosslinking of existing polymer. Part 4. Recapitulation and presentation of general results of calculations for a hypothetical crosslinking process. Polym Gels Networks 1:199–210Google Scholar
  44. te Nijenhuis K (1993c) Calculation of network parameters in cross-linking of uniform and non-uniform polymer with cross-links of various functionalities. In: Kahovec J (ed) Macromolecules 1992. Proceedings of the 34th IUPAC International Symposium on Macromolecules, Prague 1992, VSP Interscience Publishers, Utrecht, Chap 3Google Scholar
  45. te Nijenhuis K (1996) Calculation of network parameters in thermoreversible gels. Polym Gels Networks 4:415–433Google Scholar
  46. te Nijenhuis K (1997) Thermoreversible networks. Viscoelastic properties and structure of gels. Adv Polym Sci 130:1–267Google Scholar
  47. te Nijenhuis K (2001) Crosslink nature in Cr(III)-polyacrylamide gels. Macromol Symp 171:189–200Google Scholar
  48. te Nijenhuis K, Dijkstra H (1975) Investigation of the aging process of a polyvinyl chloride gel by the measurement of its dynamic moduli. Rheol Acta 14:71–84Google Scholar
  49. te Nijenhuis K, Winter HH (1989) Mechanical properties at the sol-gel transition during the ageing of concentrated PVC solutions. Macromolecules 22:411–414Google Scholar
  50. Winter HH (1989) Gel point. In: Kroschwitz JI, Bikalis N (eds), Supplement to encyclopaedia of polymer science and engineering, 2nd edn. Wiley, New York, pp 343–351Google Scholar
  51. Winter HH, Chambon F (1986) Analysis of linear viscoelasticity of a cross-linking polymer at the gel point. J Rheol 30:367–382Google Scholar
  52. Winter HH, Mours M (1997) Rheology of polymers near the liquid-solid transition. Adv Polym Sci 134:165–234Google Scholar
  53. Young TS, Willhite GP, Green DW (1986) In: Stahl GA, Schulz DN (eds) Water soluble polymers for petroleum recovery. Plenum Press, New York, p 329Google Scholar

Copyright information

© Springer-Verlag 2003

Authors and Affiliations

  • Klaas te Nijenhuis
    • 1
  • Annemiek Mensert
    • 2
  • Pacelli L. J. Zitha
    • 2
  1. 1.Laboratory of Polymer Materials and Engineering, Faculty of Applied Sciences, Delft University of Technology Julianalaan 136, 2628 BL Delft
  2. 2.Dietz Laboratory, Faculty of Technical Earth Sciences, Delft University of Technology, Mijnbouwstraat 120, 2628 RX Delft, The Netherlands

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