Abstract
The dependence of the foaming behaviour of a polymeric material on its material characteristics and foaming temperature gives rise to the research question that how the degree of dispersion/distribution of nanoparticles and the resulting viscosity changes affect the foaming behaviour and properties of nanocomposite foams. In the study reported here, styrene–ethylene–butylene–styrene was selected as a model polymer, because of its complex microstructure and its commercial importance. Styrene–ethylene–butylene–styrene nanocomposites, with different nanoclay loadings, were processed in a twin-screw extruder. The nanocomposite structure was correlated with the rheological properties to evaluate the batch-foaming performance of nanocomposite using carbon dioxide at different temperatures. At 35 °C, selective foaming of the elastomeric phase, hindered by the stiff polystyrene phase, resulted in foams with more than 74% shrinkage. At 80 °C, higher viscosities and moduli resulted in foams with higher volume expansion ratios. Increases in the degree of delamination of silicate layers in nanocomposites resulted in cell sizes up to 41% and 75% lower than that of neat polymer foams produced at 35 °C and 80 °C, respectively. Dynamic mechanical analysis results suggest heterogeneous nucleation and the presence of nanoclay in both phases. The study results show that the nanocomposite structure plays an important role in the production of thermoplastic elastomer foams of superior morphology and low shrinkage.
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Abbreviations
- C20A:
-
Cloisite®20A
- DMA:
-
dynamic mechanical analysis
- E′:
-
storage modulus (in DMA studies)
- E″:
-
loss modulus (in DMA studies)
- η app :
-
apparent viscosity
- η*:
-
complex viscosity
- \({\dot{\gamma}}_{\mathrm{app}}\) :
-
apparent shear rate
- G′:
-
storage modulus (in melt rheology)
- G″:
-
loss modulus (in melt rheology)
- MFI:
-
melt flow index
- N 0 :
-
cell density
- ρ :
-
density
- SEBS:
-
styrene–ethylene–butylene–styrene
- SEM:
-
scanning electron microscopy
- τ :
-
shear stress
- TEM:
-
transmission electron microscopy
- T g :
-
glass transition temperature
- TPE:
-
thermoplastic elastomer
- VE:
-
volume expansion ratio
- w :
-
weight
- XRD:
-
X-ray diffraction
References
Raha S, Kao N, Bhattacharya SN (2005) Effect of polypropylene on the rheology of co-continuous PS/ SEBS blends. Polym Eng Sci 45:1432–1444
Zhang Y, Kontopoulou M, Park CB, Ye X (2009) In-situ investigation of the foamability of polyolefin elastomer and PP within a rheometer. 8th World Congr Chem Eng
Zhai W, Kuboki T, Wang L, Park CB (2010) Cell structure evolution and the crystallisation behaviour of polypropylene/clay nanocomposites foams blown in continuous extrusion. Ind Eng Chem Res 49:9834–9845
Bhattacharya S, Gupta R, Jollands M, Bhattacharya SN (2009) Foaming behaviour of high melt-strength polypropylene/clay nanocomposites. Polym Eng Sci 49:2070–2084
Gendron R, Vachon C (2003) Effect of viscosity on low density foaming of poly (ethylene-co-octene) resins. J Cell Plast 39:71–85
Zhang Y, Parent JS, Kontopoulou M, Park CB (2015) Foaming of reactively modified polypropylene: effects of rheology and coagent type. J Cell Plast 51:505–522. https://doi.org/10.1177/0021955X14566209
Gunkel F, Sporrer A, Lim G et al (2008) Understanding melt rheology and foamability of polypropylene-based TPO blends. J Cell Plast 44:307–325
Sharudin R, Ohshima M (2013) Preparation of microcellular thermoplastic elastomer foams from polystyrene-b-ethylene-butylene-b-polystyrene (SEBS) and their blends with polystyrene. J Appl Polym Sci 128:2245–2254
Zhang Y, Kontopoulou M, Ansari M, Hatzikiriakos S, Park CB (2011) Effect of molecular structure and rheology on the compression foam molding of ethylene-α-olefin copolymers. Polym Eng Sci 51:1145–1154. https://doi.org/10.1002/pen.21851
Wong A, Park CB (2014) Fundamental mechanisms of cell nucleation in plastic foam processing. In: Lee ST, Park CB (eds) Foam extrusion: principles and practice2nd edn. CRC Press, Boca Raton
Colton JS, Suh NP (1987) The nucleation of microcellular thermoplastic foam with additives: part II: experimental results and discussion. Polym Eng Sci 27:493–499. https://doi.org/10.1002/pen.760270703
Ward CA, Levart E (1984) Conditions for stability of bubble nuclei in solid surfaces contacting a liquid-gas solution. J Appl Phys 56:491–500. https://doi.org/10.1063/1.333937
Ward CA, Johnson WR, Venter RD, Ho S, Forest TW, Fraser WD (1983) Heterogeneous bubble nucleation and conditions for growth in a liquid-gas system of constant mass and volume. J Appl Phys 54:1833–1843. https://doi.org/10.1063/1.332819
Harvey EN, McElroy WD, Whiteley AH (1947) On cavity formation in water. J Appl Phys 18:162–172. https://doi.org/10.1063/1.1697598
Lee S-T (1993) Shear effects on thermoplastic foam nucleation. Polym Eng Sci 33:418–422. https://doi.org/10.1002/pen.760330707
Ito Y, Yamashita M, Okamoto M (2006) Foam processing and cellular structure of polycarbonate-based nanocomposites. Macromol Mater Eng 291:773–783
Eteläaho P, Nevalainen K, Suihkonen R, Vuorinen J, Hanhi K, Järvelä P (2009) Effects of direct melt compounding and masterbatch dilution on the structure and properties of nanoclay-filled polyolefins. Polym Eng Sci 49:1438–1446
Zhu L, Xanthos M (2004) Effects of process conditions and mixing protocols on structure of extruded polypropylene nanocomposites. J Appl Polym Sci 93:1891–1899
Bureau MN, Perrin-Sarazin F, Ton-That MT (2004) Polyolefin nanocomposites: essential work of fracture analysis. Polym Eng Sci 44:1142–1151
Menard KP (2007) Dynamic mechanical analysis: a practical application. CRC Press, Boca Raton
Yang S, Taha-Tijerina J, Serrato-Diaz V, Hernandez K, Lozano K (2007) Dynamic mechanical and thermal analysis of aligned vapor grown carbon nanofiber reinforced polyethylene. Compos Part B Eng 38:228–235
Bindu P, Thomas S (2013) Viscoelastic behavior and reinforcement mechanism in rubber nanocomposites in the vicinity of spherical nanoparticles. J Phys Chem B 117:12632–12648. https://doi.org/10.1021/jp4039489
Yousfi M, Alix S, Lebeau M, Soulestin J, Lacrampe MF, Krawczak P (2014) Evaluation of rheological properties of non-Newtonian fluids in micro rheology compounder: experimental procedures for a reliable polymer melt viscosity measurement. Polym Test 40:207–217. https://doi.org/10.1016/j.polymertesting.2014.09.010
Gamon G, Evon P, Rigal L (2013) Twin-screw extrusion impact on natural fibre morphology and material properties in poly(lactic acid) based biocomposites. Ind Crop Prod 46:173–185. https://doi.org/10.1016/j.indcrop.2013.01.026
Leroy E, Jacquet P, Coativy G, Reguerre A, Lourdin D (2012) Compatibilization of starch–zein melt processed blends by an ionic liquid used as plasticizer. Carbohydr Polym 89:955–963. https://doi.org/10.1016/j.carbpol.2012.04.044
Bialleck S, Rein H (2011) Preparation of starch-based pellets by hot-melt extrusion. Eur J Pharm Biopharm 79:440–448. https://doi.org/10.1016/j.ejpb.2011.04.007
Banerjee R, Sinha Ray S, Ghosh AK (2017) Dynamic rheology and foaming behaviour of styrene–ethylene–butylene–styrene/polystyrene blends. J Cell Plast 53:389–406. https://doi.org/10.1177/0021955X16652108
Kim SG, Leung SN, Park CB, Sain M (2011) The effect of dispersed elastomer particle size on heterogeneous nucleation of TPO with N2 foaming. Chem Eng Sci 66:3675–3686
Ray SS, Okamoto M (2003) New polylactide/layered silicate nanocomposites, 6a. Melt rheology and foam processing. Macromol Mater Eng 288:936–944
Lele A, Mackley M, Galgali G, Ramesh C (2002) In situ rheo--ray investigation of flow-induced orientation in layered silicate–syndiotactic polypropylene nanocomposite melt. J Rheol 46:1091–1110
Ivanoska-Dacikj A, Bogoeva-Gaceva G, Rooj S, Wießner S, Heinrich G (2015) Fine tuning of the dynamic mechanical properties of natural rubber/carbon nanotube nanocomposites by organically modified montmorillonite: a first step in obtaining high-performance damping material suitable for seismic application. Appl Clay Sci 118:99–106. https://doi.org/10.1016/j.clay.2015.09.009
Rooj S, Das A, Stöckelhuber KW, Wießner S, Fischer D, Reuter U, Heinrich G (2015) “Expanded organoclay” assisted dispersion and simultaneous structural alterations of multiwall carbon nanotube (MWCNT) clusters in natural rubber. Compos Sci Technol 107:36–43. https://doi.org/10.1016/j.compscitech.2014.11.018
Das A, Stöckelhuber KW, Jurk R, Fritzsche J, Klüppel M, Heinrich G (2009) Coupling activity of ionic liquids between diene elastomers and multi-walled carbon nanotubes. Carbon N Y 47:3313–3321. https://doi.org/10.1016/j.carbon.2009.07.052
Rooj S, Das A, Stöckelhuber KW, Reuter U, Heinrich G (2012) Highly exfoliated natural rubber/clay composites by “propping-open procedure”: the influence of fatty-acid chain length on exfoliation. Macromol Mater Eng 297:369–383. https://doi.org/10.1002/mame.201100185
Rooj S, Das A, Stöckelhuber KW, Wang DY, Galiatsatos V, Heinrich G (2013) Understanding the reinforcing behavior of expanded clay particles in natural rubber compounds. Soft Matter 9:3798–3808. https://doi.org/10.1039/c3sm27519a
Morgan AB, Harris JD (2003) Effects of organoclay Soxhlet extraction on mechanical properties, flammability properties and organoclay dispersion of polypropylene nanocomposites. Polymer (Guildf) 44:2313–2320. https://doi.org/10.1016/S0032-3861(03)00095-8
Ray SS (2013) Clay-containing polymer nanocomposites: from fundamentals to real applications. Elsevier, Amsterdam
Tadiello L, D’Arienzo M, Di Credico B, Hanel T, Matejka L, Mauri M, Morazzoni F, Simonutti R, Spirkova M, Scotti R (2015) The filler–rubber interface in styrene butadiene nanocomposites with anisotropic silica particles: morphology and dynamic properties. Soft Matter 11:4022–4033. https://doi.org/10.1039/C5SM00536A
Bershtein VA, Egorova LM, Yakushev PN, Pissis P, Sysel P, Brozova L (2002) Molecular dynamics in nanostructured polyimide-silica hybrid materials and their thermal stability. J Polym Sci Part B Polym Phys 40:1056–1069. https://doi.org/10.1002/polb.10162
DeMaggio GB, Frieze WE, Gidley DW et al (1997) Interface and surface effects on the glass transition in thin polystyrene films. Phys Rev Lett 78:1524–1527. https://doi.org/10.1103/PhysRevLett.78.1524
Gorbatschow W, Arndt M, Stannarius R, Kremer F (1996) Dynamics of H-bonded liquids confined to nanopores. Europhys Lett 35:719–724. https://doi.org/10.1209/epl/i1996-00175-8
Daoukaki D, Barut G, Pelster R, Nimtz G, Kyritsis A, Pissis P (1998) Dielectric relaxation at the glass transition of confined N-methyl-ɛ-caprolactam. Phys Rev B 58:5336–5345. https://doi.org/10.1103/PhysRevB.58.5336
Barut G, Pissis P, Pelster R, Nimtz G (1998) Glass transition in liquids: two versus three-dimensional confinement. Phys Rev Lett 80:3543–3546. https://doi.org/10.1103/PhysRevLett.80.3543
Schüller J, Richert R, Fischer EW (1995) Dielectric relaxation of liquids at the surface of a porous glass. Phys Rev B 52:15232–15238. https://doi.org/10.1103/PhysRevB.52.15232
Dealy JM, Wissbrun KF (1990) Melt rheology and its role in plastics processing. Van Nostrand Reinhold, New York
Ray SS, Okamoto K, Okamoto M (2003) Structure-property relationship in biodegradable poly (butylene succinate)/layered silicate nanocomposites. Macromolecules 36:2355–2367
Bandyopadyhyay J, Maiti A, Kahuta BB, Ray SS (2010) Thermal and rheological properties of biodegradable poly[(butylene-succinate)-co-adipate] nanocomposites. J Nanosci Nanotechnol 10:4184–4195
Ray SS, Maiti P, Okamoto M et al (2002) New polylactide/layered silicate nanocomposites. 1. Preparation, characterization, and properties. Macromolecules 35:3104–3110
Hyun YH, Lim ST, Choi HJ, Jhon MS (2001) Rheology of poly(ethylene oxide)/ organoclay nanocomposites. Macromolecules 34:8084–8093
Ren J, Silva AS, Krishnamoorti R (2000) Linear viscoelasticity of disordered polystyrene-polyisoprene block copolymer based layered-silicate nanocomposites. Macromolecules 33:3739–3746
Zhai W, Wang J, Chen N, Naguib HE, Park CB (2012) The orientation of carbon nanotubes in poly(ethylene-co-octene) microcellular foaming and its suppression on cell coalescence. Polym Eng Sci 52:2078–2089
Okamoto M, Nam P, Maiti P et al (2001) A house of cards structure in polypropylene/clay nanocomposites under eleongational flow. Nano Lett 1:295–298
Okamoto M, Nam P, Maiti P et al (2001) Biaxial flow-induced alignment of silicate layers in polypropylene/clay nanocomposite foam. Nano Lett 1:503–505
Ray SS, Okamoto M (2003) New polylactide/layered silicate nanocomposites. Part 6. Melt rheology and foam processing. Macromol Mater Eng 288:936–944
Banerjee R, Ray SS, Ghosh AK (2017) Investigations on blending and foaming behavior of styrene–ethylene–butylene–styrene/polystyrene blends. Int Polym Process 32:434–445. https://doi.org/10.3139/217.3362
Nam P, Maiti P, Okamoto M, Kotaka T (2002) Foam processing and cellular structure of polypropylene/clay nanocomposites. Polym Eng Sci 42:1907–1917
Lee S-T (2000) Foam nucleation in gas dispersed polymeric systems. In: Lee S-T (ed) Foam extrusion: principles and practice. Boca Raton
Lee S-T, Park CB, Ramesh N (2007) Polymeric foams: science and technology. CRC Press, Boca Raton
Chen X, Feng JJ, Bertelo CA (2006) Plasticization effects on bubble growth during polymer foaming. Polym Eng Sci 46:97–107. https://doi.org/10.1002/pen.20434
Kanehashi S, Nakagawa T, Nagai K, Duthie X, Kentish S, Stevens G (2007) Effects of carbon dioxide-induced plasticization on the gas transport properties of glassy polyimide membranes. J Membr Sci 298:147–155. https://doi.org/10.1016/j.memsci.2007.04.012
Guo Z, Lee LJ, Tomasko DL (2008) CO2 permeability of polystyrene nanocomposites and nanocomposite foams†. Ind Eng Chem Res 47:9636–9643. https://doi.org/10.1021/ie8000088
Li G, Gunkel F, Wang J, Park CB, Altstädt V (2007) Solubility measurements of N2 and CO2 in polypropylene and ethene/octene copolymer. J Appl Polym Sci 103:2945–2953
Durrill PL, Griskey RG (1969) Diffusion and solution of gases into thermally softened or molten polymers: part II. Relation of diffusivities and solubilities with temperature pressure and structural characteristics. AICHE J 15:106–110. https://doi.org/10.1002/aic.690150124
Koros WJ, Paul DR (1980) Sorption and transport of CO2 above and below the glass transition of poly(ethylene terephthalate). Polym Eng Sci 20:14–19. https://doi.org/10.1002/pen.760200104
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The authors received financial support from the Department of Science and Technology (HGERA8X) and the Council for Scientific and Industrial Research (HGER74s), South Africa.
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Banerjee, R., Ray, S.S. & Ghosh, A.K. Rheology and foaming behaviour of styrene–ethylene–butylene–styrene nanocomposites. Colloid Polym Sci 299, 481–496 (2021). https://doi.org/10.1007/s00396-020-04677-6
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DOI: https://doi.org/10.1007/s00396-020-04677-6