Skip to main content
SpringerLink
Log in

A Composting Study of Membrane-Like Polyvinyl Alcohol Based Resins and Nanocomposites

  • Original Paper
  • Published:
Journal of Polymers and the Environment Aims and scope Submit manuscript

Abstract

This study presents the effect of biodegradation, in a composting medium, on properties of membrane-like crosslinked and noncrosslinked polyvinyl alcohol (PVA) and nanocomposites. The composting was carried out for 120 days and the biodegradation of these materials was characterized using various techniques. The changes in the PVA resin and nanocomposite surface topography and microstructure during composting were also characterized. The results from the analyses suggest biodegradation of PVA based materials in compost medium was mainly by enzymes secreted by fungi. The results also indicate that the enzymes degraded the amorphous regions of the specimens first and that the PVA crystallinity played an important role in its biodegradation. The surface roughness of the specimens was seen to increase with composting time as the microbial colonies grew which in turn facilitated further microorganism growth. All specimens broke into small pieces between 90 and 120 days of composting as a result of deep biodegradation. Glyoxal and malonic acid crosslinking decreased the PVA biodegradation rate slightly. Addition of highly crystalline microfibrillated cellulose and naturally occurring halloysite nanotubes in PVA based nanocomposites also decreased the biodegradation rate. The three factors: PVA crystallinity, crosslinking and additives, may be utilized effectively to extend the life of these materials in real life applications.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10

Similar content being viewed by others

References

  1. Cho D, Netravali AN, Joo YL (2012) Mechanical properties and biodegradability of electronspun soy protein isolate/PVA hybrid nanofibers. Polym Degrad Stab 97:747–954

    Article  CAS  Google Scholar 

  2. Luo S, Netravali AN (2003) A study of physical and mechanical properties of poly(hydroxybutyrate-co-hydroxyvalerate) during composting. Polym Degrad Stab 80:59–66

    Article  CAS  Google Scholar 

  3. Lodha P, Netravali AN (2005) Effect of soy protein isolate resin modifications on their biodegradation in a compost medium. Polym Degrad Stab 87:465–477

    Article  CAS  Google Scholar 

  4. Qiu K, Netravali AN (2012) Biodegradable composites of polyvinyl alcohol reinforced with microfibrillated cellulose. J Mater Sci 47(16):6066–6075

    Article  CAS  Google Scholar 

  5. Qiu K, Netravali AN (2013) ‘Green’ composites based on bacterial cellulose produced using novel low cost carbon source and soy protein resin. Recent advances in adhesion science & technology: Mittal festschrift. Taylor & Francis, London (in press)

  6. Qiu K, Netravali AN (2012) Fabrication and characterization of biodegradable composites based on microfibrillated cellulose and polyvinyl alcohol. Compos Sci Technol 72(13):1588–1594

    Article  CAS  Google Scholar 

  7. Qiu K, Netravali AN (2013) Halloysite nanotube reinforced biodegradable nanocomposites using noncrosslinked and malonic acid crosslinked polyvinyl alcohol. Polym Compos. doi:10.1002/pc.22482

  8. Stevens ES (2002) Green plastics: an introduction to the new science of biodegradable plastics. Princeton University Press, Princeton, pp 10–30

    Google Scholar 

  9. Chiellini E, Corti A, D’Antone S, Solaro R (2003) Biodegradation of poly (vinyl alcohol) based materials. Prog Polym Sci 28:963–1014

    Article  CAS  Google Scholar 

  10. Netravali AN, Chabba S (2003) Composites get greener. Mater Today 6(4):22–29

    Article  Google Scholar 

  11. Georgia Tech Research Institute (2011) ‘Breaking down plastics: new standard specification may facilitate use of additives that trigger biodegradation of oil-based plastics in landfills’. http://gtresearchnews.gatech.edu/biodegradation-of-plastics/

  12. Mittal V (2011) Nanocomposites with biodegradable polymers: synthesis, properties and future perspectives. Oxford University Press, Oxford, pp 1–27

    Book  Google Scholar 

  13. Bohlmann GM (2005) General characteristics, processability, industrial applications and market evolution of biodegradable polymers. In: Bastioli C (ed) Handbook of biodegradable polymers. Rapra Tech Ltd, Shawbury, pp 183–218

    Google Scholar 

  14. Lemm W, Krukenberg T, Regier G, Gerlach K, Bucherl ES (1981) Biodegrdation of some biomaterials after subcutaneous implantation. Proc Eur Sco Artif Org 8:71–75

    Google Scholar 

  15. Potts JE, Clendinning RA, Ackart WB, Neigisch WD (1973) The biodegradability of synthetic polymers. In: Guillet J (ed) Polymers and ecological problems. Plenum Press, New York, pp 61–80

    Chapter  Google Scholar 

  16. Swift G (1992) Biodegrdable polymers in the environment: are they really biodegradable? Pro ACS Div Polym Mater Sci Eng 66:403–404

    CAS  Google Scholar 

  17. Ratner BC, Gladhill KW, Horbett TA (1988) Analysis of in vitro enzymatic and oxidative degradation of polyurethane. J Biome Mater Res 22:509–527

    Article  CAS  Google Scholar 

  18. Hergenrother RW, Wabers HD, Cooper SL (1992) The effect of chain extenders and stabilizers on the in vivo stability of polyurethanes. J Appl Biomater 3:17–22

    Article  Google Scholar 

  19. Reich L, Stivala SS (1971) Elements of polymer degradation. McGraw-Hill, New York

    Google Scholar 

  20. Kronenthal RL (1975) Biodegradable polymers in medicine and surgery. In: Kronenthal RL, Oser Z, Martin E (eds) Polymers in medicine and surgery. Plenum Press, New York, pp 119–133

    Chapter  Google Scholar 

  21. Gilding DK (1981) Biodegradable polymers. In: Williams DF (ed) Biocompatibility of clinic implant materials. CRC Press, Boca Raton, pp 209–232

    Google Scholar 

  22. Itavaara M, Karjomaa S, Selin JF (2002) Biodegradation of polyolactide in aerobic and anaerobic thermophilic conditions. Chemosphere 46:879–885

    Article  CAS  Google Scholar 

  23. Tokiwa Y, Suzuki T (1978) Hydrolysis of polyesters by rhizopus delemar lipase. Agric Biol Chem 42:1071–1072

    Article  CAS  Google Scholar 

  24. Tokiwa Y, Suzuki T (1981) Hydrolysis of copolyesters containing aromatic and aliphatic ester blocks by lipase. J Appl Polym Sci 26:441–448

    Article  CAS  Google Scholar 

  25. Tokiwa Y, Suzuki T, Ando T (1979) Synthesis of copolyamide-esters and some aspects involved in their hydrolysis by lipase. J Appl Polym Sci 24:1701–1711

    Article  CAS  Google Scholar 

  26. Tokiwa Y, Calabia BP, Ugwu CU, Aiba S (2009) Biodegradability of plastics. Int J Mol Sci 10:3722–3742

    Article  CAS  Google Scholar 

  27. Corti A, Solaro R, Chiellini E (2002) Biodegradation of poly (vinyl alcohol) in selected mixed microbial culture and relevant culture filtrate. Polym Degrad Stab 75(3):447–458

    Article  CAS  Google Scholar 

  28. Lodha P (2004) Fundamental approaches to improving performance of soy protein isolate based ‘green’ plastics and composites. PhD Dissertation, Cornell University, Ithaca, NY, pp 101–129

  29. Semenov SA, Gumargalieva KZ, Zaikov GE (2003) Biodegrdation and durability of materials under the effect of microorganisms. VSP BV, Boston

    Google Scholar 

  30. Han SI, Lim JS, Kim DK, Kim MN, Im SS (2008) In situ polymerized poly (butylene succinate)/silica nanocomposites: physical properties and biodegradation. Polym Degrad Stab 93:889–895

    Article  CAS  Google Scholar 

  31. Yang HS, Yoon JS, Kim MN (2005) Dependence of biodegradability of plastics in compost on the shape of specimens. Polym Degrad Stab 87:131–135

    Article  CAS  Google Scholar 

  32. Ray SS, Okamoto M (2003) Biodegradable polylactide and its nanocomposites; opening a new dimension for plastics and composites. Macromol Rap Comm 24:815–840

    Article  CAS  Google Scholar 

  33. Fukuda N, Tsuji H, Ohnishi Y (2002) Physical properties and enzymatic hydrolysis of poly (-latide)-CaCO3 composites. Polym Degrad Stab 78:119–127

    Article  CAS  Google Scholar 

  34. Quynh TM, Mitomo H, Nagasawa N, Wada Y, Yoshii F, Tamada M (2007) Properties of crosslinked polylactides (PLLA & PDLA) by radiation and its biodegradability. Euro Polym J 43:1779–1785

    Article  CAS  Google Scholar 

  35. Solaro R, Corti A, Chiellini E (2000) Biodegradation of poly (vinyl alcohol) with different molecular weight and degree of hydrolysis. Polym Adv Technol 11(8–12):873–878

    Article  CAS  Google Scholar 

  36. Vijayalakshmi SP, Madras G (2006) Effects of the pH, concentration, and solvents on the ultrasonic degradation of poly(vinyl alcohol). J Appl Polym Sci 100(6):4888–4892

    Article  CAS  Google Scholar 

  37. Watanabe Y, Morita M, Hamada N, Tsujisaka Y (1975) Formation of hydrogen peroxide by a polyvinyl alcohol degrading enzyme. Agric Biol Chem 39:2447–2448

    Article  CAS  Google Scholar 

  38. Suzuki T, Ichihara Y, Yamada M, Tonomura K (1973) Some characteristics of Pesudomonas O-3 which utilize polyvinyl alcohol. Agric Biol Chem 37:747–756

    Article  CAS  Google Scholar 

  39. Sakai K, Hamada N, Watanabe Y (1986) Studies on the poly(vinyl alcohol)-degrading enzyme. Part VI. Degradation mechanism of poly(vinyl alcohol) by successive reactions of secondary alcohol oxidase and β-diketone hydrolase from Pseudomonas sp. Agric Biol Chem 50:989–996

    Article  Google Scholar 

  40. Jecu L, Grosu E, Raut I, Ghiurea M, Constantin M, Stoica A, Stroescu M, Vasilescu G (2012) Fungal degradation of polymeric materials: morphological aspects. http://www.inginerie-electrica.ro/acqu/2011/P_1_Fungal_degradation_of_polymeric_materials_Morfological_aspects.pdf

  41. Larking DM, Crawford RJ, Christie GBY, Lonergan GT (1999) Enhanced degradation of polyvinyl alcohol by Pysnoporus cinnabarinus after pretreatment with Fenton’s reagent. Appl Environ Microbiol 65(4):1798–1800

    CAS  Google Scholar 

  42. Chiellini E, Corti A, Solaro R (1999) Biodegradation of poly (vinyl alcohol) based blown films under different environmental conditions. Polym Degrad Stab 64:305–312

    Article  CAS  Google Scholar 

  43. Jayasekara R, Harding I, Bowater I, Christie GBY, Lonergan GT (2003) Biodegradation by composting of surface modified starch and PVA blended films. J Polym Environ 11(2):49–56

    Article  CAS  Google Scholar 

  44. Solaro R, Corti A, Chiellini E (1998) A new respirometric test simulating soil burial conditions for the evaluation of polymer biodegradation. J Environ Polym Degrad 6:203–208

    Article  CAS  Google Scholar 

  45. Matsumura S, Tanaka T (1994) Novel malonate-type copolymers containing vinyl alcohol blocks as biodegradable segments and their builder performance in detergent formulation. J Environ Polym Degrad 2:89–97

    Article  CAS  Google Scholar 

  46. Diaz LF, Savage GM, Eggerth LI, Golueke CG (1993) Composting and recycling-municipal solid waste. Lewis Publishers, Boca Raton

    Google Scholar 

  47. Maiti S, Ray D, Mitra D (2012) Role of crosslinker on the biodegradation behavior of starch/polyvinylalcohol blend films. J Polym Environ 20:749–759

    Article  CAS  Google Scholar 

  48. Chai W, Chou J, Chen C (2012) Effects of modified starch and different molecular weight polyvinyl alcohols on biodegradable characteristics of polyvinyl alcohol/starch blends. J Polym Environ 20:550–564

    Article  CAS  Google Scholar 

  49. Jian S, Ming SX (1987) Crosslinked PVA-PS thin-film composite membrane for reverse osmosis. Desalination 62:395–403

    Article  Google Scholar 

  50. Majumdar S, Adhikari B (2006) Polyvinyl alcohol: a taste sensing material. Sensors Actuators B-Chem 114:747–755

    Article  CAS  Google Scholar 

  51. Huang X, Netravali AN (2008) Environmentally friendly green materials from plant-based resources: modification of soy protein using Gellan and micro/nano-fibrillated cellulose. J Macromol Sci A 45:899–906

    Article  Google Scholar 

  52. Rathi P (2007) Soy protein based nanophase reins for green composites. A project report, Cornell University, Ithaca, NY, pp 13–18

  53. Rudnik E (2008) Compostable polymer materials. Elsevier, Oxford, pp 89–112

    Google Scholar 

  54. Sang BI, Hori K, Tanji Y, Unno H (2002) Fungal contribution to in situ biodegradation of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) film in soil. Appl Microbiol Biotechnol 58:241–247

    Article  CAS  Google Scholar 

  55. Taixing Shenlong Chemical Co., Ltd (2012) Crystal ortho phosphorous acid. http://www.sl-chemical.com/pages/pro4_en.htm

  56. Jeffries Group (2011) Compost creating cool cucumbers. http://www.jeffries.com.au/about-us/news/article/cucumbers

  57. BASF (2011) Glyoxal-the sustainable solution for your business. http://worldaccount.basf.com/wa/NAFTA/Catalog/ChemicalsNAFTA/doc4/BASF/PRD/30037091/.pdf?title=Brochure&asset_type=pi/pdf&language=EN&urn=urn:documentum:eCommerce_sol_EU:09007bb2800475c8.pdf

  58. Gohil JM, Bhattacharya A, Ray P (2006) Studies on the cross-linking of poly (vinyl alcohol). J Polym Res 13:161–169

    Article  CAS  Google Scholar 

  59. Mansur HS, Sadahira CM, Souza AN, Mansur AAP (2008) FTIR spectroscopy characterization of poly (vinyl alcohol) hydrogel with different hydrolysis degree and chemically crosslinked with glutaraldehyde. Mater Sci Eng C 28:539–548

    Article  CAS  Google Scholar 

  60. Kim JH, Moon EJ, Kim CK (2003) Composite membranes prepared from poly (m-animostyrene-co-vinyl alcohol) copolymers for the reverse osmosis process. J Membr Sci 216:107–120

    Article  CAS  Google Scholar 

  61. Warner SB (1995) Fiber science. Prentice Hall, Upper Saddle River, pp 205–206

    Google Scholar 

  62. Blaine RL (2011) Determination of polymer crystallinity by DSC. TA Instruments, www.tainstruments.com/library_download.aspx?file=TA123.PDF

  63. Sichina WJ (2011) DSC as problem solving tool: measurement of percent crystallinity of thermoplastics. PerkinElmer Instruments. http://www.perkinelmer.com/Content/applicationnotes/app_thermalcrystallinitythermoplastics.pdf

  64. Guirguis OW, Moselhey MTH (2012) Thermal and structural studies of poly (vinyl alcohol) and hydroxypropyl cellulose blends. Nat Sci 4(1):57–67

    CAS  Google Scholar 

  65. Netravali AN, Krstic R, Crouse JL, Richmond LE (1993) Chemical stability of polyester fibers and geotextiles without and under stress. ASTM, STP 1190:207–217

    CAS  Google Scholar 

  66. Mathur A, Netravali AN, O’Rourke D (1994) Chemical aging effects on the physic-mechanical properties on the polyester and polypropylene geotextiles. Geotext Geomembr 13:591–626

    Article  Google Scholar 

  67. Jailloux JM, Verdu J (1990) Kinetic models for the life prediction in PET hygrothermal aging: a critical survey. In: Hoedt D (ed) Proceedings of 4th international conference on geotextiles, geomembranes and related products. Balkema, Rotterdam, p 727

    Google Scholar 

  68. Bikiaris DN, Papageorgious GZ, Achili DS (2006) Synthesis and comparative biodegradability studies of three (alkylene succinate)s. Polym Degrad Stab 91(1):31–43

    Article  CAS  Google Scholar 

  69. Young RJ, Lovell PA (2011) Introduction to polymers, 3rd edn. CRC Press, Boca Raton, pp 591–622

    Google Scholar 

  70. Kim JH, Kim JY, Lee YM, Kim KY (1992) Properties and swelling characteristics of cross-linked poly (vinyl alcohol)/chitosan blend membrane. J Appl Polym Sci 45(10):1711–1717

    Article  CAS  Google Scholar 

  71. Mtshali TN, Krupa I, Luyt AS (2001) The effect of cross-linking on the thermal properties of LDPE/wax blends. Thermalchim Acta 380:47–54

    Article  CAS  Google Scholar 

  72. Gardner DJ, Oporto GS, Mills R, Samir MASA (2008) Adhesion and surface issues in cellulose and nanocellulose. J Adhes Sci Technol 22:545–567

    Article  CAS  Google Scholar 

  73. Yan C, Zhang J, Lv Y, Yu J, Wu J, Zhang J, He J (2009) Thermoplastic cellulose-graft-poly (l-lactide) copolymers homogeneously synthesized in an ionic liquid with 4-deimethylaminopyridine catalyst. Biomacromolecules 10(8):2013–2018

    Article  CAS  Google Scholar 

  74. Boudenne A, Ibos L, Candau Y, Thomas S (2011) Handbook of multiphase polymer systems. Wiley, Chichester, p 455

    Google Scholar 

  75. Liu M, Guo B, Du M, Chen F, Jia D (2009) Halloysite nanotubes as a novel β-nucleating agent for isotactic polypropylene. Polymer 50:3022–3030

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was partly supported by the National Textile Center (NTC), the Wallace Foundation and the Department of Fiber Science & Apparel Design at Cornell University. The authors also thank the Cornell Center for Materials Research (CCMR) for the use of their facilities and Cornell Poultry Research Farm for providing compost material.

Author information

Authors and Affiliations

  1. Fiber Science Program, Cornell University, Ithaca, NY, 14853-4401, USA

    Kaiyan Qiu & Anil N. Netravali

Authors
  1. Kaiyan Qiu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Anil N. Netravali
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Anil N. Netravali.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Qiu, K., Netravali, A.N. A Composting Study of Membrane-Like Polyvinyl Alcohol Based Resins and Nanocomposites. J Polym Environ 21, 658–674 (2013). https://doi.org/10.1007/s10924-013-0584-0

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10924-013-0584-0

Keywords

Search

Navigation