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Experimental and computational study of thermal behavior of PVC composites based on modified eggshell biofiller for UPVC product

Journal of Polymer Research volume 29, Article number: 2 (2022) Cite this article

Abstract

During the last years, green composites have been used as alternative compounds widely used thermoplastic such as Polyvinyl chloride (PVC) products. This semi-empirical study aims to investigate efficient biofiller prepared from waste chicken eggshell (ES), and zinc oxide (ZnO) to be used in Polyvinyl chloride (PVC) matrix for produce safe products. Prepared composite samples were characterized by X-ray pattern, and IR spectroscopy. Thermal properties of these composites were also examined with the help of Thermogravimetric Analysis (TGA/DTG) and the Differential Scanning Calorimetry (DSC) analysis. The FTIR spectra of samples confirmed structures of the ZnO and CaCO3 in eggshell powder. In addition, X-ray diffraction analysis of samples confirmed the formation of a hexagonal wurtzite structure in ZnO, and calcite form in the chicken eggshell (ES). Thermal results showed that addition of 5wt.% EZn biofiller could significantly improve thermal stability of the composites. The presence of 5wt.% of inorganic biofiller enhanced the rapidest decomposition temperature and the maximum decomposition rate by 5.6 and 1.5%, respectively. At high temperature, a compact char formed on the surface of the composites, obstructing the thermal degradation of the polymer matrix. In addition, studied samples were modeled by theoretical calculations based on the DFT/B3LYP/LanL2DZ method to gain more information aboat overall properties, mechanism, and intermolecular interactions from examined composites. Interesting comparable results and good consistency were found between experimental and the calculated results.

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References

  1. Titow M (2012) PVC technology. Springer Science & Business Media.

  2. Titow WV (2012) PVC plastics: properties, processing, and applications. Springer Science & Business Media.

  3. Liu P, Zhao M, Guo J (2006) Thermal stabilities of poly (vinyl chloride)/calcium carbonate (PVC/CaCO3) composites. J Macromol Sci Part B Phys 45(6):1135–1140

    Article  CAS  Google Scholar 

  4. Xiong C et al (2005) Microporous polyvinyl chloride: novel reactor for PVC/CaCO3 nanocomposites. Nanotechnology 16(9):1787

    Article  CAS  Google Scholar 

  5. Zhang L, Chen X, Li C (2005) Mechanical properties of PVC/nano-CaCO 3 composites. J Mater Sci 40(8):2097–2098

    Article  CAS  Google Scholar 

  6. Gong F et al (2004) Synthesis and characterization of PVC/montmorillonite nanocomposite. J Mater Sci 39(1):293–294

    Article  CAS  Google Scholar 

  7. Pagacz J, Pielichowski K (2009) Preparation and characterization of PVC/montmorillonite nanocomposites—a review. J Vinyl Add Tech 15(2):61–76

    CAS  Google Scholar 

  8. Zampronio EC, Greggio DN, Oliveira HP (2003) Preparation, characterization and properties of PVC/V2O5 hybrid organic–inorganic material. J Non-Cryst Solids 332(1–3):249–254

    Article  CAS  Google Scholar 

  9. Hefni MA, FP Hassani, Kermani MF (2018) An Investigation into the Potential Use of Calcium Carbonate Nanoparticles in Mine Backfill. in Materials Science Forum. Trans Tech Publ.

  10. Yu J et al (2016) Thermal degradation of PVC: A review. Waste Manage 48:300–314

    Article  CAS  Google Scholar 

  11. Folarin O, Sadiku E (2011) Thermal stabilizers for poly (vinyl chloride): A review. International Journal of Physical Sciences 6(18):4323–4330

    Google Scholar 

  12. Jia P et al (2015) Effect of chlorinated phosphate ester based on castor oil on thermal degradation of poly (vinyl chloride) blends and its flame retardant mechanism as secondary plasticizer. RSC Adv 5(51):41169–41178

    Article  CAS  Google Scholar 

  13. Dragan S, Ghirisan A (2019) Kinetic study of sulfur dioxide absorption into dolomite-brucite suspensions. Studia universitatis babes-bolyai chemia. 64(2):345–355.

  14. Karayildirim T et al (2006) The effect of some fillers on PVC degradation. J Anal Appl Pyrol 75(2):112–119

    Article  CAS  Google Scholar 

  15. Mousa A, Heinrich G, Wagenknecht U (2015) Bio-based fillers. Encyclopedia of Polymeric Nanomaterials. p. 106–109.

  16. Roman K, Zsoldos G (2017) Measurements of rheologycal and mechanical-, thermo-mechanical properties of pvc/corn cob foam composite. International Journal of Research-Granthaalayah. 5(10).

  17. Murugan S, Munusamy Y, Ismail H (2017) Effects of chicken eggshell filler size on the processing, mechanical and thermal properties of PVC matrix composite. Plast, Rubber Compos 46(1):42–51

    Article  CAS  Google Scholar 

  18. Villarreal-Lucio D et al (2018) Effect of nano CaCO3 particles from eggshell on mechanical and thermal properties in pp/eggshell composites. J Eng Technol 6(2):456–468

    Google Scholar 

  19. Tsutsumi R et al (2018) Surface treatment of CaCO3 with a mixture of amino-and mercapto-functional silane coupling agents and tensile properties of the rubber composites. Compos Interfaces 25(8):743–760

    Article  CAS  Google Scholar 

  20. Charde SJ et al (2018) Influence of functionalized calcium carbonate nanofillers on the properties of melt-extruded polycarbonate composites. Chem Eng Commun 205(4):492–505

    Article  CAS  Google Scholar 

  21. Sampath W, Edirisinghe D, Egodage S (2015) Improvement of physico-mechanical properties of calcium carbonate filled natural nubber and low density polyethylene blends with titanate coupling agent. in 2015 Moratuwa Engineering Research Conference (MERCon). IEEE.

  22. Irish Jr PM (1971) Stabilizer compositions employing fatty acid metal salts, epoxidized material, and organo phosphites, Google Patents.

  23. Leistner WE, Hecker AC, Knoepke OH (1961) Polyvinyl chloride stabilizer combinations of phosphorus acid with triphosphites andheavy metal salts, Google Patents.

  24. Lu M (2008) PVC nanocomposite manufacturing technology and applications. Google Patents.

  25. Drewes R et al (1996) Stabilized polyvinyl chloride, Google Patents.

  26. Gorrasi G, Bugatti V, Sorrentino A (2018) Nanohybrid active fillers in food contact bio-based materials. Bionanocomposites for packaging applications. Springer, pp 71–94

    Chapter  Google Scholar 

  27. Wang M et al (2016) A novel liquid Ca/Zn thermal stabilizer synthesized from tung-maleic anhydride and its effects on thermal stability and mechanical properties of PVC. Polym Degrad Stab 133:136–143

    Article  Google Scholar 

  28. Li P et al (2016) Enhancement of the interfacial interaction between poly (vinyl chloride) and zinc oxide modified reduced graphene oxide. RSC Adv 6(7):5784–5791

    Article  CAS  Google Scholar 

  29. Mallakpour S, Rashidimoghadam S (2017) Investigation on morphology, properties, and applications of hybrid poly (vinyl chloride)/metal oxide composites. Hybrid Polymer Composite Materials. Elsevier, pp 343–377

    Chapter  Google Scholar 

  30. Inoue T et al (2004) Mechanochemical dechlorination of polyvinyl chloride by co-grinding with various metal oxides. Adv Powder Technol 15(2):215–225

    Article  CAS  Google Scholar 

  31. Rabiee H et al (2015) Improvement in flux and antifouling properties of PVC ultrafiltration membranes by incorporation of zinc oxide (ZnO) nanoparticles. Sep Purif Technol 156:299–310

    Article  CAS  Google Scholar 

  32. Arya PK, Mathur V, Patidar D (2017) Thermo-mechanical performance of PVC/ZnO nanocomposites. Phase Transitions 90(7):695–702

    Article  CAS  Google Scholar 

  33. Liu H, Wu S (2019) Preparation of High Sorption Durability Nano-CaO–ZnO CO2 Adsorbent. Energy Fuels 33(8):7626–7633

    Article  CAS  Google Scholar 

  34. Faridi H, Arabhosseini A (2018) Application of eggshell wastes as valuable and utilizable products: A review. Res Agric Eng 64(2):104–114

    Article  CAS  Google Scholar 

  35. Yuzer NY, Hilmioglu N (2021) Applicability of membrane reactor for producing environment friendly fuel additive glycerol carbonate.

  36. Fu S-Y et al (2008) Effects of particle size, particle/matrix interface adhesion and particle loading on mechanical properties of particulate–polymer composites. Compos B Eng 39(6):933–961

    Article  Google Scholar 

  37. Zhang X et al (2019) Waste eggshell-derived dual-functional CuO/ZnO/eggshell nanocomposites:(Photo) catalytic reduction and bacterial inactivation. ACS Sustainable Chemistry & Engineering 7(18):15762–15771

    Article  CAS  Google Scholar 

  38. Tangboriboon N et al (2015) Embedded Eggshells as a Bio-Filler in Natural Rubber for Thermal Insulation Composite Foams. Progress in Rubber Plastics and Recycling Technology 31(3):189–205

    Article  Google Scholar 

  39. Hassen AA et al (2015) Utilization of chicken eggshell waste as a bio-filler for thermoplastic polymers: thermal and mechanical characterization of polypropylene filled with naturally derived CaCO3. Polym Polym Compos 23(9):653–662

    CAS  Google Scholar 

  40. Frisch MJ et al (2009) Gaussian 09, Revision D. 01, Gaussian. Inc.: Wallingford, CT.

  41. Dennington R, Keith T, Millam J (2009) GaussView, version 5. Semichem Inc., Shawnee Mission, KS

    Google Scholar 

  42. Parr RG (1980) Density functional theory of atoms and molecules. Horizons of Quantum Chemistry. Springer, pp 5–15

    Chapter  Google Scholar 

  43. Tsai W et al (2006) Characterization and adsorption properties of eggshells and eggshell membrane. Biores Technol 97(3):488–493

    Article  CAS  Google Scholar 

  44. Toledo AJ et al (2019) One-Step Synthesis of CaO-ZnO Efficient Catalyst for Biodiesel Production. Int J Chem Eng

  45. Kumar D, Ali A (2013) Transesterification of low-quality triglycerides over a Zn/CaO heterogeneous catalyst: kinetics and reusability studies. Energy Fuels 27(7):3758–3768

    Article  CAS  Google Scholar 

  46. Katz AK et al (1996) Calcium ion coordination: a comparison with that of beryllium, magnesium, and zinc. J Am Chem Soc 118(24):5752–5763

    Article  CAS  Google Scholar 

  47. Alwan RM et al (2015) Synthesis of zinc oxide nanoparticles via sol–gel route and their characterization. Nanosci Nanotechnol 5(1):1–6

    Google Scholar 

  48. Muthukumaran S, Gopalakrishnan R (2012) Structural, FTIR and photoluminescence studies of Cu doped ZnO nanopowders by co-precipitation method. Opt Mater 34(11):1946–1953

    Article  CAS  Google Scholar 

  49. Naemchanthara K et al (2008) Temperature effect on chicken egg shell investigated by XRD, TGA and FTIR. in Advanced Materials Research. Trans Tech Publ

  50. Kaya AA, Erturk K (2018) Structural and optical properties of Fe/Ni: ZnO nanoparticles: experimental and DFT studies. Appl Phys A 124(4):346

    Article  Google Scholar 

  51. Liu J et al (2010) Thermal stability of poly (vinyl chloride)/layered double hydroxide nanocomposites. J Appl Polym Sci 116(4):2058–2064

    CAS  Google Scholar 

  52. Kalaee M et al (2012) Effect of ZnO nanoparticles on kinetics of thermal degradation and final properties of ethylene–propylene–diene rubber systems. J Therm Anal Calorim 110(3):1407–1414

    Article  CAS  Google Scholar 

  53. Khaleghi M, Didehban K, Shabanian M (2017) Effect of new melamine-terephthaldehyde resin modified graphene oxide on thermal and mechanical properties of PVC. Polym Testing 63:382–391

    Article  CAS  Google Scholar 

  54. Keledi G, Hári J, Pukánszky B (2012) Polymer nanocomposites: structure, interaction, and functionality. Nanoscale 4(6):1919–1938

    Article  CAS  PubMed  Google Scholar 

  55. Mark HF (2013) Encyclopedia of polymer science and technology, concise. John Wiley & Sons.

  56. Varma A et al (2016) Solution combustion synthesis of nanoscale materials. Chem Rev 116(23):14493–14586

    Article  CAS  PubMed  Google Scholar 

  57. Phuthotham M et al (2019) Modification of egg shell powder with in situ generated copper and cuprous oxide nanoparticles by hydrothermal method. Materials Research Express.

  58. Garcıa AD (2014) Density functional approaches for the interaction of metal oxides with small molecules. Ph. D. thesis, Universität Bremen

  59. Batyrev ED, van den Heuvel JC (2011) Modification of the ZnO (0001)–Zn surface under reducing conditions. Phys Chem Chem Phys 13(28):13127–13134

    Article  CAS  PubMed  Google Scholar 

  60. Ochterski JW (2000) Thermochemistry in gaussian. Gaussian Inc, p. 1–19.

  61. Raeisi A et al (2019) A complete description on effect of β-cyclodextrin-ester as a bio-based additive for preparation of safe PVC: From synthesis to Computational study. Materials Today Communications, p. 100736.

  62. Boys S, Bernardi F (2002) The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Molecular Physics. 100(1):65–73

  63. Cao C et al (2016) Theoretical investigation on correlation between steric effects and selectivity in gas–solid chlorination of polyvinyl chloride. Chem Eng Sci 151:64–78

    Article  CAS  Google Scholar 

  64. Karelson M, Lobanov VS, Katritzky AR (1996) Quantum-chemical descriptors in QSAR/QSPR studies. Chem Rev 96(3):1027–1044

    Article  CAS  PubMed  Google Scholar 

  65. Watson L, Eisenstein O (2002) Entropy explained: the origin of some simple trends. J Chem Educ 79(10):1269

    Article  CAS  Google Scholar 

  66. Özbek N et al (2017) Synthesis, characterization, computational studies, antimicrobial activities and carbonic anhydrase inhibitor effects of 2-hydroxy acetophenone-N-methyl p-toluenesulfonylhydrazone and its Co (II), Pd (II), Pt (II) complexes. J Mol Struct 1127:437–448

    Article  Google Scholar 

  67. Boys SF, Bernardi FD (1970) The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors. Molecular Physics. 19(4):553–566.

  68. Parr RG et al (1978) Electronegativity: the density functional viewpoint. J Chem Phys 68(8):3801–3807

    Article  CAS  Google Scholar 

  69. Parr RG, Pearson RG (1983) Absolute hardness: companion parameter to absolute electronegativity. J Am Chem Soc 105(26):7512–7516

    Article  CAS  Google Scholar 

  70. Pearson RG (1987) Recent advances in the concept of hard and soft acids and bases. J Chem Educ 64(7):561

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Petrochemistry and Polymer Research Group, Chemistry and Petrochemistry Research Center, Standard Research Institute (SRI), P.O. Box 31745-139, Karaj, Iran

    Mahroo Khaleghi

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  1. Mahroo Khaleghi
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Mahroo Khaleghi conceived of the presented idea and verified the analytical methods, performed the measurements, processed the experimental data drafted the manuscript and designed the figures.

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Correspondence to Mahroo Khaleghi.

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Research Highlight

•A strategy to design hybrid inorganic structure with an inexpensive and effective natural material for thermal stability of UPVC products.

•Preparation of an eggshell-ZnO as a metal-inorganic frameworks for HCl Capture during thermal degradation of PVC pruducts.

•Comparison of the experimental results with DFT calculations reveals an expectedly relationship between experimental analysis and theoretical parameter from structure details of the metal-inorganic frameworks in PVC matrix.

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Khaleghi, M. Experimental and computational study of thermal behavior of PVC composites based on modified eggshell biofiller for UPVC product. J Polym Res 29, 2 (2022). https://doi.org/10.1007/s10965-021-02858-7

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  • DOI: https://doi.org/10.1007/s10965-021-02858-7

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